JP2003122044A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a magnetic toner which is fast in rising of electrostatic charge from the initial period of durability, keeps stable electrostatic chargeability until the late period of the durability, and does not give rise to a negative ghost and does not adhere to a fixing member. SOLUTION: The magnetic toner contains a hydrocarbon-base wax having a specific hydroxyl group value and ester value and a magnetic iron oxide containing different elements in combination.

Description

Detailed Description of the Invention

0

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic latent image in an image forming method such as electrophotography or electrostatic recording or a toner used in a toner jet type image forming method.

[0002]

2. Description of the Related Art It is known that a toner contains a wax as a releasing agent. For example, JP-A-52-33
04, JP-A-52-3305, JP-A-57.
Techniques such as Japanese Patent No. 52574 are disclosed.

Japanese Patent Laid-Open Nos. 57-52574 and 52-3304 disclose inventions in which polyalkylenes are contained in a toner as a release agent, such as low molecular weight polyethylene and low molecular weight polypropylene in styrene resin. Or a mono-polymerized wax described in JP-A-50-936.
Japanese Patent Publication No. 47 also discloses a technique of incorporating a low molecular weight olefin copolymer into a styrene resin. Many of these reports are still insufficient in effect, and the invention of a wax having a further effect is expected.

These waxes are used for improving the offset resistance of the toner at low temperature and high temperature, but on the other hand, there is a problem that the blocking resistance is deteriorated and the developability is deteriorated. there were.

Further, Japanese Patent Laid-Open No. 63-113558,
JP-A-63-188158, JP-A2-1346
48, JP-A-4-97162, and JP-A-4-97162.
Japanese Patent Laid-Open No. 97163 discloses a technique of incorporating an alcohol component in the toner. These alcohol components are found to have the effect of improving the fixability of the toner at low temperatures and the offset resistance at high temperatures, but they sometimes deteriorate the developability of the toner.

Further, Japanese Patent Application Laid-Open No. 1-109359 discloses a technique of incorporating a low molecular weight polyolefin polyol in a toner. Although such an alcohol component 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.

Japanese Unexamined Patent Publication Nos. 4-184350 and 4
Japanese Patent Application Laid-Open No. 194947, Japanese Patent Application Laid-Open No. 4-194946, and Japanese Patent Application Laid-Open No. 4-194948 disclose techniques of incorporating a partial ester of polyglycerin in a toner. However, the addition of such a polyglycerin compound has not yet satisfied the insufficient fixability and offset resistance.

Further, conventionally, there is a problem that toner adheres to the surface of the fixing roller by offsetting, etc., and the adhered toner accumulates on the separation claw portion of the paper, and as a result, it peels off and stains the image. In order to solve this problem, a method of adding a release agent such as low molecular weight polyethylene or low molecular weight polypropylene to the toner has been proposed. However, if such an additive is added in a large amount in order to obtain a sufficient effect, on the contrary, the filming on the photoreceptor and the surface of the toner carrier such as the carrier and the sleeve are contaminated, and the image is deteriorated for practical use. It becomes a problem.

On the other hand, as a developing method, a magnetic brush method, a cascade method, and a liquid developing method, which use a two-component developer mainly composed of toner and carrier, have been put into practical use. All of these developing methods are excellent methods that can obtain a good image relatively stably, but on the other hand, deterioration of the carrier,
There is a problem associated with two-component developers, that is, variation in the mixing ratio of toner carriers.

In order to solve such a problem, various developing methods using a one-component developer consisting of only toner have been proposed. Among them, many are excellent in the method of using a one-component developer composed of a magnetic toner.

US Pat. No. 3,909,258 proposes a developing method of developing with a magnetic toner having conductivity. In this method, a conductive magnetic toner is supported on a cylindrical conductive sleeve having magnetism inside, and this is brought into contact with an electrostatic latent image holding member having an electrostatic latent image for development. At this time, in the developing section, a conductive path is formed by the toner particles between the surface of the electrostatic latent image holding member and the surface of the sleeve, and the electric charges are introduced from the sleeve to the magnetic toner particles through the conductive path, so that the electrostatic latent image The toner particles adhere to the image portion and are developed by the Coulomb force between the image portion and the magnetic toner particles. This developing method using a conductive magnetic toner is an excellent method that avoids the problems associated with the conventional two-component developing method, but on the other hand, since the toner is conductive, an electrostatic latent image holding member having a toner image is provided. There is a problem in that it is difficult to electrostatically transfer from to a final transfer material such as plain paper.

As a developing method using a high-resistance magnetic toner that can be electrostatically transferred, there is a developing method using dielectric polarization of toner particles. However, such a method inherently has a problem that the developing speed is slow and it is difficult to obtain a sufficient density of a developed image.

As another developing method using a high-resistance insulating magnetic toner, the magnetic toner particles are triboelectrically charged by friction between the magnetic toner particles and friction between the magnetic toner particles and a friction member such as a sleeve, so that a triboelectric charge is generated. A developing method is known in which an electrostatic latent image is developed with a magnetic toner contained therein. However, these methods have a problem that the number of times of contact between the magnetic toner particles and the friction member is small and triboelectrification is apt to be insufficient, and the charged magnetic toner particles are apt to aggregate on the sleeve due to the increased Coulomb force with the sleeve. Have a point.

Japanese Patent Laid-Open No. 55-18656 (corresponding US Pat. Nos. 4,395,476 and 4,473,627) proposes a new jumping developing method which eliminates the above-mentioned problems. There is. This is an extremely thin coating of magnetic toner on the sleeve, which is triboelectrically charged,
Then, the magnetic toner layer on the sleeve is developed in the vicinity of the electrostatic latent image. This method increases the chances of contact between the sleeve and the magnetic toner by applying the magnetic toner on the sleeve extremely thinly, and enables sufficient triboelectric charging of the magnetic toner, and supports the magnetic toner by magnetic force, Further, by moving the magnet and the magnetic toner as a whole to release the agglomeration of the magnetic toner particles and to sufficiently rub them with the sleeve, an excellent image can be obtained.

A considerable amount of magnetic iron oxide in the form of fine powder is mixed and dispersed in the insulating toner used in the above developing method.
Since a part of the magnetic iron oxide is exposed on the surface of the toner particles, the type of magnetic iron oxide affects the fluidity and triboelectricity of the magnetic toner. As a result, it affects various characteristics required for the magnetic toner such as the developing characteristics and durability of the magnetic toner.

More specifically, in the conventional jumping developing method using a magnetic toner containing magnetic iron oxide, the developing process is repeated for a long period of time (for example, copying), and a one-component developing method containing magnetic toner particles is carried out. The fluidity of the agent is lowered, sufficient triboelectrification cannot be obtained, charging is likely to be non-uniform, and a fog phenomenon is likely to occur in a low temperature and low humidity environment, which is likely to cause a problem on an image. When the adhesiveness between the binder resin forming the magnetic toner particles and the magnetic iron oxide is weak, the magnetic iron oxide is desorbed from the surface of the magnetic toner particles by repeating the developing process, and the density of the toner image may decrease. It tends to have an adverse effect.

When the dispersion of the magnetic iron oxide in the magnetic toner particles is not uniform, the magnetic toner particles containing a large amount of magnetic iron oxide and having a small particle size are accumulated on the sleeve, resulting in a decrease in image density and a sleeve ghost. Occurrence of unevenness of light and shade, which is called as ".

Conventionally, regarding the magnetic iron oxide contained in the magnetic toner, JP-A-62-279352 (corresponding US Pat. No. 4,820,603) and JP-A-62-2781 are known.
No. 31 (corresponding US Pat. No. 4,975,214)
Proposes a magnetic toner containing magnetic iron oxide particles containing silicon element. In such magnetic iron oxide particles, silicon element is positively present inside the magnetic iron oxide particles.

Japanese Patent Publication No. 3-9045 (corresponding European Patent Application Publication EP-A187434) proposes to control the shape of magnetic iron oxide particles to be spherical by adding a silicate. In the magnetic iron oxide particles obtained by this method, since a silicate is used for controlling the particle size, a large amount of silicon element is distributed inside the magnetic iron oxide particles.

JP-A-61-34070 proposes a method for producing ferric tetroxide by adding a hydroxosilicate solution during the oxidation reaction to ferric tetroxide. The ferrosoferric oxide particles obtained by this method have a silicon element in the vicinity of the surface, and are present in layers near the surface of the iron particles.

In Japanese Unexamined Patent Publication (Kokai) No. 5-72801 (corresponding European Patent Application Publication No. EP-A533069), 0.4 to 4% by weight of silicon element is contained in the magnetic iron oxide particles, and the surface of the magnetic iron oxide particles is contained. A magnetic toner containing magnetic iron oxide particles having a total silicon element content of 44 to 84% in the vicinity thereof has been proposed.

Japanese Unexamined Patent Publication (Kokai) No. 4-362954 (corresponding European Patent Application Publication No. EP-A468525) discloses magnetic iron oxide particles containing both silicon element and aluminum element. JP-A-5-213620 discloses magnetic iron oxide particles containing a silicon component and having the silicon component exposed on the surface. However, in order to exert the above-described effects of the magnetic iron oxide, it is necessary to uniformly disperse the magnetic iron oxide in the toner and prevent the magnetic iron oxide from falling off from the toner particles. In addition, if the toner is not supplied or the toner cannot be sufficiently charged and a large amount of toner such as a solid portion is consumed, the density decreases according to the pattern.
The phenomenon of negative ghost may occur.

[0023]

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

An object of the present invention is to provide a toner having a rapid charging rise from the initial stage of durability and a stable charging property from the latter stage of durability.

An object of the present invention is to provide a toner in which the diameter of the wax dispersed in the toner particles is small and which has the same excellent image characteristics as in the initial stage even in the long-term durability.

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

Further, an object of the present invention is to provide a toner exhibiting excellent image characteristics in a long-term durability without developing defects such as negative ghost.

[0028]

The present invention has at least toner particles containing at least a binder resin, a magnetic iron oxide and a hydrocarbon wax, and the hydroxyl value (H _v ) of the wax is 5 to 150 mgKOH / g, the ester value (E _v ) is 1 to 50 mgKOH / g, the relationship between the hydroxyl value (H _v ) and the ester value (E _v ) is H _v > E _v , and the magnetic iron oxide is Mg or Al. , Si, P, S, C
at least 1 different element selected from a, Cu, Zn
The present invention relates to a toner containing a seed, wherein the content of the different element is 0.1 to 5.0% by weight based on the iron element in the magnetic iron oxide.

The toner of the present invention contains the following constitution as a preferable embodiment. The acid value (A _v ) of the wax is 1 to 30 mgKOH / g, and the relationship between the acid value (A _v ) and the hydroxyl value (H _v ) of the wax is H _v > A _v . The melting point of the wax is 65 to 130 ° C. The viscosity of the wax at 150 ° C. is 200 mPa · s
ec or less. The wax is a wax obtained by converting an aliphatic hydrocarbon wax into an alcohol. The content of the different element of the magnetic iron oxide is 0.2 to 4% by weight based on the iron element in the magnetic iron oxide. The ratio of the different elements present in the magnetic iron oxide having an iron element dissolution rate of up to 20% by weight is 3 in the total content of the different elements in the magnetic iron oxide.
It is 0% or more. The different element is at least silicon, and the content of silicon element in the magnetic iron oxide is 0.2 to 4.0% by weight based on the iron element. The atomic ratio of Fe / Si on the outermost surface of the magnetic iron oxide is 1.2 to 4.0. The magnetic iron oxide contains Al and a different element other than Al, and the content of the Al element is 0.01 based on the iron element.
Is about 2.0% by weight. The Fe / Al atomic ratio on the outermost surface of the magnetic iron oxide is 0.3 to 10. The smoothness of the magnetic iron oxide is 0.3 to 0.8. The specific surface area of the magnetic iron oxide is 20.0 m ² / g or less.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.

As a result of diligent studies, the present inventors have found that the hydroxyl value (H _v ) is 5 to 150 mgKOH / g (preferably 10).
~ 100 mg KOH / g, more preferably 20-90 m
gKOH / g) and an ester value (E _v ) of 1 to 50
mgKOH / g (preferably 1-40 mgKOH / g
g, more preferably 1 to 30 mgKOH / g, and particularly preferably 1 to 20 mgKOH / g), and the relationship between the hydroxyl value (H _v ) and the ester value (E _v ) is H _v > E _v The present invention has been accomplished by finding that a toner exhibiting good fixing performance in a wide temperature range from a low temperature region to a high temperature region can be obtained by using a system wax as a constituent component of toner particles.

The hydroxyl group in the wax used in the present invention has the effect of enhancing the wax dispersion in the toner particles. In addition, the dispersion diameter can be made to exist finely,
The dispersibility of the magnetic iron oxide can be improved by the interaction with the magnetic iron oxide having a different element contained in the toner particles, so that the charging inhibiting factor is reduced and the toner can be uniformly charged, and the durability can be improved. Since the charge is stable until the latter stage, the developability is good. Further, since the charging is stable, it is less likely that defective development such as negative ghost due to defective charging will occur, and good image formation can be performed for a long period of time.

When the hydroxyl group of the wax is less than 5 mgKOH / g, the wax cannot be sufficiently finely dispersed in the toner particles, the wax exists as a large domain, and the dispersibility of the magnetic iron oxide is improved. The effect is also small, and as a result, it becomes a charge inhibiting factor and sufficient developability cannot be obtained. In addition, since the charge rises slowly in the initial stage of durability and the charging is unstable in a low temperature and low humidity environment, development defects such as negative ghost are likely to occur.

Further, when the hydroxyl group exceeds 150 mgKOH / g, it is likely to be affected by a high temperature and high humidity environment and a phenomenon such as blocking is likely to occur.

The ester group of the wax used in the present invention has a high affinity with the binder resin component constituting the toner particles, and the wax is likely to be uniformly dispersed in the toner particles. Further, the interaction between the magnetic iron oxide having a different element present on the surface and the hydroxyl group can reduce release of the magnetic iron oxide from the toner particle surface.

If the ester group exceeds 50 mgKOH / g, the blocking resistance of the toner is deteriorated. Further, when the ester group is less than 1 mgKOH / g, the wax cannot be sufficiently dispersed in the toner particles.

The present invention is characterized in that the hydroxyl value of the wax is larger than the ester value, whereby
Adhesion of toner to the fixing member can be reduced.
That is, since the hydroxyl group in the wax enhances the slipperiness of the toner, the releasability of the toner from the fixing member is enhanced. When the ester value of the wax is higher than the hydroxyl value, the affinity between the wax and the binder resin becomes high, the wax does not easily exude to the toner surface, the wax slipperiness becomes difficult to work, and the adhesion of the toner to the fixing member becomes difficult. Image smear caused by this occurs.

The wax used in the present invention has an acid value (A
_v ) is 1 to 30 mg KOH / g (preferably 1 to 20 m)
gKOH / g, more preferably 1 to 15 mgKOH /
g), the acid value (A _v ), and the hydroxyl value (H _v ) are H _v > A _v , the affinity with the magnetic iron oxide in the toner particles in the presence of the different element is high. high. This allows
During the production of the toner, the magnetic iron oxide can be uniformly dispersed in the toner particles together with the wax, and the wax and the magnetic iron oxide are less likely to be released from the surface of the toner particles. Therefore, even after long-term durability, it is possible to have excellent charging characteristics as in the initial period of durability.

The acid value of the wax is 30 mgKOH / g
If it is larger than this, the compatibility between the magnetic iron oxide and the wax becomes extremely strong, and the wax may adhere strongly to the magnetic iron oxide, causing aggregation of the magnetic iron oxides. As a result, the charge is not uniformly generated, and the toner is likely to deteriorate during image formation.

The acid value of the wax is 1 mgKOH / g
When it is smaller, the interaction is reduced and the dispersion of the magnetic iron oxide may be reduced accordingly, so that the release of wax and magnetic iron oxide may occur.

Further, since the acid group of the wax has a high adhesive force with other constituent components of the toner particles, the wax component is retained on the surface of the toner on the fixing member. As a result, the wax releasability effectively works at the interface between the toner and the fixing member. When the acid value of the wax is higher than the hydroxyl value, the slipperiness of the wax becomes insufficient, and image stains occur due to the adhesion of the toner to the fixing member. Further, the ester group in the wax has a high affinity with the binder resin, and since the wax has a hydroxyl group at the same time, the slipperiness between the fixing member and the binder resin component in the toner particles is improved, Adhesion of toner to the fixing member can be reduced. Further, since the wax used in the present invention has an acid group and an ester group at the same time, the wax can have an appropriate dispersion diameter in the toner particles, and the wax releasability can be effectively exerted. be able to. If either the acid group or the ester group is lacking, the dispersed diameter of the wax in the toner particles becomes uneven, and the releasability of the wax may not work sufficiently.

The wax used in the present invention is a hydrocarbon wax having a functional group. Since the main chain of the wax is composed of carbon bonds, it has a non-polar part and a polar part in the molecule, and the wax molecule itself can have appropriate phase separation and compatibility. As a result, the wax can be present in the toner particles with an appropriate dispersion diameter,
While exhibiting the effect of slipperiness and release property as a wax,
Each of the substituents of the acid group, the hydroxyl group, and the ester group easily functions in the toner, and good fixability and offset resistance can be obtained. When other elements are contained in the main chain of the wax, for example, the presence of an ether bond containing oxygen, such as polyglycerin, hinders the function of each substituent and causes sufficient charging characteristics. Can't get

The wax used in the present invention is preferably a wax obtained by converting an aliphatic hydrocarbon wax into an alcohol, since it is easy to control the acid value, hydroxyl value and ester value of the wax.

As the above-mentioned aliphatic hydrocarbon wax,
The number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 100 to 3000, preferably 200 to 200, in terms of polyethylene.
Saturated or unsaturated aliphatic hydrocarbons in the range of 0, more preferably 250 to 1000 are preferably used.

The GPC of the wax according to the present invention will be described below.
The method of measuring the molecular weight distribution by is shown.

[GPC measurement conditions] Device: HLC-8121 GPC / HT (manufactured by Tosoh Corporation) Column: "TSKgel GMHHR-H HT" 7.
8 cmI. D × 30 cm L2 (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% sample .4 ml injection

The molecular weight calibration curve prepared by the monodisperse polystyrene standard sample is used for the measurement of the molecular weight of the sample under the above conditions. In addition, Mark-Hou
It is calculated by performing conversion according to the wax such as polyethylene conversion using a conversion formula derived from the wink viscosity formula.

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

As a production example of the wax used in the present invention, for example, it is obtained by subjecting an aliphatic hydrocarbon wax to liquid phase oxidation with a molecular oxygen-containing gas in the presence of boric acid and boric anhydride. . 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, and preferably 1.2 to 1.7 in terms of mol 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, particularly 0.1 to 1 mol, based on 1 mol of the aliphatic hydrocarbon as a raw material, in terms of the amount of boric acid in the mixture. Is preferred.

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, but the oxygen concentration is 1 to 30.
It is preferably a volume% and more preferably 3 to 20 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.

Boric acid and boric anhydride are preferably mixed in advance 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 solvent 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 was added to the reaction mixture to hydrolyze and purify the borate ester of the produced wax,
The desired wax is obtained.

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

[Measurement of Acid Value] ・ Devices 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:
For the standardization, 25 ml of 0.1 kmol / m ³ hydrochloric acid was placed in an Erlenmeyer flask using a whole pipette, phenolphthalein solution was added, and titrated with 0.1 kmol / m ³ potassium hydroxide ethanol solution to obtain the amount required for neutralization. Find the factor from. Phenolphthalein solution solvent: Diethyl ether and ethanol (Purity: 99.5
(Volume% or more) mixed in a volume ratio of 1: 1 or 2: 1. Immediately before use, a few drops of a phenolphthalein solution are added to these, and they are neutralized with a 0.1 kmol / m ³ potassium hydroxide ethanol solution. Measurement method (a) 1 to 20 g of wax is precisely weighed in an Erlenmeyer flask. (B) Add 100 ml of solvent and a few drops of phenolphthalein solution as an indicator, and shake well on a water bath until the 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.

[0058]

[Equation 1]

In the above formula, A: Acid value B: Amount of 0.1 kmol / m ³ potassium hydroxide ethanol solution used for titration (ml) f: 0.1 kmol / m ³ Potassium hydroxide ethanol solution factor S: Weight of wax (g) 5.611: Formula weight of potassium hydroxide (56.11 × 1 /
10)

[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 a 100-liter flask.
Take up to ml and add pyridine to bring the total volume to 100 ml,
Shake well. Phenolphthalein solution 0.5kmol / m ³ Potassium hydroxide ethanol solution

・ Measuring method (A) Precisely weigh 0.5-6.0 g of wax into a flat-bottomed flask.
Then, add 5 ml of acetylation reagent using a pipette.
Add (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 allowing to cool, add 1 ml of water from the funnel and shake to add anhydrous vinegar.
Decomposes acid. (D) Further, in order to complete the decomposition, the flask is again opened.
Heat in a glycerin bath for 10 minutes, allow to cool, then ethanol
(Purity: 95% by volume) 5 ml on the wall of the funnel and flask.
wash. (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) In the blank test, (a) to (e) without wax.
I do. (G) If the sample is difficult to dissolve, add a small amount of pyridine.
Add or dissolve by adding xylene or toluene.

[0063]

[Equation 2]

In the above formula, A: hydroxyl value B: amount of 0.5 kmol / m ³ potassium hydroxide ethanol solution used in blank test (ml) C: 0.5 kmol / m ³ potassium hydroxide ethanol used in titration Amount of solution (ml) f: 0.5 kmol / m ³ Factor of potassium hydroxide ethanol solution S: Weight of 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.

[0066] (Ester value) = (Saponification value)-(Acid value)

[Measurement of Saponification Value] Equipment and instruments Erlenmeyer flask: 200 to 300 ml Air cooler: Glass tube having an outer diameter of 6 to 8 mm and a length of 100 cm, or a reflux condenser, both of which are rubbed on the mouth of the Erlenmeyer flask. Those that can be connected together. Water bath, sand bath, or hot plate (which can be adjusted to a temperature of about 80 ° C) Burette: 50 ml 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) 1-meter of 1.5-3.0 g of wax in an Erlenmeyer flask
Weigh to the nearest g. (B) Add 25 ml of 0.5 kmol / m ³ potassium hydroxide ethanol solution using a pipette. (C) An air cooler is attached to the Erlenmeyer flask, and the contents are shaken occasionally for 30 minutes to gently react on a water bath, sand bath or hot plate to react. When heating, adjust the heating temperature so that the circulating ethanol ring does not reach the upper end of the air cooler. (D) Immediately after the reaction is finished, the contents are cooled and the inner wall is washed by spraying a small amount of water or a mixed solution of xylene: ethanol = 1: 3 from the top of the air cooler before the contents solidify in agar form. 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) without wax.
I do. (G) When the sample is difficult to dissolve, it is dissolved in advance using xylene or a xylene-ethanol mixed solvent.

[0070]

[Equation 3]

In the above formula, A: saponification value B: amount of 0.5 kmol / m ³ hydrochloric acid used in the 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: Weight of wax (g) 28.05: Formula weight of potassium hydroxide (56.11 × 1 /)
2)

When the acid value, the hydroxyl value, the ester value and the saponification value of the wax contained in the toner of the present invention are measured, the wax is separated from the toner particles and then the above measurement method is applied. You may measure it.

The wax used in the present invention preferably has a melting point of 65 to 130 ° C, preferably 70 to 125 ° C, and more preferably 75 to 120 ° C. By using a wax having a melting point in the above range for the toner, the effect of the wax to plasticize the toner can be further improved, and the fixing property of the toner can be enhanced. Further, when the melting point of the wax is within the above range, the wax easily exudes from the toner when the fixing member is excessively heated, and the high temperature offset resistance of the toner can be improved. If the melting point of the wax is less than 65 ° C, the blocking resistance of the toner may deteriorate. If the melting point exceeds 130 ° C., the fixing performance of the toner may be adversely affected.

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

[Measuring Method of Melting Point of Wax] Sample: 0.5 to 2 mg, preferably 1 mg Measuring method: A sample is put in an aluminum pan and an empty aluminum pan is used 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 / min)

The endothermic peak temperature measured at the temperature rise II in the above temperature curve is taken as the melting point.

The wax used in the present invention is 1
It is preferable that the viscosity at 50 ° C. is 200 mPa · sec or less, preferably 180 mPa · sec or less, because the melt viscosity of the toner is lowered and the wax is uniformly dispersed in the toner particles. Viscosity at 120 ° C is 200
If it exceeds mPa · sec, not only wax dispersion but also
The dispersion of magnetic iron oxide during toner preparation may also deteriorate. In the present invention, the viscosity of wax is determined as follows.

[Kinematic Viscosity Measuring Conditions] In the present invention, the viscosity of the wax is measured using a rotational viscometer. As the viscometer, for example, "VT-500" manufactured by HAAKE can be used. Measurement temperature: 150 ° C. Sample: 10 to 50 mg Cone used (cone): HAAKE PK 1; 0.5 The value measured at a stress of 1/6000 sec was taken as the melt viscosity.

The amount of wax added to the toner particles in the present invention is preferably 0.2 to 20 parts by weight, preferably 0.5 to 15 parts by weight, and more preferably 1 to 100 parts by weight of the binder resin. Used in the range of 15 parts by weight.

Next, the magnetic iron oxide used in the present invention will be described.

The magnetic iron oxide used in the present invention is magnetic iron oxide containing different elements such as magnetite, maghemite, ferrite and the like, and a mixture thereof. The foreign element is
It is an element selected from Mg, Al, Si, P, S, Ca, Cu and Zn. Preferred elements are Mg, Al, S
i, P, S, and Zn, more preferable elements are Mg, Al, Si, and Zn, and particularly preferable elements are Al and Si. These elements may be incorporated into the iron oxide crystal lattice, incorporated into iron oxide as an oxide, or may be present on the surface as an oxide or a hydroxide. Further, it is a preferable form that it is contained as an oxide.

The magnetic iron oxide containing these different elements is well compatible with the binder resin and has very good dispersibility, so that free magnetic iron oxide is unlikely to be produced in the pulverizing step during toner production.

Further, these magnetic iron oxides have a uniform particle size distribution, and in combination with the dispersibility in the binder resin, the chargeability of the toner can be stabilized. Further, in recent years, the toner particle size has been reduced, and even in the case where the weight average particle size is 10 μm or less, the charging uniformity is promoted, the cohesiveness of the toner is reduced, the image density is improved, and the fog is improved. Developability is improved. In particular, the effect is remarkable with toner having a weight average particle diameter of 6.0 μm or less, and an extremely high-definition image can be obtained. In the present invention, the toner has a weight average particle diameter of 2.5.
It is preferable that the thickness is at least μm because a sufficient image density can be obtained.

The content of these different elements in the magnetic iron oxide is 0.1 to 5% by weight based on the iron element of the magnetic iron oxide.
Is characterized in that. More preferably 0.2 to 4
%, Particularly preferably 0.3 to 3% by weight, and further 0.4 to 2% by weight. If it is less than 0.1% by weight, the effect of containing these elements cannot be obtained, good dispersibility cannot be obtained, free magnetic iron oxide is increased, adhesion to members occurs, and charging uniformity cannot be obtained. . 5% by weight
When the amount is larger, the amount of discharged electric charges increases, resulting in insufficient charging, which may lower the image density or increase fog.

If the total amount of the different elements exceeds 5% by weight, the magnetic properties become unstable and non-uniform, the magnetic properties required for the toner cannot be obtained, the developability deteriorates, and the density decreases. Occurrence of fogging and scattering may be observed.

In addition, in the content distribution of these different elements, it is preferable that many are present near the surface of the magnetic iron oxide. For example, it is preferable that the content of the different element existing in the iron oxide in the iron oxide up to 20% by weight is 30% or more of the total content of the different element. Furthermore 4
0-80% is preferable and 60-80% is especially preferable.
In this way, by increasing the amount of existing on the surface, the dispersion effect and the electric diffusion effect can be further improved. Further, as the amount contained in the toner particles, the binder resin 10
20 to 200 parts by weight, particularly preferably 40 to 150 parts by weight, based on 0 parts by weight.

In the toner of the present invention, the magnetic iron oxide contains silicon as a different element, and the content of the silicon element is 0.2 to 4.0% by weight (more preferably, based on the iron element).
It is preferable that the atomic ratio of Fe / Si on the outermost surface of the magnetic iron oxide is 1.2 to 4.0.

The Fe / Si atomic ratio on the outermost surface of the magnetic iron oxide is measured by X-ray photoelectron spectroscopy (XPS).

When the content of the elemental silicon is less than 0.2% by weight or the Fe / Si atomic ratio exceeds 4.0, the improvement effect on the toner, especially the improvement of the fluidity of the toner is low. . Further, the content of elemental silicon is 4.0% by weight.
When the ratio is more or the Fe / Si atomic ratio is less than 1.2, the chargeability is apt to be deteriorated in the environmental characteristics, especially in the long-term storage under high humidity. Further, the durability of the toner and the dispersibility of the magnetic iron oxide in the binder resin start to decrease, which may cause release of the magnetic iron oxide from the toner particles during pulverization.

The content of silicon on the outermost surface of the magnetic iron oxide is
It has a correlation with the fluidity and water absorption of the magnetic iron oxide, and is a factor that affects the physical properties of the toner containing the magnetic iron oxide.

Further, the magnetic iron oxide used in the present invention contains a heterogeneous element other than Al and has Al on its surface.
It is preferable to have an element, and the Al element content is
The magnetic iron oxide, which is 0.01 to 2.0% by weight (more preferably 0.05 to 1.0% by weight) based on the iron element and contains other different elements, is treated with aluminum hydroxide. It is desirable to obtain it.

In the present invention, although the reason is not clear, it has been confirmed that the treatment of the surface of the magnetic iron oxide with aluminum hydroxide makes it possible to further stabilize the charge of the toner. If the Al element content contained in the magnetic iron oxide is less than 0.01% by weight, the effect is small,
On the contrary, when it exceeds 2.0% by weight, the environmental characteristics of the toner,
In particular, the charging characteristics may be deteriorated under high humidity.

Further, when the above-mentioned Al element is contained in the magnetic iron oxide surface, the Fe / Al atomic ratio on the outermost surface of the magnetic iron oxide (XPS measurement) is 0.3 to 10.0 (more preferably 0). 0.3-5.0, more preferably 0.3-
2.0) is preferable. When the Fe / Al atomic ratio on the outermost surface of the magnetic iron oxide is less than 0.3, the environmental characteristics of the toner, particularly the effect of improving the charging characteristics at high humidity, decreases,
If it exceeds 10.0, the effect of stabilizing the charge by adding Al cannot be obtained.

Further, the magnetic iron oxide used in the present invention is
The average particle size is 0.1 to 0.4 μm, preferably 0.1 to
It is preferably 0.3 μm. The smoothness is 0.
3 to 0.8 are preferable, and the specific surface area (by BET method) is preferably 20.0 m ³ / g or less.

When the smoothness of the magnetic iron oxide is less than 0.3, the unevenness of the surface of the magnetic iron oxide becomes large, and the cohesiveness of the particles becomes large, so that the magnetic iron oxide is mixed in the binder resin at the time of toner production, especially at the time of toner kneading. The magnetic iron oxide has poor dispersibility.

Further, when the smoothness of the magnetic iron oxide exceeds 0.8, it is difficult to obtain sufficient adhesion between the binder resin used in the toner and the magnetic iron oxide, and the dispersibility in the toner is adversely affected. Will be given.

The specific surface area of magnetic iron oxide is 20 m ³ /
If it is larger than g, the physical properties of the magnetic iron oxide with respect to the environment such as humidity and temperature tend to fluctuate, so that the charging of the toner becomes unstable and the image formation is adversely affected.

When the smoothness of the magnetic iron oxide is 0.3 to 0.8 and the specific surface area of the magnetic iron oxide is 20.0 m ³ / g or less, the dispersibility of the magnetic iron oxide in the binder resin. Is good, and a good image can be formed without environmental changes.

The method of measuring various physical property data in the present invention will be described in detail below.

[Toner Particle Size Distribution] The toner particle size distribution can be measured by various methods, but in the present invention, it is measured using a Coulter counter. As a measuring device,
"Coulter Multisizer IIE" manufactured by Coulter, Inc. is used. The electrolyte is about 1 using first-grade sodium chloride.
% NaCl aqueous solution is prepared. For example, "ISOTON (R)-" manufactured by Coulter Scientific Japan
II ”can be used. As a measuring method, a surfactant (preferably alkylbenzene sulfonate) was added as a dispersant in 100 to 150 ml of the electrolytic aqueous solution in an amount of 0.1.
Add ~ 5 ml, and then add 2 to 20 mg of the measurement sample.
The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes by an ultrasonic disperser, and the volume and number of toner particles are measured by the measuring device using a 100 μm aperture as an aperture to obtain a volume distribution. And the number distribution.
Then, the weight-based weight average particle diameter (D4) obtained from the volume distribution according to the present invention (the median value of each channel is a representative value for each channel), and the number-based number average particle obtained from the number distribution The diameter (D1), the weight-based coarse powder amount (20.2 μm or more) determined from the volume distribution, and the number-based fine powder number (6.35 μm or less) determined from the number distribution are determined.

[Fe / Si atomic ratio, Fe / Al atomic ratio]
In the present invention, Fe / S on the outermost surface of magnetic iron oxide
The i atomic ratio and the Fe / Al atomic ratio are determined by XPS measurement. The conditions are as follows: XPS measuring device: "ESCALAB, 200-" manufactured by VG.
"X type" X-ray photoelectron spectrometer X-ray source: Mg Kα (300 W) Analysis area: 2 × 3 mm.

[Smoothness] In the present invention, the smoothness D of the magnetic iron oxide is determined as follows.

[0103]

[Equation 4]

[BET Specific Surface Area] The specific surface area of magnetic iron oxide is measured by the BET method as follows.

The BET specific surface area is determined by the BET multipoint method using a fully automatic gas adsorption amount measuring device "Autosoap 1" manufactured by Yuasa Ionics Inc., using nitrogen as an adsorption gas. As a pretreatment of the sample, deaeration is performed at 50 ° C. for 10 hours.

[Content of different elements] Content of different elements in the magnetic iron oxide according to the present invention (based on iron element)
Is measured by fluorescent X-ray analysis using a fluorescent X-ray analyzer SYSTEM3080 (manufactured by Rigaku Denki Kogyo Co., Ltd.) in accordance with JIS K0119 “General rules for fluorescent X-ray analysis”.

[Content of Different Element, Dissolution Ratio of Iron Element] Content of different elements other than iron in the magnetic iron oxide according to the present invention (based on iron element), dissolution rate of iron element and dissolution rate of iron element The content of the different element other than iron with respect to is determined by the following method.

For example, about 3 liters of deionized water is put into a 5 liter beaker and heated in a water bath so as to be 45 to 50 ° C. While washing about 25 g of magnetic iron oxide slurried with about 400 ml of deionized water with about 300 ml of deionized water, 5
Add to liter beaker.

Next, while maintaining the temperature at about 50 ° C., special grade hydrochloric acid or a mixed acid of hydrochloric acid and hydrofluoric acid is added to start dissolution. At this time, the hydrochloric acid aqueous solution is about 3N. Approximately 20 ml of the sample is sampled several times from the start of the dissolution to the time when everything is dissolved and becomes transparent, filtered through a 0.1 μm membrane filter, and the filtrate is collected. Quantitative analysis of the iron element and other elements other than the iron element is performed on the filtrate by plasma emission spectroscopy (ICP).

The iron element dissolution rate for each sample is calculated by the following equation.

[0111]

[Equation 5]

The content of different elements other than iron element in each sample is calculated by the following formula.

[0113]

[Equation 6]

The total content of the different elements other than the iron element in the magnetic iron oxide corresponds to the concentration of different elements (ml / g) per unit weight of the dissolved magnetic iron oxide.

The content of the different element other than iron in the magnetic iron oxide is the concentration of different element other than iron element per unit weight of magnetic iron oxide (ml / Corresponds to g).

As a method for producing magnetic iron oxide having a different element according to the present invention, the case where the different element is silicon will be described as an example.

A ferrous hydroxide colloid obtained by reacting a ferrous salt aqueous solution with an aqueous alkali hydroxide solution in an amount of 0.90 to 0.99 equivalent to Fe ^{2+ in} the ferrous salt aqueous solution is prepared. In producing the magnetite particles by aerating an oxygen-containing gas to the ferrous salt reaction aqueous solution containing, either the aqueous solution of alkali hydroxide or the ferrous salt containing the ferrous hydroxide colloid is previously water-soluble. Addition of 50 to 99% of the total content (0.1 to 5% by weight) of a soluble silicate in terms of silicon element to iron element, and heating in a temperature range of 85 to 100 ° C. while containing oxygen A magnetic iron oxide containing a silicon element is produced from the ferrous hydroxide colloid by passing a gas through the mixture to cause an oxidation reaction. Then, with respect to the Fe ²⁺ remaining in the suspension after the completion of the oxidation reaction, 1.
Alkali hydroxide aqueous solution of 00 equivalents or more and the remaining water-soluble silicate [1 to 50% of the total content (0.1 to 5 wt%)
%] Is further added, and the mixture is further heated in a temperature range of 85 to 100 ° C. to cause an oxidation reaction to generate a magnetic iron oxide containing a silicon element. In the case of other elements, a water-soluble salt of the corresponding element is used instead of the above silicate.

In the present invention, when the magnetic iron oxide is further treated with aluminum hydroxide, the aqueous solution is added to the alkaline suspension in which the magnetic iron oxide containing a different element obtained in the above step is produced. After adding the water-soluble aluminum salt, the pH is adjusted to the range of 6 to 8 to deposit aluminum hydroxide on the surface of the magnetic iron oxide. Then filtration,
The magnetic iron oxide according to the present invention is obtained by washing with water, drying and crushing. Further, as a method for adjusting the smoothness and the BET specific surface area within the preferable ranges, it is preferable to perform compression, shearing and spatula using a mix muller or a raker machine.

As the above-mentioned water-soluble silicate, commercially available sodium silicate or the like is used, and silicic acid such as sol-like silicic acid generated by hydrolysis is exemplified.

Examples of the water-soluble aluminum salt include aluminum sulfate and the like.

As the ferrous salt, iron sulfate generally produced as a by-product in the production of titanium by the sulfuric acid method and iron sulfate produced as a by-product when the surface of a steel sheet is washed can be used. Further, iron chloride or the like can be used.

The magnetic iron oxide used in the magnetic toner of the present invention may be treated with a silane coupling agent, a titanium coupling agent, titanate, aminosilane, an organic silicon compound or the like.

Examples of the organosilicon compound used for the surface treatment of magnetic iron oxide include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane and allyl. Phenyldichlorosilane, benzyldimethylchlorosilane, brommethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane,
Chlormethyldimethylchlorosilane, triorganosilane mercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldimethyl Examples include siloxane and 1,3-diphenyltetramethyldisiloxane.

Examples of the titanium coupling agent include isopropoxy titanium triisostearate; isopropoxy titanium dimethacrylate isostearate; isopropoxy titanium tridodecyl benzene sulfonate; isopropoxy titanium tris dioctyl phosphate; isopropoxy titanium tri N-ethylamino. Ethyl aminato; titanium bis dioctyl pyrophosphate oxyacetate; bis dioctyl phosphate ethylene dioctyl phosphite; di-n-butoxy bis triethanol aminato titanium and the like.

Other organic silicon compounds include silicone oil. The preferred silicone oil has a viscosity of 30 to 1,000 m at a temperature of 25 ° C.
m ² / sec is used.

For example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, fluorine modified silicone oil and the like are preferable.

The binder resin used as a constituent of the toner particles in the present invention includes styrene resins, styrene copolymer resins, polyester resins, polyol resins, polyvinyl chloride resins, phenol resins, and natural modified phenols. Resin, natural resin modified maleic 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, petroleum-based Resins may be mentioned.

Examples of the comonomer for the styrene monomer of the styrene copolymer include styrene derivatives such as vinyltoluene, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate and 2-acrylic acid. Acrylic esters such as ethylhexyl and phenyl acrylate; Methacrylic acid esters such as methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate and octyl methacrylate; maleic acid; butyl maleate, methyl maleate and dimethyl maleate A dicarboxylic acid ester having a double bond such as; acrylamide, acrylonitrile, methacrylonitrile, butadiene; vinyl chloride; a vinyl ester such as vinyl acetate or 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, GPC of toner or binder resin using THF (tetrahydrofuran) as a solvent
The molecular weight distribution by is measured under the following conditions.

The column is stabilized in a heat chamber at 40 ° C., tetrahydrofuran (THF) as a solvent is caused to flow through the column at a flow rate of 1 ml / min, and about 100 μl of a THF solution of a sample is injected for measurement. In measuring the molecular weight of a sample, the molecular weight distribution possessed by the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared using several kinds of monodisperse polystyrene standard samples and the count number.
As a standard polystyrene sample for preparing a calibration curve, for example, the molecular weight of Tosoh or Showa Denko is 10 ²
Used of about 10 ^7, it is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, shodex GPC K manufactured by Showa Denko KK
F-801, 802, 803, 804, 805, 80
Combination of 6,807,800P and Tosoh T
SKgel G1000H (H _XL ), G2000H
(H _XL ), G3000H (H _XL ), G4000H
(H _XL ), G5000H (H _XL ), G6000H
(H _XL ), G7000H (H _XL ), TSKguardc
A combination of columns can be mentioned.

The sample is manufactured as follows.

The sample is placed in a THF solution, left for several hours, shaken well, mixed well with the THF solution (until the coalescence of the sample disappears), and left still for 12 hours or more. At this time, the sample is left in the THF solution for 24 hours or longer. After that, a sample processing filter (pore size: 0.45 to 0.5 μm, for example, “Mysholydisc H-25-5” manufactured by Tosoh Corporation, Germane)
Science Japan Co., Ltd. "Equiclo disk 25C
R ”or the like can be used as a measurement sample of GPC. The sample concentration is 0.5-5m for resin component
Adjust to g / ml.

The binder resin used in the present invention may have an acid value. Examples of the monomer that adjusts the acid value of the binder resin include acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, cinnamic acid, vinylacetic acid, isocrotonic acid, and angelic acid and its α-
Or β-alkyl derivatives, fumaric acid, maleic acid, citraconic acid, alkenyl succinic acid, itaconic acid, mesaconic acid, dimethyl maleic acid, unsaturated dicarboxylic acids such as dimethyl fumaric acid and its monoester derivatives or anhydrides, A desired polymer can be produced by copolymerizing such monomers alone or in combination with other monomers. Among these, it is particularly preferable to use a monoester derivative of unsaturated dicarboxylic acid in order to control the acid value.

More specifically, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate,
Monoesters of α, β-unsaturated dicarboxylic acids such as monophenyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monophenyl fumarate, etc .; monobutyl n-butenyl succinate, monomethyl n-octenyl succinate, Examples include monoesters of alkenyldicarboxylic acids such as monoethyl n-butenylmalonate, monomethyl n-dodecenyl glutarate, and monobutyl n-butenyl adipate.

The above-mentioned carboxyl group-containing monomer may be added in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, based on 100 parts by weight of all the monomers constituting the binder resin.

The binder resin according to the present invention preferably has a glass transition temperature (Tg) of 45 to 80 from the viewpoint of storage stability.
C., preferably 50 to 70.degree. If the Tg is lower than 45 ° C., it may cause deterioration of the toner in a high temperature atmosphere and offset at the time of fixing. When Tg exceeds 80 ° C,
Fixability tends to decrease.

Examples of the method for synthesizing the binder resin used in 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) almost insoluble in water is dispersed as small particles in an aqueous phase with an emulsifier, and polymerization is performed 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 water phase are different, the termination reaction rate is low, and as a result, the polymerization rate is high and a high degree of polymerization is obtained. Further, the reason is that the polymerization process is relatively simple, and that the polymerization product is fine particles, so that it is easy to mix with a colorant, a charge control agent and other additives in the production of toner. Therefore, there is an advantage as a method for producing a binder resin for toner.

However, in this method, the polymer produced is liable to become impure due to the added emulsifier, and an operation such as salting out is required to take out the polymer. In order to avoid this inconvenience, suspension polymerization is convenient. Is.

In suspension polymerization, 100 parts by weight or less (preferably 1
0 to 90 parts by weight) 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 weight is used with respect to 100 parts by weight 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-tert-butylperoxy-3,3,5-trimethylcyclohexane and 1,3.
-Bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5- (tert-butylpearloxy) hexane, 2,5-dimethyl-2,5
-Di (tert-butylperoxy) hexane, tris (tert-butylperoxy) triazine, 1,1-
Di-tert-butylperoxycyclohexane, 2,
2-di-tert-butylperoxybutane, 4,4-
Di-tert-butyl peroxyvaleric acid-
n-butyl ester, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyazelate, di-t-butylperoxytrimethyl adipate, 2,2-bis- (4,4-di-te)
rt-butylperoxycyclohexyl) propane,
A polyfunctional polymerization initiator having a functional group having a polymerization initiation function such as two or more peroxide groups in one molecule such as 2,2-tert-butylperoxyoctane and various polymer oxides, and diallylperoxydiene Carbonate, tert-butyl peroxymaleic acid, ter
t-butyl peroxyallyl carbonate and tert
-Butylperoxyisopropyl fumarate or the like is selected from polyfunctional polymerization initiators having both a functional group having a polymerization initiation function such as a peroxide group and a polymerizable unsaturated group in one molecule.

Of these, more preferred are 1,1
-Di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, di-tert-butylperoxyhexahydroterephthalate, di-tert-
Butyl peroxyazelate and 2,2-bis (4,4
-Di-tert-butylperoxydicyclohexyl) propane and tert-butylperoxyallyl carbonate. These polyfunctional polymerization initiators are preferably used in combination with a monofunctional polymerization initiator in order to satisfy various performances required as a binder resin for toner. 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 (tert-butylperoxy) -3,3
5-trimethylcyclohexane, n-butyl-4,4-
Organic peroxides such as di (tert-butylperoxy) valerate, dicumyl peroxide, α, α′-bis (tert-butylperoxydiisopropyl) benzene, tert-butylperoxycumene, di-tert-butylperoxide And azo compounds such as azobisisobutyronitrile and diazoaminoazobenzene, and diazo compounds.

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 initiators are preferably used in an amount of 0.05 to 2 parts by weight based on 100 parts by weight of the monomer.

The binder resin used in the present invention 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-hydroxydiphenyl) propane diacryle) DOO, polyoxyethylene (4) -
2,2-bis (4-hydroxyphenyl) propanediacrylate, and those in which the acrylates of the above compounds are replaced with methacrylates; and further, polyester type diacrylate compounds (for example, "MA manufactured by Nippon Kayaku Co., Ltd."
NDA "). As the polyfunctional crosslinking agent, pentaerythritol acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, and acrylates of the above compounds into methacrylate. And the like; triallyl cyanurate, triallyl trimellitate; and the like.

These cross-linking agents are used as the other monomer component 10
It is preferable to use 0.00001 to 1 part by weight, preferably 0.001 to 0.05 part by weight, relative to 0 part by weight.

Among these crosslinkable monomers, those which are preferably used from the viewpoints of toner fixing property and anti-offset property are those which are linked by a chain containing an aromatic divinyl compound (particularly divinylbenzene), an aromatic group and an ether bond. Diacrylate compounds mentioned above. As other synthetic methods, a bulk polymerization method and 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 initiator used is minimized and the influence of the residual initiator is minimized.

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

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 the following formula (A) and derivatives thereof;

[0153]

[Chemical 1]

(Wherein R is an ethylene or propylene group, x and y are integers of 0 or more, and
The average value of x + y is 0-10. ), Diols represented by the following formula (B):

[0155]

[Chemical 2] Is mentioned.

As the divalent acid component, for example, phthalic acid,
Benzenedicarboxylic acids such as 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,
Lower alkyl ester; n-dodecenyl succinic acid, n-
Alkenyl succinic acids such as dodecyl succinic acid or alkyl succinic acids, or their anhydrides, lower alkyl esters; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid or their anhydrides,
Lower alkyl ester; and other dicarboxylic acids and their derivatives.

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.

As the polyhydric alcohol component having a valence of 3 or more,
For example, 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 etc. are mentioned.

Examples of the trivalent or higher polycarboxylic acid component include, for example, trimellitic acid, hiromellitic 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-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8- Octane tetracarboxylic acid, empol trimer acid, and their anhydrides and lower alkyl esters;

[0160]

[Chemical 3]

(Wherein, X is an alkylene group having 5 to 30 carbon atoms or an alkenylene group having at least one side chain having 3 or more carbon atoms) and the like, and their anhydrides and lower alkyl esters. And polyvalent carboxylic acids and derivatives thereof.

The alcohol component is 40 to 60.
mol%, preferably 45-55 mol%, as an acid component 60-40 mol%, preferably 55-45 mol
% Is preferable.

The content of trivalent or higher polyvalent components is preferably 5 to 60 mol% of all components.

The polyester resin is also obtained by a generally known polycondensation.

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

As the charge control agent used in the present invention, for controlling the toner to be negatively charged, organic metal complexes and chelate compounds are effective, for example, monoazo metal complexes, acetylacetone metal complexes, and aromatic hydroxycarboxylic acids. Examples thereof include metal complexes of acids and aromatic dicarboxylic acids. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives of bisphenol.

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

[0168]

[Chemical 4]

Particularly, M is preferably Fe or Cr, and a halogen, an alkyl group or an anilide group is preferably used as a substituent.

Further, the basic organometallic complex represented by the following formula (2) is also preferable as the charge control agent imparting negative chargeability.

[0171]

[Chemical 5]

Particularly, M is preferably Fe, Cr, Si, Zn or Al, the substituent is preferably an alkyl group, anilide group, aryl group or halogen, and the counter ion is preferably hydrogen, ammonium or aliphatic ammonium.

The following compounds control the toner to be positively charged.

Nigrosine modified with nigrosine and fatty acid metal salts; tributylbenzylammonium-1-
Hydroxy-4-naphthosulfonates, quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts which are analogs thereof and lake pigments thereof; triphenylmethane dyes and lake pigments thereof , (As the laker, phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.);
Metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide and dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate, dioctyltin borate and dicyclohexyltin borate; guanidine compounds; imidazole compounds. These may 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. Formula (3) below

[0175]

[Chemical 6]

[Wherein R ¹ represents H or CH ₃ , and R ² and R ³ represent a substituted or unsubstituted alkyl group (preferably,
Monomers of monomers having 1 to 4 carbon atoms]: A copolymer with a polymerizable monomer such as the above-mentioned styrene, acrylic acid ester, and methacrylic acid ester may be used as a positive charge control agent. it can. In this case, the homopolymer and the copolymer have a function as a charge control agent and a function as (all or part of) a binder resin.

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

[0178]

[Chemical 7]

As a method of incorporating the charge control agent into the toner, there are a method of adding (internal addition) to the inside of the toner particles and a method of external addition. The amount of these charge control agents used is
It is determined by the type of the binder resin, the presence or absence of other additives, and the toner production method including the dispersion method, and is not uniquely limited. 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the resin, and when externally added, preferably 0.0 to 100 parts by weight of the toner particles.
It is used in an amount of 1 to 5.0 parts by weight, preferably 0.1 to 3.0 parts by weight.

Inorganic fine powder or hydrophobic inorganic fine powder is preferably externally added to the toner of the present invention. For example,
Examples include silica fine powder, titanium oxide fine powder, and hydrophobized products thereof. They are preferably used alone or in combination.

Examples of the fine silica powder include dry silica produced by vapor phase oxidation of a silicon halogen compound or dry silica called fumed silica, and wet silica produced from water glass. Preference is given to dry silica, which has few silanol groups inside and has no production residues.

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 the fine silica 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 / sec. 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.

As the method for treating silicone oil, the silica fine powder treated with the silane compound and the silicone oil may be directly mixed using a mixer such as a Hengel mixer, or the base silica fine powder may be mixed with the silicone oil. The method of injecting Alternatively, it may be produced by dissolving or dispersing silicone oil in an appropriate solvent, mixing it with the silica fine powder of the base, and removing the solvent.

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

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

It is also preferable that the fine silica powder is subjected to a hydrophobic treatment and further an oil treatment to fine titanium oxide powder as in the case of the silica-based powder.

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

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, an abrasive, etc.

The resin fine particles have an average particle diameter of 0.
It is preferably from 03 to 1.0 μm. The polymerizable monomer constituting the resin is 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 Teflon (registered trademark), zinc stearate and polyvinylidene fluoride (polyvinylidene fluoride is preferred among them); abrasives such as cerium oxide, silicon carbide and strontium titanate (among others, titanium). Strontium acid is preferred); flowability-imparting agents such as titanium oxide and aluminum oxide (particularly hydrophobic ones are preferred); anti-caking agents; conductivity-imparting agents such as carbon black, zinc oxide, antimony oxide and tin oxide. Can be mentioned. Further, a small amount of white fine particles and black fine particles having a polarity opposite to that of the toner may be used as a developing property improver.

The resin fine particles, the inorganic fine powder or the hydrophobic inorganic fine powder mixed with the toner particles are the toner particles 10.
0.1 to 5 parts by weight (preferably, 0.
1 to 3 parts by weight) is preferably used.

As a method for producing the toner of the present invention,
After thoroughly mixing the toner constituent materials as described above with a ball mill or other mixer, they are well kneaded with a heat kneader such as a heat roll kneader or an extruder, cooled and solidified, and then mechanically ground to obtain a ground powder. A method of obtaining a toner by classifying is preferable. In addition, a polymerization method of producing a toner by mixing a predetermined material with a monomer that constitutes a binder resin to form an emulsion suspension, and a toner manufacturing method; a so-called core material and a shell material In the microcapsule toner, a method of incorporating a predetermined material into the core material or the shell material, or both of them, and a method of obtaining the toner by dispersing the constituent materials in the binder resin solution and then spray-drying are mentioned. Further, if desired, desired additives and toner particles can be sufficiently mixed with a mixer such as a Henschel mixer to produce the toner of 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 Manufacturing Co., Ltd.); A spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.); a Ledige mixer (manufactured by Matsubo Co., Ltd.), and the kneading machine includes KRC kneader (manufactured by Kurimoto Iron Works Co., Ltd.); Bus Co Kneader (manufactured by Buss Co.); TEM. 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 router (manufactured by Moriyama Seisakusho); Banbury mixer (manufactured by Kobe) As a crusher, examples of the crusher include a counter jet mill, a micron jet, an inomizer (made by Hosokawa Micron Co.); an IDS type mill, a PJM jet crusher (made by Nippon Pneumatic Mfg. Co., Ltd.); a cross jet mill (Kurimoto Tekko Co., Ltd.). Ulmax (manufactured by Nisso Engineering); SK Jet
O-mill (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); Turbo Mill (manufactured by Turbo Kogyo Co., Ltd.), and classifiers include glass seal, micron classifier, and spedic classifier (Seishin company). Manufactured by Nisshin Engineering Co., Ltd .; micron separator, turbo flex (ATP), TSP separator (manufactured by Hosokawa Micron), elbow jet (manufactured by Nippon Steel Mining Co., Ltd.), dispersion separator (Nippon Pneumatic Mfg. Co., Ltd.) Made);
YM Micro Cut (manufactured by Yasukawa Shoji Co., Ltd.) is mentioned, and as a sieving device used for sieving coarse particles and the like, there are Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resona Sieve, Gyro Shifter (Tokuju Kosakusho Co., Ltd.); Vibra Sonikku system (manufactured by Dalton); Soniclean (manufactured by Shinto Kogyo); Turbo Screener (manufactured by Turbo Kogyo); Microshifter (manufactured by Makino Sangyo); circular vibrating sieve and the like.

[0197]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention in any way.

[Synthesis Example of Wax] (Wax 1) 1000 Fischer-Tropsch wax (number average molecular weight (Mn): 740) as a raw material
g into a cylindrical glass reactor and add a small amount of nitrogen gas (3
(Liter / min), the temperature was raised to 140 ° C. while blowing. After adding 29.82 g (0.43 mol) of a mixed catalyst of boric acid / boric anhydride = 1.5 (mol ratio), air (22 liter / min) and nitrogen (17 liter / mi) were added.
The reaction was carried out at 180 ° C. for 2.5 hours while blowing n). After completion of the reaction, an equal amount of warm water (95 ° C.) was added to the reaction mixture, and the reaction mixture was hydrolyzed to obtain Wax 1. Wax 1 has an acid value of 8 mgKOH / g and a hydroxyl value of 70 m
gKOH / g, ester value was 18 mgKOH / g, melting point was 93 ° C., and viscosity was 13.3 mPa · sec. Table 1 shows the synthesis conditions and physical properties of the wax.

(Wax 2) Wax 2 was prepared in the same manner as in Wax Synthesis Example 1 except that 1000 g of polyethylene wax (Mn: 830) was used as a raw material and the addition amount of boric acid / boric anhydride mixed catalyst and the reaction time were changed. Got Table 1 shows the synthesis conditions and physical properties of the wax.

(Wax 3) 1000 g of paraffin wax (Mn: 370) was used as a raw material, and boric acid /
Wax 3 was obtained in the same manner as in Wax Synthesis Example 1 except that the addition amount of the boric anhydride mixed catalyst and the reaction time were changed. Table 1 shows the synthesis conditions and physical properties of the wax.

(Wax 4) Wax 4 was prepared in the same manner as in Wax Synthesis Example 1 except that 1000 g of olefin wax (Mn: 1500) was used as a raw material and the addition amount of boric acid / boric anhydride mixed catalyst and the reaction time were changed. Got Table 1 shows the synthesis conditions and physical properties of the wax.

(Wax 5) 1000 g of paraffin wax (Mn: 380) was used as a raw material, and boric acid /
Wax 5 was obtained in the same manner as in Wax Synthesis Example 1 except that the addition amount of boric anhydride mixed catalyst and the reaction time were changed. Table 1 shows the synthesis conditions and physical properties of the wax.

(Wax 6) 1000 g of paraffin wax (Mn: 340) was used as a raw material and boric acid /
Wax 6 was obtained in the same manner as in Wax Synthesis Example 1 except that the addition amount of the boric anhydride mixed catalyst and the reaction time were changed. Table 1 shows the synthesis conditions and physical properties of the wax.

(Wax 7) A wax was prepared in the same manner as in Wax Synthesis Example 1 except that 1000 g of microcrystalline wax (Mn: 580) was used as a raw material and the addition amount of boric acid / boric anhydride mixed catalyst and the reaction time were changed. 7
Got Table 1 shows the synthesis conditions and physical properties of the wax.

(Wax 8) Wax 8 was obtained in the same manner as in Wax Synthesis Example 1 except that 1000 g of polyethylene wax (Mn: 670) was used as a raw material, metaboric acid was used as a catalyst, and the reaction time was changed. Table 1 shows the synthesis conditions and physical properties of the wax.

[Manufacturing Example of Magnetic Iron Oxide] Next, a manufacturing example of the magnetic iron oxide used in this example is shown. The physical properties are shown in Table 2.

(Magnetic iron oxide 1) In an aqueous solution of ferrous sulfate,
After mixing 0.95 equivalent of sodium hydroxide aqueous solution with respect to Fe ²⁺ , a first salt aqueous solution containing Fe (OH) ₂ was produced. Further, to this suspension was added a sodium hydroxide aqueous solution in which sodium silicate (equivalent to 1.1% by weight in terms of silicon with respect to iron element) was added in an amount of 1.05 equivalent to the residual Fe ²⁺ . , Magnesium sulfate was added to the iron element so that the content of the magnesium element was 1.2% by weight, and the mixture was heated at a temperature of 90 ° C. to cause an oxidation reaction to contain silicon element and magnesium element. Iron oxide was produced.

After washing the produced magnetic iron oxide by a conventional method and before the filtration step, a predetermined amount of aluminum sulfate was added to the slurry solution to adjust the pH to a range of 7 to 10 to remove the magnetic iron oxide with aluminum hydroxide. Surface treatment was performed. Next, the aggregated magnetic iron oxide was crushed (consolidated crushing treatment using a mix muller) to obtain magnetic iron oxide 1 containing silicon, magnesium and aluminum.

(Magnetic iron oxide 2) Magnetic iron oxide 1 except that a predetermined amount of sodium silicate and a predetermined amount of zinc sulfate are added, and the magnetic iron oxide contains silicon element and zinc element by the oxidation reaction.
Same as the manufacturing method of, and then crushing aggregated magnetic iron oxide (consolidation crushing treatment by mix muller)
Then, magnetic iron oxide particles 2 containing silicon and zinc were generated.

(Magnetic Iron Oxide 3) The production method of magnetic iron oxide 1 is the same as that for producing magnetic iron oxide 1 except that the amount of sodium silicate added is changed, magnesium sulfate is not used, and only crushing treatment is performed after surface treatment with aluminum sulfate. Thus, a magnetic iron oxide 3 containing silicon, magnesium and aluminum was produced.

(Magnetic iron oxide 4) A predetermined amount of sodium silicate,
Silicon was prepared in the same manner as in the method for producing magnetic iron oxide 1 except that a predetermined amount of zinc sulfate and a predetermined amount of magnesium sulfate were added.
Magnetic iron oxide containing zinc, magnesium and aluminum 4
Was produced.

(Magnetic iron oxide 5) Magnetic iron oxide 5 was prepared in the same manner as magnetic iron oxide 2 except that the amounts of sodium silicate and zinc sulfate were changed.

(Magnetic iron oxide 6) Without using sodium silicate,
A magnetic iron oxide 6 was prepared in the same manner as the magnetic iron oxide 2 except that only the amount of zinc sulfate was changed and used.

(Magnetic Iron Oxide 7) A magnetic iron oxide 7 was produced in the same manner as the magnetic iron oxide 1 except that a predetermined amount of sodium silicate and a predetermined amount of magnesium sulfate were used.

(Magnetic iron oxide 8) Magnetic iron oxide 8 was prepared in the same manner as magnetic iron oxide 1 except that a predetermined amount of sodium silicate was used.
Was produced.

(Magnetic Iron Oxide 9) Magnetic iron oxide 9 was produced in the same manner as magnetic iron oxide 1 except that a predetermined amount of sodium silicate, a predetermined amount of magnesium sulfate, and a predetermined amount of aluminum sulfate were used.

[0217]   [Example of toner production]   (Toner A) Styrene-acrylic copolymer 100 parts by weight Magnetic iron oxide 1 100 parts by weight Negatively charged charge control agent (monoazo iron complex) 2 parts by weight Wax 1 14 parts by weight

The above mixture was melt-kneaded with a twin-screw extruder heated to 130 ° C., the cooled kneaded product was coarsely pulverized with a hammer mill, and the coarsely pulverized product was finely pulverized with a jet mill. The powder was fixed and coarsely pulverized with a hammer mill, the coarsely pulverized product was finely pulverized with a jet mill, and the obtained finely pulverized powder was classified with a fixed wall type air classifier to produce classified powder. Further, the weight-average particle diameter (D4) is obtained by strictly classifying and removing the obtained classified powder at the same time by using a multi-division classifier (“Elbowjet classifier” manufactured by Nittetsu Mining Co., Ltd.) that utilizes the Coanda effect. ) 6.8 μm negatively chargeable magnetic toner particles were obtained.

Toner A was prepared by mixing 100 parts by weight of the magnetic toner particles and 1.2 parts by weight of the hydrophobic silica fine powder with a Henschel mixer.

(Toners B to T) Example 1 except that the combination of wax 1 and magnetic iron oxide 1 was changed to those shown in Table 3.
The same treatment as described above was performed to obtain toners B to T.

[Evaluation] Toner A manufactured by the above method
Using T as a developer, its characteristics were evaluated by the following methods.

The above toner is put in a process cartridge, and a laser beam printer "LBP-3 manufactured by Canon" is used.
"260" was used with A4 transverse feed at 32 sheets / min. The process speed at this time was 145 mm / sec.

Under the above setting conditions, in a high temperature and high humidity environment (32.
5 ℃, 80% RH) and low temperature and low humidity environment (15 ℃, 10
% RH), an image output test of 20,000 sheets was continuously performed, and the obtained images were evaluated for the following items. The evaluation results are shown in Table 3.

(1) Image Density 20,000 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 was measured by using a "Macbeth reflection densitometer" (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to the printout image of the white background portion whose current density is 0.00. The value is an average value during durability.

(2) Fog 20,000 sheets were printed out on ordinary plain paper for copiers (75 g / m ² ) at low temperature and low humidity (15 ° C., 10% RH) to evaluate the fog at the start and end. went. Fog was calculated by comparing the whiteness of the transfer paper measured with a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness of the transfer after printing solid white. The larger this value is, the worse the fog is.

(3) Ghost evaluation 20,000 sheets are printed out on ordinary plain paper for copiers (75 g / m ² ) at low temperature and low humidity (15 ° C., 10% RH), and negative ghosts are evaluated every 5000 sheets. went. For image evaluation regarding the ghost, a half-tone image was output after outputting a solid black band for one round of the sleeve. A schematic diagram of the pattern is shown in FIG. The evaluation method was carried out by a Macbeth densitometer at a place where a black image was formed in the first turn of the sleeve (black print part) and a place where the black image was not formed (non-image part) in one print image. The difference in the measured reflection density was calculated as follows. In the negative ghost, in general, in the density appearing in the second round of the sleeve, the first round is the image part (B in FIG. 1), and the first image density is the non-image part (FIG. 1).
A) is a phenomenon in which the image density is low, and when it becomes terrible, it is a ghost phenomenon in which the shape of the pattern produced in the first round appears as it is. The difference in reflection density was used to evaluate the difference.

Reflection Density Difference = Reflection Density (No Image Formed; A) -Reflection Density (Image Formed; B)

The average value is shown in Table 3. The smaller the reflection density difference, the less the ghost occurs and the better the level.

As a comprehensive evaluation of ghosts, ○, ○ △, △,
The evaluation was made in five levels of Δ × and X. ◯: When the reflection density difference is 0.00 to 0.02 ○ Δ: When 0.03 to 0.04 Δ: When 0.04 to 0.05 Δ ×: When 0.05 to 0.07 × : In case of 0.07 ~

(4) Blocking resistance About 10 g of the toner is put in a 100 cc poly cup, and 50
After left at 3 ° C for 3 days, it was visually evaluated. ⊚: Aggregates are not seen. ◯: Aggregates are seen, but they easily collapse. Δ: Aggregates are seen, but collapse if shaken. X: Aggregates can be grabbed and do not easily collapse.

(5) Fixing Member Adhesion Whether or not toner adheres to the separating claw of the fixing roller, and the toner is discharged from the fixing claw to stain the image, whether there is a lump of toner discharged in the image during running, In addition, the degree of dirt on the separation nail was evaluated. ◯: No toner lumps appear on the image, and almost no toner adheres to the separation claw. Δ: Toner is not discharged on the image, but the separation claw is stained with toner. Δx: A state in which the toner is ejected from the separation claw and the image is stained. ×: Toner dirt adheres to the separation claw, and paper jam occurs at the claw part.

Table 3 shows the developability of toners A to T, image density, fog, negative ghost, and blocking test results.

[0233]

[Table 1]

[0234]

[Table 2]

[0235]

[Table 3]

[0236]

As described above, in the present invention, by using the specific wax and the magnetic iron oxide in combination, the magnetic iron oxide and the wax are uniformly dispersed in the toner particles. Toner deterioration can be prevented, and stable and favorable image formation can be achieved even in long-term durability.

[Brief description of drawings]

FIG. 1 is a diagram showing an image pattern used for ghost evaluation in an example of the present invention.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Tsutomu Onuma             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Tsuneo Nakanishi             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Katsuhisa Yamazaki             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 AA02 AA06 CA14 EA03 EA10

Claims (13)

[Claims] 1. At least toner particles containing at least a binder resin, a magnetic iron oxide and a hydrocarbon wax, and the hydroxyl value (H _v ) of the wax is 5 to 150 mgK.
OH / g, ester value (E _v ) is 1 to 50 mgKOH /
g, the relationship between the hydroxyl value (H _v ) and the ester value (E _v ) is H _v > E _v , and the magnetic iron oxide is Mg, Al, Si, P, S or C.
at least 1 different element selected from a, Cu, Zn
A toner containing a seed, wherein the content of the different element is 0.1 to 5.0% by weight based on the iron element in the magnetic iron oxide. 2. The acid value (A _v ) of the wax is 1 to 30 m.
The toner according to claim 1, wherein the toner has a value of gKOH / g, and the relationship between the acid value (A _v ) and the hydroxyl value (H _v ) of the wax is H _v > A _v . 3. The toner according to claim 1, wherein the melting point of the wax is 65 to 130 ° C. 4. The viscosity of the wax at 150 ° C.
4. The toner according to claim 1, wherein the toner has a viscosity of 200 mPa · sec or less. 5. The toner according to claim 1, wherein the wax is a wax obtained by converting an aliphatic hydrocarbon wax into an alcohol. 6. The content of the different element of the magnetic iron oxide is 0.2 to 4.0% by weight based on the iron element in the magnetic iron oxide. The toner according to any one. 7. The ratio of the different elements present in the magnetic iron oxide having an iron element dissolution rate of up to 20% by weight is 30% or more of the total content of the different elements in the magnetic iron oxide. 7. The toner according to any one of claims 1 to 6. 8. The different element is at least silicon,
8. The toner according to claim 1, wherein the content of silicon element in the magnetic iron oxide is 0.2 to 4.0% by weight based on the iron element. 9. Fe / S on the outermost surface of the magnetic iron oxide.
The toner according to claim 8, wherein the atomic ratio of i is 1.2 to 4.0. 10. The magnetic iron oxide contains Al and a different element other than Al, and the content of the Al element is 0.01 to 2.0% by weight based on the iron element. The toner according to claim 1. 11. Fe / on the outermost surface of the magnetic iron oxide
The toner according to claim 10, wherein the atomic ratio of Al is 0.3 to 10. 12. The magnetic iron oxide has a smoothness of 0.3 to 0.
The toner according to claim 1, wherein the toner is 8. 13. The specific surface area of the magnetic iron oxide is 20.0 m.
The toner according to any one of claims 1 to 12, which has a content of ² / g or less.