JPH09156906A - Hydrophobic metal oxide powder and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hydrophobic metal oxide powder useful as an additive for an electrophotographic developer by treating the surface of metal oxide powder (e.g. silica powder produced by dry process), thereby imparting the metal oxide powder with frictional electrification property controlled over a wide range from negative charge to positive charge and high hydrophobicity and fluidity by the use of a relatively small amount of a coating material. SOLUTION: A silicone oil having epoxy group (e.g. a silicone oil having glycidyl groups on both terminals) is made to react with a non-polymerizable primary and/or secondary amine compound of an amount less than the amount reacting with the total epoxy group and the surface of metal oxide powder is treated with the obtained silicone oil having epoxy group and amine group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophobic metal oxide powder which is suitable for addition to a developer for electrophotography for the purpose of improving fluidity of toner and controlling charge property, and an electron containing the same. It relates to a photographic developer.

[0002]

2. Description of the Related Art The development process in electrophotography is carried out by attaching toner to an electrostatic latent image on a photoconductor. A typical electrophotographic developer contains, in addition to the toner, a carrier for imparting an electric charge to the toner by frictional charging and for transporting the toner to a developing area on the photoreceptor. Generally, a toner is composed of a thermoplastic resin, a colorant and a charge control agent, and a magnetic powder such as iron or ferrite (iron oxide) is used as a carrier. In addition to the toner and carrier, it is known that various additives can be added to the developer for the purpose of controlling the charge of the toner, improving the fluidity and cleaning property of the toner, and the like.

For example, a hydrophobic metal oxide powder obtained by hydrophobizing the surface of a metal oxide powder of silica, alumina, titania or the like with an organic substance is a developer for electrophotography as an agent for improving fluidity and cleaning property of toner. Has been added to. It is also known to use such a hydrophobic metal oxide powder as a charge control agent. Therefore, in this kind of hydrophobic metal oxide powder, hydrophobicity and triboelectrification properties are important properties, and these properties are controlled by the type and coating amount of the organic substance used for the surface treatment of the metal oxide powder.

Generally, in the surface treatment of metal oxide powder, when the surface treatment of the powder is performed with an amine-based organic compound,
It is known that the negative chargeability of the powder is reduced or the powder is given a positive chargeability, and thus the metal oxide powder surface-treated with an amine-based organic compound is used as a toner charge. It has already been proposed to use it as a control agent.

For example, Japanese Patent Publication No. 53-22447 proposes to use a metal oxide powder surface-treated with aminosilane (an amino group-containing silane coupling agent) as a positive charge control agent for toner. In addition, JP-A-62-52
Japanese Patent No. 561 discloses an electrophotographic toner containing a powder obtained by treating vapor-phase process silica with an silane containing an epoxy group and then with an amine as a positive charge control agent. In general, the metal oxide powder surface-treated with such a silane cannot have sufficiently high hydrophobicity, and the effect of improving the fluidity and cleaning property of the toner becomes insufficient.

Japanese Unexamined Patent Publication No. 6-80406 and 6-8309
No. 9 discloses that a metal oxide powder surface-treated with an epoxy group-containing organopolysiloxane and polyalkyleneimine is added to an electrophotographic developer for the purposes of both improving fluidity and controlling toner chargeability. It is described to do. However, polyalkyleneimines used as amines
(Example, polyethyleneimine) is a high molecular weight polymeric amine containing a large number of amino groups per molecular weight, because the surface of the powder is covered with a polyalkyleneimine chain having a relatively high hydrophilicity, It was found that the hydrophobicity and fluidity were insufficient. According to the embodiment of Japanese Patent Laid-Open No. 6-80406, the silica powder is converted into the silica powder by the above surface treatment.
%, A high hydrophobizing rate is imparted. This is because the surface treatment was performed with a composition containing dimethylpolysiloxane as a hydrophobizing agent in addition to the above two components. Otherwise, the hydrophobization rate will drop significantly.

JP-A-63-155155 describes an electrostatic image developer containing inorganic fine particles which are first treated with a silicone oil having an epoxy group and then treated with an amino compound. However, the inorganic fine particles thus treated in two stages have uncertain chargeability control and / or insufficient hydrophobicity.

[0008]

DISCLOSURE OF THE INVENTION The object of the present invention is to provide a hydrophobic metal oxide capable of controlling the triboelectric chargeability in a wide range with a relatively small amount of coating and at the same time imparting high hydrophobicity and fluidity. A powder and an electrophotographic developer containing the powder are provided.

[0009]

The above object can be achieved according to the present invention by a hydrophobic metal oxide powder having a surface coating formed from a silicone oil having an epoxy group and an amino group.

A silicone oil having an epoxy group and an amino group is a silicone oil having an epoxy group,
Less than the amount needed to react with all of the epoxy groups,
It can be prepared by reacting a non-polymeric amine compound having a primary and / or secondary amino group.

The hydrophobic metal oxide powder of the present invention preferably exhibits a hydrophobization rate of 60% or more as measured by the transmittance method. The present invention also provides an electrophotographic developer containing the hydrophobic metal oxide powder.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The kind of the metal oxide powder to be surface-coated in the present invention is not particularly limited and can be selected according to the application. Preferred metal oxides for improving the fluidity of the toner are silica, alumina or titania (titanium oxide), but depending on the application, powders of other metal oxides such as zirconia (zirconium oxide), zinc oxide and tin oxide. The body can also be used.

The particle size of the metal oxide powder may be selected according to the application. A specific surface area of 50
It is preferable to use a powder of m ² / g or more. The metal oxide may be a composite oxide of two or more metals or a mixture of two or more metal oxides.

The metal oxide powder is preferably one synthesized by a vapor phase method. The metal oxide powder synthesized by the gas phase method is suitable for improving the fluidity of the toner because the particles do not aggregate much. As a method for synthesizing a metal oxide powder by a gas phase method, for example, a method in which a metal chloride such as silicon tetrachloride is decomposed is known, and an industrially synthesized product is commercially available.

According to the present invention, a silicone oil having an epoxy group and an amino group on the surface of a metal oxide powder.
A coating is formed by a surface treatment using (hereinafter referred to as epoxy / amino modified silicone oil). The epoxy group of this modified silicone oil mainly strengthens the binding force with the metal oxide powder, the amino group changes the chargeability of the metal oxide powder in the positive direction, and the silicone oil itself is the metal oxide powder. It acts to impart hydrophobicity to the body. Then, the chargeability imparted to the powder changes greatly depending on the type of amino group.

The epoxy / amino-modified silicone oil is a silicone oil having an epoxy group (hereinafter referred to as an epoxy-modified silicone oil), which is smaller than the stoichiometric amount necessary for reacting with all the epoxy groups, and a primary and / or Alternatively, it is preferably prepared by reacting an amine compound having a secondary amino group. Conversely, a silicone oil having a primary and / or secondary amino group (hereinafter referred to as an amino-modified silicone oil)
It is also possible to prepare a silicone oil having an epoxy group and an amino group by reacting a bifunctional or higher epoxy compound in an amount larger than that required to react with all of the primary and secondary amino groups. It is possible. However, since the types of difunctional or higher functional epoxy compounds that are easily available are extremely limited, the types of silicone oil that can be prepared are significantly reduced compared to the first reaction. It is disadvantageous in controlling a certain triboelectrification property in a wide range.

The epoxy-modified silicone oil and amine compound have a molar ratio of the total number of primary and secondary amino groups in the amine compound to the total number of epoxy groups in the silicone oil in the range of 0.1 to 0.9, particularly 0.2 to 0.8. It is preferred to use in proportion. By this reaction, part of the epoxy groups in the silicone oil reacts with the primary or secondary amino group of the amine compound to open the ring, and instead of the epoxy group, -OH group and -NR group (amino group) become silicone oil. Will be introduced to. As a result, an epoxy / amino-modified silicone oil having unreacted epoxy groups and reaction-introduced amino groups is obtained.

When the amine compound contains a primary amine group, a --NH group may be generated in the above reaction, and this group may further react with an epoxy group, but it is considered to be low. Therefore, the stoichiometric amount can be estimated by the ratio of the reactive amino group and the epoxy group as described above.

When the above molar ratio is less than 0.1, the number of amino groups introduced is small and the control of charging property becomes insufficient. On the other hand, when the above molar ratio exceeds 0.9, the number of unreacted epoxy groups decreases, the bond of the coating to the powder becomes insufficient, and unreacted amine compound tends to remain. It is not preferable because it adversely affects the stability or hydrophobicity. The above reaction proceeds by simply mixing both components at room temperature or stirring in a polar solvent such as alcohol, but may be heated to a temperature at which the reaction components do not volatilize, if desired.

When the amount of the amine compound used in the reaction becomes larger than the stoichiometric amount, the epoxy group highly reactive with the metal oxide powder completely reacts with the amine and disappears from the silicone oil. However, the surface treatment needs to be performed at a higher temperature, and the binding force of the formed coating with the powder surface is reduced.

The epoxy-modified silicone oil is an oily organopolysiloxane having an epoxy group. For example, an epoxy-modified silicone oil having a structure having a glycidyl group and / or an alicyclic epoxy group at a terminal and / or a side chain of a dimethylpolysiloxane skeleton is commercially available.

A preferred epoxy-modified silicone oil has a glycidyl group as an epoxy group, and the epoxy equivalent is preferably 200 to 3000 g / mol. When the epoxy equivalent exceeds 3000 g / mol, the cause is unknown, but it becomes difficult to obtain a sufficient effect when reacted with an amine compound. The viscosity of the silicone oil is preferably in the range of 5 to 100 cSt at 25 ° C. If the viscosity exceeds 100 cSt, the fluidity decreases, and if the viscosity is less than 5 cSt, the metal oxide powder tends to volatilize during the surface treatment.

A particularly preferred epoxy-modified silicone oil has a glycidyl group at both ends of the molecule, an epoxy equivalent of 300 to 1000 g / mol and a viscosity at 25 ° C. of 10 to 50 cSt. More preferably, the epoxy-modified silicone oil has glycidyl groups only at both ends of the molecule. The presence of a glycidyl group in the side chains in addition to both ends may reduce the hydrophobicity.

Examples of commercially available epoxy-modified silicone oils are KF-101, KF-102, KF manufactured by Shin-Etsu Silicone Co., Ltd.
-103, KF-105, X-22-163A, X-22-169AS, X-22-163B, X-
22-163C, X-22-169B etc .; Toray Dow Corning Silicone's SF8411, SF8413, SF8421 etc .; and Toshiba Silicone's TSF4730, TSF4731, TSL9946, TSL9986,
Examples include TSL9906 and the like.

As the amine compound to be reacted with the epoxy-modified silicone oil, a non-polymeric amine compound having a primary and / or secondary amino group reactive with an epoxy group is used. When a polymer type amine compound such as polyalkyleneimine is used, the coated surface is substantially covered with a high molecular weight amine (having relatively high hydrophilicity) as described above, and the metal oxide powder after surface treatment is used. The hydrophobicity of the body is low, and thus the fluidity improving effect is also insufficient.

As will be illustrated later in Examples, the chargeability of the hydrophobic metal oxide powder of the present invention is greatly changed depending on the kind of the amine compound. That is, when an amine compound adheres to the surface of the metal oxide powder, the amine compound generally changes the chargeability in the positive direction, but the degree of change (the effect of imparting the positive chargeability) depends on the type of amine compound. different. Therefore, by changing the type and amount of the amine compound, the chargeability of the hydrophobic metal oxide powder, for example, silica powder (the triboelectric charge amount measured by the method described below) can be reduced to a negative value of about -500 μC / g. 300 μC / g due to electrostatic properties
It is possible to control to a desired value within a wide range that extends to a positive chargeability exceeding 10%. Therefore, the type of amine compound may be selected according to the desired chargeability level required for the toner.

The influence of the amine compound on the chargeability is generally as follows. (A) An amine having a relatively small positive charge imparting effect (1) Aliphatic primary amine (R ¹ NH ₂ : R ¹ is an alkyl group having 4 to 20 carbon atoms, even if an ether bond is present in the alkyl group. Good), (2) aromatic amines (aromatic amines having one or more primary or secondary amino groups such as aniline, toluidine, etc.), (3) heterocyclic amines (one or more primary or secondary amino groups) Heterocyclic amines, such as pyrrole, imidazole, indole, etc.).

(B) Amine having a large positive charge imparting effect (1) Aliphatic secondary amine (R ¹ R ² NH: R ¹ and R ² are both the same or different alkyl groups having 1 to 10 carbon atoms) , An alkyl group may have an ether bond), (2) diamine (R ¹
R ² NXNHR ³ : R ¹ , R ² and R ³ may be the same or different in each case of a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, there may be an ether bond in the alkyl group, and X is An alkylene group having 1 to 10 carbon atoms), (3) triamine (R ¹ R ²
NXNR ³ YNHR ⁴ : R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms or alkyl groups having 1 to 10 carbon atoms (provided that they are not all hydrogen atoms), which may be the same or different, and are alkyl. There may be an ether bond in the group, and X and Y are both alkylene groups having 1 to 10 carbon atoms), and similar higher amines such as tetraamine, (4) alicyclic amine (one or more) Alicyclic amine having a primary or secondary amino group, such as piperazine, piperidine, etc.), (5) heterocyclic amine having a primary or secondary aminoalkyl group (e.g., triazine) or alicyclic amine (e.g., Piperazine). The heterocyclic amine or alicyclic amine in this case may have only a tertiary amino group.

The above is only a guideline, and the amine compound to be actually used may be selected after investigating its charge imparting effect by an experiment. Also, two or more amine compounds can be used. In that case, as a result of the mixing, the behavior of imparting the charging property of the amine compound may change from the above.

Particularly preferred amine compounds for imparting positive chargeability are the above diamines, that is, the general formula: R ¹ R ² N
It is a compound represented by XNHR ³ . Compared with other amine compounds, this compound can impart high positive chargeability with a relatively small amount of addition, so that it is useful as a fluidity improver for positively chargeable toner at +10 to +250 μC / g. A metal oxide powder having a triboelectric charge amount within the range can be efficiently and stably obtained. Among them, R ¹ and R ² are an alkyl group having 1 to 6 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and X is-(CH) n- (n is 2 to 4). Integer)
And the diamine is preferable for imparting positive chargeability. The larger the carbon number of the alkyl bonded to the nitrogen atom, the higher the hydrophobicity of the metal oxide powder, and the more stable the chargeability tends to be.

On the other hand, stable negative chargeability (for example, -100
Metal oxide powders with ~ -200 μC / g) are also useful for negatively charged toners. In this case, the above-mentioned positive chargeability-providing effect is compared with the method of obtaining a desired metal oxide having negative chargeability by controlling the addition amount of the amine compound having a large positive-chargeability imparting effect. There is a method of using a small amine compound. When an amine compound having a large positive charge imparting effect is used, the target negative chargeability can be obtained with a small addition amount, and in an amine compound having a relatively small positive charge imparting effect, the chargeability is It is easy to obtain a stable negative charging property because it is hard to change.

The surface treatment of the metal oxide powder with the epoxy / amino-modified silicone oil may be carried out by a conventionally known method, and may be either a wet method or a dry method. However, when the metal oxide powder is synthesized by a vapor phase method, the dry method is preferable because aggregation is less likely to occur.
The dry method is also advantageous in that the amount of treatment liquid used is small, the amount of coating on the powder is easy to control, and the operation is simple.

In the surface treatment by the dry method, for example, the above modified silicone oil is added dropwise or sprayed while the metal oxide powder is sufficiently stirred in a suitable closed type container. If necessary, add modified silicone oil to the solvent (e.g.,
It can also be used after diluting with (alcohol, ketone, hydrocarbon, etc.).

After adding the epoxy / amino-modified silicone oil, the metal oxide powder is heated under a nitrogen stream at a temperature in the range of 80 to 250 ° C., preferably in the range of 100 to 170 ° C. to obtain a silicone oil. Is strongly bonded to the surface of the metal oxide powder, and the solvent is simultaneously removed if necessary. Since the silicone oil has an epoxy group having high reactivity with the surface of the metal oxide powder, surface coating can be achieved by such heat treatment at a relatively low temperature.

When the dry treatment as described above is difficult depending on the type of the metal oxide powder, the metal oxide powder is immersed in a solution prepared by dissolving silicone oil in an appropriate organic solvent. After recovering from the solution, it is possible to perform surface treatment by a wet method such as heating as described above.

By this surface treatment, the modified silicone oil is bonded to the powder surface by reacting the epoxy group with the OH group existing on the surface of the metal oxide powder.
As a result, the amino groups present in the silicone oil are firmly bound to the surface of the powder, the chargeability of the powder changes, and at the same time, the surface of the powder becomes hydrophobic due to the silicone oil. Further, since the silicone oil is firmly bonded to the surface of the powder, it is not easily affected by the environment such as moisture, and the characteristics such as hydrophobicity and chargeability do not change with time, and the stability is excellent.

The amount of the epoxy / amino-modified silicone oil adhered to the surface of the metal oxide powder is such that the desired chargeability is obtained as described above, and at the same time, sufficient hydrophobicity (fluidity) is imparted. select. Therefore, in order to secure sufficient hydrophobicity, it is usually 5 to 40 parts by weight per 100 parts by weight of the metal oxide powder, although it depends on the kind of amine compound used for the preparation of the modified silicone oil and the amount thereof used.
It is preferred to use the modified silicone oil described above in an amount of parts by weight, especially in the range of 10 to 30 parts by weight. Further, the molar ratio of the OH groups present on the surface of the metal oxide powder and the total number of primary, secondary and tertiary amino groups in the silicone oil,
It is preferable to use the modified silicone oil in the range of 0.1 to 1.0, particularly 0.2 to 0.6, from the viewpoint of the effect of imparting electrostatic properties.

The higher the degree of hydrophobicity of the hydrophobic metal oxide powder obtained by the surface treatment, the lower the hygroscopicity of the metal oxide powder, and the smaller the change in the charge amount of the toner with respect to humidity. In addition, the effect of preventing aggregation (fluidity improvement effect) is enhanced and the utility value is high. Practically, the value of the hydrophobicity measured by the transmittance method may be 60% or more, preferably 70% or more, more preferably 80% or more.

The transmittance method is a method for experimentally obtaining the hydrophobicity of powder. According to this method, 1.0 g of powder and 10 parts of water
Add 0 ml to the extraction funnel and shake vigorously for 10 minutes. Then, let stand for 10 minutes, and withdraw a small amount of suspension from the bottom of the separatory funnel. The value obtained by expressing the transmittance of the extracted suspension for light at 550 nm with the transmittance of pure water being 100% is the hydrophobicity of the powder.

The chargeability of the obtained hydrophobic metal oxide powder can be evaluated by measuring the triboelectric charge amount by the blow-off method. The method of measuring the triboelectric charge amount for iron by the blow-off method is, for example, “Color material” 55 [9] 630-636 (1
982) and other documents. In the present invention, the triboelectric charge amount was determined by the method specified for this "color material".

The hydrophobic metal oxide powder of the present invention is added to an electrophotographic developer used in a copying machine or a printer as an additive for improving the fluidity and cleaning properties of a toner, or as a charge control agent. Can be included.
Thereby, an electrophotographic developer having stable chargeability and excellent fluidity can be obtained. It can also be used for controlling the charging property by incorporating it in a silicone rubber roll used in a copying machine or the like.

When it is contained in the electrophotographic developer, the amount of the hydrophobic metal oxide powder added is practically desirable to be in the range of 0.1 to 20% by weight based on the total weight of the toner. When used as a charge control agent, the added amount is generally larger than when it is used as a fluidity improver. In the case of fluidity improvers, a range of 0.1 to 3% by weight is usually sufficient. The other components of the toner and the carrier to be blended with the toner may be the same as those of conventionally known electrophotographic developers.

In the present invention, the fluidity of the toner containing the hydrophobic metal oxide powder is evaluated by the sieving and shaking method described below. In this method, a styrene-acrylic copolymer resin in which 18% by weight of carbon is dispersed is pulverized to obtain an average particle size of 7 ± 3 μm.
To 10 g of the resin powder obtained by classification into m, 0.05 g of the surface-treated metal oxide powder is added and mechanically mixed for 30 seconds to prepare a toner. 5 g of the obtained toner was put into a 100-mesh sieve (opening 150 μm), shaken for 1 minute with an electromagnetic sieve shaker, and the percentage (%) of the weight of the toner that passed through this sieve was calculated. Liquidity. The higher the fluidity of the toner, the less likely it is that fog will occur and the image density will not decrease when electrophotographic development is performed using the toner.

The hydrophobic metal oxide powder of the present invention is
In addition to the toner, the fluidity of the resin powder can be improved, and the resin powder can be used as a fluidizing agent for powdered plastics and an additive for powder coatings.

[0045]

Example 20 g of the metal oxide powder described in Table 2 was heated and dried, then charged into a stainless steel container equipped with a stirrer, and floated while stirring at room temperature in a nitrogen atmosphere. The epoxy / amine-modified silicone oil obtained by previously reacting the epoxy-modified silicone oil and the amine compound by mixing at 50 ° C. for one day was diluted with alcohol and sprayed onto the powder.

The amount of epoxy-modified silicone oil used in the reaction is the total number of epoxy groups, and the amount of amine compounds is the total number of amino groups (primary, secondary, tertiary) (= total N number) and primary + secondary. The total number of reactive amino groups (reactive N number) (each unit is mmol) is shown in Table 2. The symbols of the epoxy-modified silicone oil and amine compound shown in Table 2 have the following meanings.

[0047]

[Table 1]

Among the above amine compounds, the polyethyleneimine i is a polymer type compound and is not suitable for use in the present invention. After spraying, the metal oxide powder is further stirred at room temperature for 30 minutes, then externally heated under a nitrogen stream, heated to 150 ° C over 30 minutes, heated to this temperature for 1 hour, and then stirred. It was allowed to cool to room temperature while continuing.

Table 2 shows the results obtained by measuring the hydrophobicity of the obtained hydrophobic metal oxide powder, the triboelectric charge amount with respect to the iron powder, and the fluidity of the toner containing the powder as described above.
In addition, the toner containing the metal oxide used in the fluidity test
Table 2 also shows the results of a life test in which 30 g was mixed with 1000 g of iron oxide powder to prepare an electrophotographic developer, and the developer was put in a commercially available electrophotographic copying machine. In the developer using the metal oxide powder of the example, the high temperature and high humidity (28
A good image was also shown in the environment of ℃ and 85% RT).

[0050]

[Table 2]

[0051]

As can be seen from Table 2, according to the present invention, depending on the kind and amount of the amine compound used in the preparation of the epoxy / amino modified silicone oil, the triboelectric charge amount is about −500 μC / g. From a chargeability to a positive chargeability exceeding 300 μC / g, it can be freely controlled in a wide range, and the present invention can be applied to toners having any chargeability level, positive or negative. The above hydrophobic metal oxide powder can be used. In addition, the accuracy of charging control is high.

Further, the heating temperature for the surface treatment may be low, whereby a hydrophobic metal oxide powder in which the coating of silicone oil is firmly bonded to the metal oxide powder is obtained.
This metal oxide powder has excellent stability with time of hydrophobicity and chargeability, and has little property deterioration during use or storage. Therefore, the electrophotographic developer containing the hydrophobic metal oxide powder has good fluidity even under high temperature and high humidity conditions, and the number of copies for obtaining a good image without fog increases.

On the other hand, in the comparative examples shown in Table 2, the number of reactive N of the amine is larger than the total number of epoxy groups, so that the epoxy groups react almost completely with the amine and the silicone oil used for the surface treatment is Since almost no epoxy group remains, the silicone oil is insufficiently bonded to the metal oxide powder. In addition, a large amount of unreacted reactive amino groups that adversely affect the hydrophobicity remains. As a result, the results of the hydrophobization rate, fluidity, and life test were significantly reduced. On the other hand, in the control test in which the surface was treated with the epoxy-modified silicone oil, the triboelectric charging property could not be made positive,
The result of the life test was also slightly insufficient.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03G 9/08 374

Claims (8)

[Claims] 1. A hydrophobic metal oxide powder having a surface coating formed from a silicone oil having an epoxy group and an amino group. 2. A silicone oil having an epoxy group and an amino group is added to the silicone oil having an epoxy group in an amount smaller than the amount necessary to react with all the epoxy groups. The hydrophobic metal oxide powder according to claim 1, which is prepared by reacting a non-polymeric amine compound having the same. 3. The silicone oil having an epoxy group has an epoxy equivalent of 200 to 3000 g / mol, and the amine compound has a general formula: R ¹ R ² NXNHR ³ (wherein R ¹ , R ² and
R ³ may be the same or different, each is hydrogen or an alkyl group having 1 to 10 carbon atoms, an ether bond may be present in the alkyl group, and X is an alkylene group having 1 to 10 carbon atoms) Is a compound represented by +10 to +25
The hydrophobic metal oxide powder according to claim 2, having a triboelectric charge amount within a range of 0 µC / g. 4. In the general formula of an amine compound, R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms, R ³ is hydrogen or an alkyl group having 1 to 6 carbon atoms, and X is — (CH) n— ( The hydrophobic metal oxide powder according to claim 3, wherein n is an integer of 2 to 4. 5. The silicone oil having an epoxy group is a silicone oil having a glycidyl group at both ends of a molecule, an epoxy equivalent of 300 to 1000 g / mol, and a viscosity at 25 ° C. of 10 to 50 cSt. Any one from 2 to 4
The hydrophobic metal oxide powder according to the item. 6. The hydrophobic metal oxide powder according to claim 1, wherein the metal oxide is silica, alumina or titania. 7. The hydrophobicity measured by the transmittance method is
The hydrophobic metal oxide powder according to any one of claims 1 to 6, which exhibits a value of 60% or more. 8. A hydrophobic metal oxide powder according to any one of claims 1 to 7 is contained.
Developer for electrophotography.