JP4347201B2 - Toner external additive and toner for developing electrostatic image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an external additive for toner which does not react or interact with an organic photoreceptor, causes neither deterioration nor cracking of the photoreceptor, does not aggregate, causes no toner adhesion to the photoreceptor because of good fluidity, and is free of problems due to freeing of silicone oil, and to provide a toner with the external additive added. <P>SOLUTION: The toner external additive for electrostatic image development comprises spherical polydiorganosiloxanated silica fine particles having an average particle diameter of primary particles of 0.01-5 &mu;m obtained by mixing (A) spherical hydrophilic silica fine particles prepared by cohydrolysis and condensation reaction of a tetraalkoxysilane and/or a partial hydrolytic condensation product thereof with (B) a polydiorganosiloxane having a hydrolyzable silyl group but not having a hydrophilic group, reacting the hydrophilic silica fine particles with the polydiorganosiloxane (B), and reacting the silica fine particles after the reaction with (C) a silazane compound and/or a silane compound. The toner with the external additive added is also provided. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a toner external additive for developing an electrostatic charge image used for developing an electrostatic charge image in an electrophotographic method, an electrostatic recording method, and the like, and a toner using the same, for example, for improving image quality The present invention relates to an external additive for small-diameter toner used in the invention and a toner using the same.

  Dry developers used in electrophotography and the like can be broadly classified into a one-component developer using a toner itself in which a colorant is dispersed in a binder resin, and a two-component developer in which the toner is mixed with a carrier, and When performing a copying operation using these developers, in order to have process compatibility, the developer needs to be excellent in fluidity, caking resistance, fixing properties, charging properties, cleaning properties, and the like. . In order to improve fluidity, caking resistance, fixing properties, cleaning properties, etc., inorganic fine particles are often added to the toner. However, the inorganic fine particles have a great influence on the chargeability. For example, generally used silica-based fine powder has a strong negative polarity, and excessively increases the chargeability of the negatively chargeable toner, particularly under low temperature and low humidity, while taking in moisture under high temperature and high humidity. Therefore, there is a problem that a large difference is caused in the chargeability between the two. As a result, density reproduction failure and background fogging may occur. In addition, the dispersibility of the inorganic fine particles has a great influence on the toner characteristics. If the dispersibility is not uniform, desired characteristics cannot be obtained in the fluidity, caking resistance, and fixability, or the cleaning performance becomes insufficient. As a result, toner sticking or the like may occur on the photoreceptor, which may cause black spot image defects. In order to improve these points, various types in which the surface of inorganic fine particles has been subjected to a hydrophobic treatment have been proposed (Patent Documents 1 to 4).

  However, sufficient effects cannot always be obtained by using these inorganic fine powders. In addition, it has been proposed to treat silicone oil with a powder such as silica (Patent Documents 5 to 6). However, in a toner to which such surface-treated silica is added, the offset resistance is lowered and the toner is heated. The problem of adhering to the roll and fouling the next copy occurs. This occurs because when the wax added for imparting releasability to the toner and the silicone oil-treated silica fine powder are mixed, the wax is thickened and the releasing effect is inhibited. The thickening of the wax is due to the fact that the silicone oil is only physically adsorbed on the silica fine powder, and the silicone oil is released when it comes into contact with the wax. In addition, when silicone oil is used as the treatment agent, the viscosity thereof is high, so that silica is agglomerated at the time of treatment, and there is a disadvantage that powder fluidity is deteriorated.

  In addition, when using an organic photoreceptor for higher image quality or using a toner having a smaller particle diameter, sufficient performance cannot be obtained by using the above-mentioned inorganic fine particles. Yes. Organic photoreceptors tend to have a shorter life because their surfaces are softer and more reactive than inorganic photoreceptors. Therefore, when such an organic photoreceptor is used, the photoreceptor is easily altered or scraped by the inorganic fine particles added to the toner. Further, when the toner has a small particle size, the powder fluidity is poor as compared with a toner having a particle size that is usually used, so that a larger amount of inorganic fine particles must be added and used. The fine particles sometimes cause toner adhesion to the photoreceptor.

JP-A-46-5782 JP-A-48-47345 JP-A-48-47346 JP 2000-330328 A JP-A-49-42354 JP 55-26518 A

  Accordingly, the problem of the present invention is that there is no reaction or interaction with the organic photoconductor, it does not cause alteration or cracking of the photoconductor, and since there is no aggregation and fluidity is good, toner adheres to the photoconductor. An object of the present invention is to provide an external additive for toner which does not occur and is free from problems caused by liberation of silicone oil.

As a result of intensive studies in order to solve the above problems, the present inventors have made the present invention.
That is, the present invention firstly
(A) General formula (I):
Si (OR ¹ ) ₄
(Wherein R ¹ is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms)
A spherical hydrophilic silica fine particle obtained by a co-hydrolysis and condensation reaction of a tetraalkoxysilane or a partial hydrolysis-condensation product thereof, or a combination thereof, represented by:
(B) After mixing the polydiorganosiloxane having a hydrolyzable silyl group and not having a hydrophilic group and reacting the spherical hydrophilic silica fine particles with the polydiorganosiloxane of (B), after the reaction Silica fine particles
(C) General formula (II):
R ² ₃ SiNHSiR ² ₃
(Wherein R ² is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms)
Or a general formula (III):
R ² ₃ SiX
(Wherein R ² is as described above, and X is an OH group or a hydrolyzable group)
Or a combination thereof,
A toner external additive for developing an electrostatic image comprising spherical polydiorganosiloxane silica fine particles having an average primary particle diameter of 0.01 to 5 μm, obtained by reacting with
I will provide a.

  Secondly, the present invention provides a toner obtained by externally adding the toner external additive for developing an electrostatic charge image.

  The toner external additive for developing an electrostatic charge image of the present invention not only has excellent fluidity, caking resistance, fixability, and cleaning properties of the toner or developer, but also does not cause deterioration or shaving of the photoreceptor. There are obtained effects such as no adhesion of toner to the body and no problem caused by the release of silicone oil. Further, the external toner additive also provides effects such as imparting toner chargeability independent of environmental conditions and easy control of the toner charge amount.

  The spherical polydiorganosiloxane silica fine particles of the present invention are produced as described above. Details will be described below.

-(A) Spherical hydrophilic silica fine particles-
(A) As described above, the spherical hydrophilic silica fine particles are composed of the tetraalkoxysilane represented by the general formula (I) or a partial hydrolysis condensate thereof, or a combination thereof (hereinafter referred to as “tetraalkoxysilane etc.”). Obtained by cohydrolysis and condensation reactions. Note that hydrolyzable groups such as alkoxy groups involved in the hydrolysis / condensation reaction described below remain in the molecule of the partially hydrolyzed condensate.

In the general formula (I), examples of the monovalent hydrocarbon group represented by R ¹ include alkyl groups such as a methyl group, an ethyl group, an isopropyl group, and a butyl group.

  Examples of the (A) component tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetrabutoxysilane. Examples of the partially hydrolyzed condensate of tetraalkoxysilane include alkyl silicates such as methyl silicate and ethyl silicate. These tetraalkoxysilanes may be used alone or in combination of two or more.

-Co-hydrolysis / condensation reaction-
The above-mentioned co-hydrolysis and condensation reaction of (A) tetraalkoxysilane or the like is usually performed in the presence of water, a hydrophilic organic solvent, a basic compound, or the like. By this reaction, spherical hydrophilic silica fine particles (dispersion) are obtained. In addition, substantially no hydrolyzable groups such as alkoxy groups remain in the molecules of the spherical hydrophilic silica fine particles. Here, “substantially does not remain” means that the abundance is 0 or 1% by mass or less.

  The hydrophilic organic solvent is not particularly limited as long as it has (A) tetraalkoxysilane and the like (B) polydiorganosiloxane having a hydrolyzable silyl group, which does not have a hydrophilic group, and water. Not. Specific examples thereof include alcohols; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and cellosolve acetate; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and tetrahydrofuran; and preferably alcohols .

Examples of alcohols include, for example, general formula (V):
R ⁵ OH
(Wherein R ⁵ is a monovalent hydrocarbon group having 1 to 6 carbon atoms)
The alcohol shown by is mentioned.

In the general formula (V), examples of the monovalent hydrocarbon group represented by R ⁵ include a methyl group, an ethyl group, an isopropyl group, and a butyl group. Examples of the alcohol represented by the general formula (V) include methanol, ethanol, isopropanol, butanol and the like. As the number of carbon atoms of the alcohol increases, the particle size of the silica fine particles to be generated increases. Therefore, it is desirable to select the type of alcohol depending on the particle size of the target silica fine particles.

  Examples of the basic compound include ammonia, dimethylamine, diethylamine and the like, preferably ammonia. The basic compound is usually prepared by dissolving a required amount in water and then mixing the obtained aqueous solution (basic aqueous solution) with the hydrophilic organic solvent.

  The amount of water used at this time is preferably 0.5 to 5 moles per mole of alkoxy group (A) such as tetraalkoxysilane. Moreover, it is preferable that the ratio of water and a hydrophilic organic solvent is 0.5-10 by mass ratio. Furthermore, it is preferable that the quantity of a basic compound is 0.01-1 mol with respect to 1 mol of alkoxy groups, such as (A) tetraalkoxysilane.

  The cohydrolysis / condensation reaction of (A) tetraalkoxysilane or the like may be performed, for example, by a method of dropping (A) tetraalkoxysilane or the like into a mixture of a basic compound, a hydrophilic organic solvent and water.

  The spherical hydrophilic silica fine particles are usually obtained in the form of a dispersion using the hydrophilic organic solvent and water as a dispersion medium. The spherical hydrophilic silica fine particles may be reacted with a polydiorganosiloxane having a hydrolyzable silyl group (described later) and having no hydrophilic group, and (C) a silazane compound / silane compound. However, the reaction may be carried out after converting the dispersion medium to an organic solvent having no active hydrogen.

  Examples of the organic solvent having no active hydrogen include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, and the like. When converting the dispersion medium into an organic solvent having no active hydrogen, an operation of adding an organic solvent having no active hydrogen to the dispersion and distilling off the hydrophilic solvent and water is performed (if necessary). Repeat this operation). The amount of the organic solvent having no active hydrogen added is usually 0.5 to 5 times, preferably 1 to 2 times the mass ratio of the spherical hydrophilic silica fine particle dispersion. is there.

-(B) Polydiorganosiloxane having a hydrolyzable silyl group and no hydrophilic group-
By adding polydiorganosiloxane having a hydrolyzable silyl group (B) component and not having a hydrophilic group to the spherical hydrophilic silica fine particles (for example, in a dispersion state), the surface of the silica fine particles is added. Is polydiorganosiloxaned.

  The polydiorganosiloxane having a hydrolyzable silyl group (B) and not having a hydrophilic group is not particularly limited. The polydiorganosiloxane having a hydrolyzable silyl group (B) and not having a hydrophilic group may be used alone or in combination of two or more.

The hydrolyzable silyl group is a silyl group to which a hydrolyzable group is bonded. For example, the formula: (R ^a ) _x (R ^b ) _3−x Si— (wherein R ^a is a hydrolyzable group. ^Rb is a monovalent hydrocarbon group having 1 to 10 carbon atoms, for example, an alkyl group and a phenyl group, and x is an integer of 1 to 3. Examples of the hydrolyzable group include an alkoxy group, an amino group, an acyloxy group, an alkenooxy group, a ketoximo group, and an N-methylbenzamide group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a hexyloxy group.

  A hydrophilic group is a polar group that can interact strongly with water. Examples of the hydrophilic group include a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, and a group having a polyoxyalkylene chain (for example, a polyoxyalkylene chain such as a polyoxyethylene group or a polyoxypropylene group). It is done.

The polydiorganosiloxane having a hydrolyzable silyl group (B) and not having a hydrophilic group is preferably substantially linear and has a hydrolyzable group at one end of the molecule. General formula (IV):
Q _a R ³ _(3-a) Si [R ⁴ (R ³ ₂ Si)] _b O (R ³ ₂ SiO) _x SiR ³ ₃
(In the formula, Q is a hydrolyzable group, R ³ is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R ⁴ is independently a divalent hydrocarbon group having 1 to 6 carbon atoms. A is 1, 2 or 3, b is 0 or 1, and x is an integer of 0-100.
The compound shown by these is preferable.

  In the general formula (IV), examples of the hydrolyzable group represented by Q include those exemplified above.

Examples of the monovalent hydrocarbon group represented by R ³ include alkyl groups such as a methyl group, an ethyl group, an isopropyl group, an n-propyl group, a butyl group, a pentyl group, and a hexyl group.

Examples of the divalent hydrocarbon group represented by R ⁴ include alkylene groups such as ethylene group, trimethylene group, and propylene group.

Specific examples of the compound represented by the general formula (IV) include
(MeO) ₃ SiO (Me ₂ SiO) ₉ SiMe ₃ ,
(MeO) ₃ SiCH ₂ CH ₂ (Me ₂ Si) O (Me ₂ SiO) ₈ SiMe ₃
Etc. “Me” means a methyl group (hereinafter the same).

(B) The blending amount of the polydiorganosiloxane having a hydrolyzable silyl group and not having a hydrophilic group is not particularly limited, but is usually (A) based on the mass of the SiO ₂ unit in tetraalkoxysilane and the like. 0.1 to 20% by mass, preferably 1 to 10% by mass. When this blending amount satisfies such a range, the obtained toner or developer is excellent in various properties such as fluidity, caking resistance, fixing property, cleaning property, and charging property independent of environmental conditions.

-(C) Silazane compound / Silane compound-
By adding (C) silazane compound / silane compound to the silica fine particles whose surface is polydiorganosiloxane, the silanol groups remaining on the surface of the silica fine particles are trialkylsilylated to prevent aggregation. .

  (C) The silazane compound and the silane compound are represented by the general formula (II) and the general formula (III), respectively.

In the general formula (II) and general formula (III), examples of the monovalent hydrocarbon group represented by R ² include alkyl such as methyl, ethyl, isopropyl, butyl, pentyl, and hexyl groups. Groups and the like.

  In the general formula (III), examples of the hydrolyzable group represented by X include those exemplified above and halogen atoms such as chlorine atom.

  Examples of the silazane compound represented by the general formula (II) include hexamethyldisilazane. Examples of the silane compound represented by the general formula (III) include monosilanol compounds such as trimethylsilanol and triethylsilanol; monochlorosilanes such as trimethylchlorosilane and triethylchlorosilane; monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane; Examples thereof include monoaminosilanes such as trimethylsilyldimethylamine and trimethylsilyldiethylamine; monoacyloxysilanes such as trimethylacetoxysilane. These silazane compounds and silane compounds may be used alone or in combination of two or more.

The amount of the silazane compound and / or silane compound used is usually 0.05 to 0.5 mol, preferably 0.1 to 1 mol of SiO ₂ units in (A) tetraalkoxysilane and the like. ~ 0.3 mol.

-Spherical polydiorganosiloxane silica particles-
The reaction yields spherical polydiorganosiloxane silica particles (usually as a dispersion). Furthermore, the spherical polydiorganosiloxane-modified silica fine particles can be obtained as a dry powder from the above dispersion by a conventional method.

  Further, the spherical polydiorganosiloxane-modified silica fine particles may be subjected to further surface hydrophobization treatment with various silane coupling agents and silanes such as dimethyldimethoxysilane as necessary.

  Since the spherical polydiorganosiloxane-modified silica fine particles exhibit a function as an external additive in the form of primary particles, it is preferable that secondary particles are not formed by coalescence or aggregation.

  The average particle size of the primary particles of the spherical polydiorganosiloxane-modified silica fine particles is 0.01 to 5 μm from the viewpoint of improving the flowability, caking resistance and fixability of the developer, and reducing adverse effects on the photoreceptor. And preferably 0.05 to 0.5 μm. When the primary particle size is smaller than 0.01 μm, the developer fluidity, caking resistance, and fixing property may not be obtained due to aggregation. When the primary particle size exceeds 5 μm, the photoreceptor may be modified or scraped. In some cases, adhesion to the toner may be reduced.

In the present specification, the “average particle diameter” means the volume average particle diameter of primary particles of spherical polydiorganosiloxane silica fine particles. In addition, “spherical” means the following formula:
(Spherical coefficient) = (Surface area of sphere having the same volume as actual particle) / (Surface area of actual particle)
It means that the spherical coefficient of the particle defined by is usually 0.6 to 1, preferably 0.8 to 1.

  The spherical polydiorganosiloxane-modified silica fine particles used in the present invention are (i) the polydiorganosiloxane is chemically bonded to the surface and the polydiorganosiloxane is not liberated, (ii) the surface is hydrophobized, and reaction such as silanol groups (Iii) High dispersibility, low cohesiveness, good fluidity, etc., for example, when used as a toner external additive as described later. The toner or developer has various properties such as excellent fluidity, caking resistance, fixing property, cleaning property, and charging property independent of environmental conditions.

  The spherical polydiorganosiloxaneized silica fine particles used in the present invention can be used as an external toner additive. The amount of the toner external additive composed of the fine particles (hereinafter, also simply referred to as “spherical polydiorganosiloxane silica fine particles”) to the toner is usually 0.01 to 20 parts by mass with respect to 100 parts by mass of the toner. The amount is preferably 0.1 to 5 parts by mass. When the blending amount satisfies such a range, the amount of adhesion to the toner becomes appropriate, and more excellent fluidity can be obtained, and further, the toner charging property and economical efficiency are also excellent.

  As the toner particles to which the toner external additive is added, known particles produced by a pulverization method or a polymerization method, which contain a binder resin and a colorant, can be used. Moreover, the charge control agent may be added as needed.

  The positive charge image developing toner to which the toner external additive of the present invention is added can be used as a one-component developer, but it can also be used as a two-component developer by mixing it with a carrier. When used as a two-component developer, the toner external additive may not be added to the toner particles in advance, but may be added when the toner and the carrier are mixed to coat the surface of the toner. As the carrier, iron powder or the like, or a known one whose surface is resin-coated is used.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to these Examples.

Example 1
[Synthesis of spherical polydiorganosiloxane silica particles 1]
To a 3 liter glass reactor equipped with a stirrer, a dropping funnel and a thermometer, 623.7 g of methanol, 41.4 g of water, and 49.8 g of 28% by mass ammonia water were added and mixed. This mixed solution was adjusted to 35 ° C., and 1163.7 g (7.65 mol) of tetramethoxysilane and 418.1 g of 5.2% by mass ammonia water were simultaneously added while stirring. The former was added dropwise over 5 hours and the latter over 4 hours. did. Stirring was continued for 0.5 hour after completion of the dropping, and hydrolysis and condensation reaction were performed to obtain a dispersion of spherical hydrophilic silica fine particles. In the obtained dispersion, the following general formula (VI):
(MeO) ₃ SiO (Me ₂ SiO) ₉ SiMe ₃
After adding 33.6 g (0.0384 mol) of a polydiorganosiloxane having a hydrolyzable silyl group and having no hydrophilic group, the mixture was reacted at 65 ° C. for 4 hours. To the obtained dispersion, 123.3 g (0.766 mol) of hexamethyldisilazane was added at room temperature, heated to 60 ° C. and reacted for 3 hours to trimethylsilylate the silica fine particles. Thereafter, the solvent was distilled off from the dispersion under reduced pressure to obtain 537 g of spherical polydiorganosiloxane silica particles. The obtained spherical polydiorganosiloxane silica particles were tested according to the following criteria. The results obtained are shown in Table 1.

[Measurement of average particle size]
After adding spherical polydiorganosiloxaneized silica fine particles to methanol so as to have a mass ratio of 1: 0.005, the spherical polydiorganosiloxaneized silica fine particles were dispersed in methanol using an ultrasonic irradiator. The particle size distribution of the spherical polydiorganosiloxane silica particles treated in this way was measured with a laser diffraction / scattering particle size distribution measuring device (trade name: LA910, manufactured by HORIBA, Ltd.), and the average particle size was determined (thus determined) The average particle diameter is a so-called volume average particle diameter). In addition, the average particle diameter of the spherical polydiorganosiloxaneized silica fine particles was measured using an electron microscope, and compared with the average particle diameter obtained from the measurement result by the apparatus, it was confirmed that those values were consistent. Further, by confirming that the spherical polydiorganosiloxane silica fine particles were not aggregated, it was determined that the average particle size was that of primary particles.

[Hydrophobicity]
The degree of hydrophobicity was measured by a methanol titration test. Specifically, methanol was added dropwise from the burette while stirring the spherical polydiorganosiloxane silica fine particle mixture solution until 0.2 g of the spherical polydiorganosiloxane silica fine particle added in 50 ml of water was wet. Titration was carried out, and the value represented by the percentage of methanol in the mixture of methanol and water at the end point was taken as the degree of hydrophobicity. The larger the value of the degree of hydrophobicity, the higher the hydrophobicity, and the smaller the value, the higher the hydrophilicity.

[Production of external additive mixed toner]
96 parts by mass of a polyester resin having a glass transition point (Tg) of 60 ° C. and a softening point of 110 ° C. and 4 parts by mass of a colorant (trade name: Carmine 6BC, manufactured by Sumika Color Co., Ltd.) are melted and kneaded and pulverized. After classification, a toner having an average particle diameter of 7 μm was obtained. 10 g of this toner was mixed with 0.3 g of spherical polydiorganosiloxane silica fine particles by a sample mill to obtain an external additive mixed toner. Using this, the degree of aggregation was evaluated by the following method.

[Cohesion]
The degree of aggregation is a value representing the fluidity of the powder. This degree of aggregation was measured using a powder tester (manufactured by Hosokawa Micron Corporation) and a three-stage sieve in which 200, 100 and 60 mesh sieves were stacked in this order from the bottom. As a measuring means, a powder consisting of 5 g of toner is placed on the upper 60 mesh screen of the three-stage sieve, a voltage of 2.5 V is applied to the powder tester, and the three-stage sieve is vibrated for 15 seconds. From the powder mass a (g) remaining on the mesh screen, the powder mass b (g) remaining on the 100 mesh screen, and the powder mass c (g) remaining on the 200 mesh screen, Calculate the degree of aggregation (%).
Aggregation degree (%) = (a + b × 0.6 + c × 0.2) × 100/5
It can be evaluated that the smaller the degree of aggregation, the better the fluidity, and the higher the degree of aggregation, the poorer the fluidity.

[Preparation of developer]
A developer was prepared by mixing 3 parts of the external additive mixed toner and 97 parts of ferrite (trade name: FL100, manufactured by Powdertech) as a carrier. Using this, the toner charge amount and toner adhesion to the photoreceptor were evaluated by the following methods.

[Toner charge amount]
The developer was allowed to stand for 1 day under conditions of high temperature and high humidity (30 ° C., 90% RH) and low temperature and low humidity (10 ° C., 15% RH), and then sufficiently mixed under the same conditions for triboelectric charging. The charge amount of each sample was measured using a blow-off powder charge amount measuring device (Toshiba Chemical Co., Ltd., TB-200 type) under the same conditions.

[Toner adherence to photoconductor and photoconductor wear]
The developer was put into a two-component modified developing machine equipped with an organic photoreceptor, and a print test of 30000 sheets was performed. At this time, the adhesion of the toner to the photoconductor can be detected as white spots in all solid images. In this case, the extent of white spots, the white number in the missing point is "often" a more than 10 / cm ^2, 1-9 / cm ² or "small", and the 0 / cm ² was evaluated as "none" .

  Further, the photoconductor wear is detected as image disturbance in the print test. Here, an image having no image disturbance is evaluated as good and indicated as A, and an image having no large image disturbance (no problem in practical use) is evaluated as slightly good and indicated as B. If there is any, it is evaluated as defective and indicated as C.

-Example 2-
[Synthesis of spherical polydiorganosiloxane silica particles 2]
In Example 1, instead of the polydiorganosiloxane having a hydrolyzable silyl group represented by the general formula (VI) and having no hydrophilic group, the following general formula (VII):
(MeO) ₃ SiCH ₂ CH ₂ (Me ₂ Si) O (Me ₂ SiO) ₈ SiMe ₃
In the same manner as in Example 1 except that 34.1 g (0.0384 mol) of a polydiorganosiloxane having a hydrolyzable silyl group and having no hydrophilic group is used, 529 g of spherical polydiorganosiloxane silica particles Got. The obtained spherical polydiorganosiloxaneized silica fine particles were tested according to the above-mentioned criteria. The external additive mixed toner was prepared in the same manner as in Example 1. The results obtained are shown in Table 1.

-Comparative Example 1-
[Synthesis of spherical hydrophobic silica fine particles 1]
623.7 g of methanol, 41.4 g of water, and 49.8 g of 28% by mass ammonia water were added and mixed in a 3 liter glass reactor equipped with a stirrer, a dropping funnel and a thermometer. The mixed solution was adjusted to 35 ° C., and 1163.7 g of tetramethoxysilane and 418.1 g of 5.4 mass% aqueous ammonia were simultaneously added while stirring. The former was added dropwise over 6 hours and the latter over 4 hours. Stirring was continued for 0.5 hour after the dropwise addition of tetramethoxysilane to carry out hydrolysis to obtain a dispersion of silica fine particles. Attach an ester adapter and a condenser to a glass reactor, heat to 60 to 70 ° C., distill away 1132 g of methanol, add 1200 g of water, then heat to 70 to 90 ° C., distill off 273 g of methanol, An aqueous dispersion of silica fine particles was obtained. To this aqueous dispersion, 11.6 g of methyltrimethoxysilane (a molar ratio of 0.1 with respect to tetramethoxysilane) was added dropwise at room temperature over 0.5 hours and stirred for 12 hours after the addition. The surface was hydrophobized.

  After 1440 g of methyl isobutyl ketone was added to the dispersion thus obtained, the mixture was heated to 80 to 110 ° C., and methanol water was distilled off from the dispersion over 7 hours. To the obtained dispersion, 357.6 g of hexamethyldisilazane was added at room temperature, heated to 120 ° C., and reacted for 3 hours to trimethylsilylate the silica fine particles. Thereafter, the solvent was distilled off from the dispersion under reduced pressure to obtain 477 g of spherical hydrophobic silica fine particles.

  The obtained spherical hydrophobic silica fine particles were tested according to the above-mentioned criteria. The external additive mixed toner was prepared in the same manner as in Example 1. The results obtained are shown in Table 2.

-Comparative Example 2-
[Synthesis of spherical hydrophobic silica fine particles 2]
To a 3 liter glass reactor equipped with a stirrer, a dropping funnel and a thermometer, 623.7 g of methanol, 38.9 g of water, and 52.3 g of 28% by mass ammonia water were added and mixed. The mixed solution was adjusted to 35 ° C., and 1163.7 g (7.65 mol) of tetramethoxysilane and 418.1 g of 5.48% by mass ammonia water were simultaneously added while stirring. The former was added dropwise over 6 hours and the latter over 5 hours. Stirring was continued for 0.5 hours after the addition of tetramethoxysilane, followed by hydrolysis to obtain a dispersion of silica fine particles. To the obtained dispersion, 184.7 g (1.14 mol) of hexamethyldisilazane was added at room temperature, heated to 120 ° C. and reacted for 3 hours to trimethylsilylate the silica fine particles. Thereafter, the solvent was distilled off from the dispersion under reduced pressure to obtain 540 g of spherical hydrophobic silica fine particles.
The obtained spherical hydrophobic silica fine particles were tested according to the above-mentioned criteria. The external additive mixed toner was prepared in the same manner as in Example 1. The results obtained are shown in Table 2.

-Comparative Example 3-
[Synthesis of spherical polydiorganosiloxane silica particles]
In a 3 liter glass reactor equipped with a stirrer, a dropping funnel and a thermometer, 623.7 g of methanol, 41.4 g of water, and 49.8 g of 28% by mass ammonia water were added and mixed. This mixed solution was adjusted to 35 ° C., and 1163.7 g (7.65 mol) of tetramethoxysilane and 418.1 g of 5.2% by mass ammonia water were simultaneously added while stirring. The former was added dropwise over 5 hours and the latter over 4 hours. did. Stirring was continued for 0.5 hour after completion of the dropping, and hydrolysis and condensation reaction were performed to obtain a dispersion of spherical hydrophilic silica fine particles. In the obtained dispersion, the following general formula (VI):
(MeO) ₃ SiO (Me ₂ SiO) ₉ SiMe ₃
After adding 33.6 g (0.0384 mol) of a polydiorganosiloxane having a hydrolyzable silyl group represented by the following formula and having no hydrophilic group, the mixture was reacted at 65 ° C. for 4 hours. Thereafter, the solvent was distilled off from the dispersion under reduced pressure to obtain 531 g of spherical polydiorganosiloxane silica particles.
The obtained spherical polydiorganosiloxaneized silica fine particles were tested according to the above-mentioned criteria. The external additive mixed toner was prepared in the same manner as in Example 1. The results obtained are shown in Table 2.

-Comparative Example 4-
Example 1 except that hydrophobic silica (trade name: Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.) obtained by hydrophobizing fumed silica was used instead of the spherical polydiorganosiloxane silica fine particles obtained in Example 1. In the same manner, an external additive mixed toner was obtained. The obtained external additive mixed toner was tested in the same manner as in Example 1. The results obtained are shown in Table 2.

-Comparative Example 5-
Example except that high-purity spherical amorphous silica (trade name: Admafine SO-22R, manufactured by Admatech Co., Ltd.) having an average particle size of 0.3 μm was used in place of the spherical polydiorganosiloxane silica fine particles obtained in Example 1. In the same manner as in Example 1, an external additive mixed toner was obtained. The obtained external additive mixed toner was tested in the same manner as in Example 1. The results obtained are shown in Table 2.

-Comparative Example 6
After dispersing 100 g of the spherical polydiorganosiloxane silica fine particles obtained in Example 1 in 400 g of toluene, the following formula (VIII):
R (R ₂ SiO) _m SiR ₃
(In the formula, R is a methyl group, and m is an integer of 80 to 100)
5 g of dimethyl silicone oil represented by the formula was added and mixed. Toluene was distilled off from the dispersion by heating to obtain 105 g of surface-treated silica fine particles.
The obtained surface-treated silica fine particles were tested according to the above-mentioned criteria. The external additive mixed toner was prepared in the same manner as in Example 1. The results obtained are shown in Table 2.

Claims (2)

(A) General formula (I):
Si (OR ¹ ) ₄
(Wherein R ¹ is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms)
A spherical hydrophilic silica fine particle obtained by a co-hydrolysis and condensation reaction of a tetraalkoxysilane or a partial hydrolysis-condensation product thereof, or a combination thereof, represented by:
(B) General formula (IV):
Q _a R ³ _(3-a) Si [R ⁴ (R ³ ₂ Si)] _b O (R ³ ₂ SiO) _x SiR ³ ₃
(In the formula, Q is a hydrolyzable group, R ³ is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R ⁴ is independently a divalent hydrocarbon group having 1 to 6 carbon atoms. A is 2 or 3, b is 0 or 1, and x is an integer of 0 to 100)
A compound having a hydrolyzable silyl group and a polydiorganosiloxane having no hydrophilic group, and reacting the spherical hydrophilic silica fine particles with the polydiorganosiloxane of (B). , The silica fine particles after the reaction,
(C) General formula (II):
R ² ₃ SiNHSiR ² ₃
(Wherein R ² is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms)
Or a general formula (III):
R ² ₃ SiX
(Wherein R ² is as described above, and X is an OH group or a hydrolyzable group)
Or a combination thereof,
Toner additive for developing electrostatic images, comprising spherical polydiorganosiloxane silica fine particles having an average primary particle diameter of 0.01 to 5 [mu] m, obtained by reacting with. A toner obtained by externally adding the toner external additive for developing an electrostatic charge image according to claim 1 .