WO2016013673A1 - シリカ微粉末及びその用途 - Google Patents
シリカ微粉末及びその用途 Download PDFInfo
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- WO2016013673A1 WO2016013673A1 PCT/JP2015/071159 JP2015071159W WO2016013673A1 WO 2016013673 A1 WO2016013673 A1 WO 2016013673A1 JP 2015071159 W JP2015071159 W JP 2015071159W WO 2016013673 A1 WO2016013673 A1 WO 2016013673A1
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- fine powder
- silica fine
- toner
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- spherical silica
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3081—Treatment with organo-silicon compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
- B01J2/04—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a gaseous medium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0819—Developers with toner particles characterised by the dimensions of the particles
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0827—Developers with toner particles characterised by their shape, e.g. degree of sphericity
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09708—Inorganic compounds
- G03G9/09716—Inorganic compounds treated with organic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09708—Inorganic compounds
- G03G9/09725—Silicon-oxides; Silicates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
Definitions
- the present invention relates to fine silica powder and its use.
- the present invention particularly relates to a hydrophobized spherical silica fine powder and its use.
- silica fine powder has been used as an external additive to improve fluidity and stabilize charging characteristics. ing.
- This silica fine powder is required to have high hydrophobicity in order to reduce the change in charge amount due to humidity, and to be highly dispersed with little aggregation so that the toner surface can be uniformly coated.
- an ultrafine powder of about 200 to 500 m 2 / g is used. As the image formation is repeated, the ultrafine powder of silica is buried in the surface of the toner particles. It has been confirmed that fluidity, triboelectric charge, transferability, and the like are deteriorated to cause image defects.
- Patent Document 1 Patent Document 2, and Patent Document 3
- inorganic fine powder having a specific surface area of less than 80 m 2 / g and a relatively large particle diameter is used in combination.
- An inorganic fine powder having a relatively large particle size exhibits a spacer effect that reduces stress caused by direct contact between toners. In this way, a method of suppressing the burying of the ultrafine silica powder and extending the life of the toner is taken.
- the inorganic fine powder having a relatively large particle size tends to have a smaller charge amount than the ultrafine powder, and if the external addition amount is increased in order to improve the spacer effect, the charge amount is lowered. Further, in recent years, due to the acceleration of the low-temperature fixing of the toner, when the toner is stored for a long period of time, the problem that the storage stability of the toner is deteriorated due to the blocking of the toners is increasing. Therefore, further improvement is required for the storage stability and chargeability of fine powder having a relatively large particle size.
- An object of the present invention is to provide a toner external additive suitable for preparing a toner having excellent storage stability and chargeability, and to provide a fine silica powder suitable for addition to the toner external additive. That is.
- the present inventor conducted intensive studies to achieve the above object, and found a fine silica powder that achieves this.
- the present invention is based on such knowledge and has the following gist.
- Hydrophobized spherical silica fine powder obtained by surface treatment of spherical silica fine powder with hexamethyldisilazane, specific surface area of 15 m 2 / g or more and 90 m 2 / g or less, loose bulk density of 0.09 g / cm 3 or more
- a hydrophobized spherical silica fine powder characterized by 0.18 g / cm 3 or less, a carbon content of 0.25 wt% or more and 0.90 wt% or less, and a degree of hydrophobicity of 60% or more and 75% or less.
- the ratio (A) / (B) of the loose bulk density (A) of the hydrophobized spherical silica fine powder after the surface treatment to the loose bulk density (B) of the spherical silica fine powder before the surface treatment is 1.05 or more.
- a toner external additive for developing an electrostatic charge image comprising the hydrophobized spherical silica fine powder described in any one of (1) to (3).
- the specific surface area is 15 m 2 / g or more and 90 m 2 / g or less, the loose bulk density is 0.09 g / cm 3 or more and 0.18 g / cm 3 or less, the carbon amount is 0.25 wt% or more and 0.90 wt% or less, Silica fine powder having a degree of hydrophobicity of 60% to 75%.
- a toner external additive for developing an electrostatic charge image comprising the silica fine powder according to any one of (5) to (9).
- a toner for developing an electrostatic image comprising the toner additive for developing an electrostatic image according to (4) or (10).
- a toner external additive suitable for preparing a toner excellent in storage stability and chargeability is provided. Further, a fine silica powder suitable for the toner external additive is provided.
- the silica fine powder of the present invention needs to have a specific surface area of 15 m 2 / g or more and 90 m 2 / g or less.
- the specific surface area is preferably 20 m 2 / g or more and 75 m 2 / g or less, more preferably 25 m 2 / g or more and 60 m 2 / g or less.
- the specific surface area of the silica fine powder of the present invention is a value based on the BET method, and is measured by a BET one-point method using a specific surface area measuring machine “Macsorb HM model-1208” manufactured by Mountec. Prior to the measurement, pretreatment was performed by heating at 300 ° C. for 18 minutes in a nitrogen gas atmosphere. The adsorbed gas was a mixed gas of 30% nitrogen and 70% helium, and the flow rate was adjusted so that the indicated value of the main body flow meter was 25 ml / min.
- Fine silica powder of the present invention it is necessary to loosen the bulk density is less than 0.09 g / cm 3 or more 0.18 g / cm 3. If the loose bulk density is less than 0.09 g / cm 3 , there may be insufficient surface treatment, and the effect of improving the chargeability may be insufficient. On the other hand, when the loose bulk density exceeds 0.18 g / cm 3 , it becomes difficult to uniformly adhere to the toner surface when used as an external toner additive, and the effect of improving the storage stability becomes insufficient.
- the preferred loose bulk density is 0.10 g / cm 3 or more and 0.17 g / cm 3 or less, more preferably 0.11 g / cm 3 or more and 0.16 g / cm 3 or less.
- the loose bulk density of the fine silica powder of the present invention is measured using a powder tester “PT-E type” manufactured by Hosokawa Micron Corporation. Silica fine powder in a 100 cm 3 bulk density measuring cup is dropped from a height of 25 cm at a rate of 5 to 10 g per minute until it overflows from the cup, and the silica is spilled over the overflowed surface. The loose bulk density was calculated by measuring the weight of the fine powder.
- the silica fine powder of the present invention is required to have a carbon content of 0.25 wt% or more and 0.90 wt% or less.
- the amount of carbon represents the amount of deposited hexamethyldisilazane on the surface of silica fine powder in terms of carbon. If the amount of carbon is less than 0.25 wt%, the amount of hexamethyldisilazane attached to the surface of the silica fine powder is small, so when used as a toner external additive, the effect of suppressing the cohesive force between the toners becomes insufficient, The effect of improving the storage stability is reduced.
- a preferable carbon amount is 0.30 wt% or more and 0.70 wt% or less, and more preferably 0.35 wt% or more and 0.50 wt% or less.
- the amount of carbon in the silica fine powder of the present invention is measured by a calibration curve method using a standard sample of 63 carbon steel, a Japanese steel standard sample, using a carbon-sulfur simultaneous analyzer “CS-444LS” manufactured by LECO.
- the amount of silica fine powder charged was 0.05 g, metallic iron (IRON CHIP made by LECO) and metallic tungsten (CECOCEL II made by LECO) were used as auxiliary combustors, and oxygen having a purity of 99.5% by volume or more.
- the amount of carbon was measured by burning in.
- the silica fine powder of the present invention preferably has a degree of hydrophobicity of 60% to 75%. If the degree of hydrophobicity is less than 60%, the effect of improving the chargeability becomes insufficient due to the influence of humidity when used as a toner external additive. On the other hand, when the degree of hydrophobicity exceeds 75%, there may be a portion where hexamethyldisilazane is unevenly distributed in the fine silica powder. Such a portion tends to be an aggregate, and when used as an external toner additive, it is difficult to adhere to the toner surface, and the storage stability cannot be sufficiently improved. A more preferable degree of hydrophobicity is 65% or more and 73% or less.
- the hydrophobicity of the silica fine powder of the present invention is measured by the following method. That is, 50 ml of ion-exchanged water and 0.2 g of a sample are put in a beaker, and methanol is dropped from a burette while stirring with a magnetic stirrer. As the methanol concentration in the beaker increases, the powder gradually settles, and the volume% of methanol in the mixed solution of methanol and ion-exchanged water at the end point when the total amount of the powder is settled is defined as the degree of hydrophobicity (%).
- the silica fine powder of the present invention is preferably “spherical”.
- Spherical means that the average sphericity of particles having a projected area equivalent circle diameter of 0.050 ⁇ m or more is 0.75 or more, and the degree of “spherical” is a particle having a projected area equivalent circle diameter of 0.050 ⁇ m or more.
- the average sphericity is preferably 0.80 or more. When the average sphericity is 0.80 or more, dispersibility is improved, and a toner having good storage stability can be obtained when used as an external toner additive.
- the average sphericity of the silica fine powder of the present invention is measured by the following method. After fixing silica fine powder on the sample stand with carbon paste, osmium coating was performed, and an image taken with a scanning electron microscope “JSM-6301F type” manufactured by JEOL Ltd. with a magnification of 100,000 times and a resolution of 2048 ⁇ 1356 pixels was put on a personal computer. I took it in. Using this image analysis apparatus “MacView Ver. 4” manufactured by Mountec Co., Ltd., particles were recognized using a simple capture tool, and the sphericity was measured from the projected area (A) and the perimeter (PM) of the particles. .
- the ratio (A) / (B) of the loose bulk density (A) of the silica fine powder after the surface treatment to the loose bulk density (B) of the silica fine powder before the surface treatment is 1.05. It is preferable that it is 1.60 or more.
- (A) / (B) shows the degree of formation of aggregated particles by the surface treatment of the silica fine powder. When this is 1.05 or more and 1.60 or less, the storage stability and charging effect of the present invention are further enhanced. It becomes possible. When (A) / (B) exceeds 1.60, it indicates that the formation of aggregated particles by the surface treatment is remarkable, and when used as an external toner additive, the number of adhesion to the toner surface decreases.
- the silica fine powder of the present invention is preferably a silica fine powder obtained by surface-treating a silica fine powder obtained by reacting metal silicon with oxygen with a hydrophobizing agent such as hexamethyldisilazane.
- Silica fine powder treated with a hydrophobizing agent such as hexamethyldisilazane can have an alkyl group on its surface, and preferably has a trimethylsilyl group.
- Hydrophobizing agents include, but are not limited to, hexamethyldisilazane, N-methyl-hexamethyldisilazane, N-ethyl-hexamethyldisilazane, hexamethyl-N-propyldisilazane, hexaethyldisilazane, hexapropyl
- Examples include silazane compounds such as disilazane, 1,3-diethyl-1,1,3,3 tetramethyldisilazane, 1,3-dimethyl-1,1,3,3 tetraethyldisilazane, and the like.
- trimethylsilylating agents such as hexamethyldisilazane, N-methyl-hexamethyldisilazane, N-ethyl-hexamethyldisilazane, and hexamethyl-N-propyldisilazane are preferred, and hexamethyldisilazane is more preferred.
- the silica fine powder obtained by the oxidation reaction of metal silicon is easy to obtain particles with high sphericity, has low dispersibility and has a low water content because it contains less structure structure particles and coalesced particles.
- a toner having excellent storage stability and chargeability can be obtained.
- a method for producing spherical silica fine powder a method in which metal silicon is spheroidized while being subjected to an oxidation reaction by being applied to a high temperature field formed by a chemical flame or an electric furnace (for example, Japanese Patent No. 1568168), metal silicon Examples thereof include a method in which a particle slurry is sprayed into a flame and spheroidized while undergoing an oxidation reaction (for example, JP-A-2000-247626).
- the fine silica powder according to the present invention may have a water content of 0.03 wt% or more and 0.50 wt% or less.
- a preferable moisture content is 0.05 wt% or more and 0.40 wt% or less.
- the moisture content is measured by the Karl Fischer method.
- Karl Fischer measurement a moisture vaporizer VA-122 manufactured by Mitsubishi Chemical Corporation and a moisture analyzer CA-100 manufactured by Mitsubishi Chemical Corporation are used.
- Aquamicron AX manufactured by Mitsubishi Chemical Corporation
- catholyte is used as the anolyte of the moisture analyzer.
- Aquamicron CXU (Mitsubishi Chemical Corporation) was used.
- the background value was fixed at 0.20 ( ⁇ g / sec), and the measurement was continued until the detected water content fell below the background value.
- the silica fine powder is not exposed to the outside air, the moisture generated from the moisture vaporizer is introduced into the Karl Fischer device along with 300 ml / min of high purity argon, and the moisture content is measured. did.
- the silica fine powder was allowed to stand for 24 hours under conditions of a temperature of 25 ° C. and a relative humidity of 55%, and then charged into the apparatus, which occurred until the heating temperature of the electric heater of the moisture vaporizer reached 200 ° C. The water content was determined from the water content.
- a surface treatment method using a hydrophobizing agent such as hexamethyldisilazane of silica fine powder will be described.
- the silica fine powder of the present invention is coated with a hydrophobizing agent such as hexamethyldisilazane so that the surface is uniformly coated. Since the adhesion amount of the agent is small, the increase in the loose bulk density due to the surface treatment is remarkably suppressed, and in order to obtain the silica fine powder of the present invention, hydrophobization such as hexamethyldisilazane is performed. Rather than spraying the agent in liquid form, it is preferable to contact the silica fine powder in a gasified state.
- the surface of the silica fine powder By reacting with the silica fine powder in a gasified state, the surface of the silica fine powder can be uniformly coated, and the storage stability can be improved when used as an external toner additive.
- a hydrophobizing agent such as hexamethyldisilazane into contact
- silanol groups are activated by pre-existing moisture on the surface of the silica fine powder, and a hydrophobizing agent such as hexamethyldisilazane is applied to the surface of the silica fine powder. Bonding can be performed at a high reaction rate, and charging properties can be improved when used as an external toner additive.
- silica fine powder when water is present on the surface of the silica fine powder, it is preferable to contact the silica fine powder in a gasified state. If the silica fine powder surface-treated with a hydrophobizing agent such as hexamethyldisilazane after contact with moisture is lower than the desired degree of hydrophobization, it is again hydrophobized such as hexamethyldisilazane after contact with moisture. The operation of performing the surface treatment with the agent may be repeated until the desired degree of hydrophobicity is achieved.
- a hydrophobizing agent such as hexamethyldisilazane after contact with moisture
- the amount of water added in one surface treatment is 0.5 mg to 1.5 mg per 1 m 2 of silica fine powder, and the addition of a hydrophobizing agent such as hexamethyldisilazane.
- the amount is preferably 0.8 mg to 2.5 mg per m 2 of silica fine powder.
- the silica fine powder of the present invention may be treated with a hydrophobizing agent such as hexamethyldisilazane alone, or treated with two or more types of surface treating agents by combining hexamethyldisilazane and other surface treating agents. May be.
- a hydrophobizing agent such as hexamethyldisilazane alone
- two or more types of surface treating agents by combining hexamethyldisilazane and other surface treating agents. May be.
- the aminosilane coupling agent is used in combination with an aminosilane coupling agent for imparting positive chargeability
- the silica fine powder is first subjected to the aminosilane treatment and then the hydrophobic treatment method of the present invention is carried out.
- aminosilane treatment is performed, a method of contacting the aminosilane coupling agent in a gasified state is preferable.
- the blending amount of the silica fine powder of the present invention into the toner is usually preferably 0.3 to 5 parts by mass, more preferably 0.5 to 4 parts by mass with respect to 100 parts by mass of the toner. If the blending amount is too small, the amount of adhesion to the toner is small and a sufficient storage stability improving effect cannot be obtained, and if it is too large, the silica fine powder may be detached from the toner surface.
- the silica powder of the toner external additive containing the silica fine powder of the present invention is not limited to the silica fine powder of the present invention used alone, for example, 200-500 m 2 / It can also be used in combination with ultrafine powder silica of about g.
- the electrostatic image developing toner to which the external toner additive containing the silica fine powder of the present invention is added a known toner composed mainly of a binder resin and a colorant can be used. Moreover, the charge control agent may be added as needed.
- the electrostatic image developing toner to which the toner external additive containing silica fine powder of the present invention is added can be used as a one-component developer, and can be mixed with a carrier to be used as a two-component developer. You can also.
- 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.
- the carrier iron powder or the like, or a known one whose surface is resin-coated is used.
- the formation of the flame was performed by providing several tens of pores at the outlet of the double tube burner and injecting a mixed gas of LPG and oxygen therefrom.
- the spherical silica fine powder generated from the two-fluid nozzle and passed through the flame was pneumatically transported through a collection line by a blower and collected by a bag filter.
- the specific surface area of the spherical silica fine powder was adjusted by adjusting the slurry concentration, the slurry feed amount, and the LPG amount. Specifically, when reducing the specific surface area, adjustment was made by increasing the slurry concentration, the slurry feed amount, and the LPG amount. On the other hand, when increasing the specific surface area, it was adjusted by decreasing the slurry concentration, the slurry feed amount, and the LPG amount.
- spherical silica fine powders having various specific surface areas and loose bulk density.
- 500 g of the obtained spherical silica fine powder was set in a stainless steel cylindrical container having a diameter of 250 mm.
- a ribbon heater is installed on the outer periphery of the stainless steel cylindrical container.
- a 20 ⁇ m wire mesh is provided at the lower inlet to uniformly supply gas, and a filter cloth is attached to the upper outlet to prevent powder from scattering outside the system. ing.
- the ribbon heater was operated to keep the internal temperature at 135 ° C to 150 ° C.
- nitrogen gas circulated by a suction blower is fed from the lower inlet of the container at a flow rate of 150 NL / min to fluidize the spherical silica fine powder, while water is 0.3 mg to 1.8 mg per 1 m 2 of the spherical silica fine powder.
- the gas was supplied to the bottom of the container so as to be gasified, and brought into contact with the spherical silica fine powder along with the circulating nitrogen gas.
- hexamethyldisilazane (“SZ-31” manufactured by Shin-Etsu Chemical Co., Ltd.) is supplied in an amount of 0.5 mg to 3.0 mg per 1 m 2 of spherical silica fine powder, gasified, and circulated.
- the spherical silica fine powder was brought into contact with nitrogen gas.
- the supply amounts of water and hexamethyldisilazane to the lower part of the container were 2.0 g / sec.
- the powder was recovered. This operation was repeated 1 to 5 times to obtain hydrophobized spherical silica fine powders A to U.
- the amount of water added in one surface treatment is 0.5 mg to 1.5 mg per 1 m 2 of the spherical silica fine powder, hexamethyldisilazane.
- the amount of water added in one surface treatment is 0.5 mg to 1.5 mg per 1 m 2 of the spherical silica fine powder, hexamethyldisilazane.
- the loose bulk density, carbon amount, and degree of hydrophobicity were adjusted by adjusting the number of repetitions of water and hexamethyldisilazane treatment and the amount added per one of these.
- the above stainless steel cylindrical container is set to room temperature, water is sprayed from the top of the container, water is sprayed with hexamethyldisilazane after 5 minutes of water spray, and the powder is recovered after being flown for 10 minutes.
- Spherical silica fine powders V to X were obtained.
- the liquid spray rates of water and hexamethyldisilazane were each 2.0 g / sec. Also, adjust the spray amount of water to 0.6 mg to 1.2 mg per 1 m 2 of spherical silica fine powder, and adjust the spray amount of hexamethyldisilazane to 1.0 mg to 2.0 mg per 1 m 2 of spherical silica fine powder.
- the mixture was placed in “FM-10B type” manufactured by Miike Chemical Industries Ltd. and mixed at 1000 rpm for 1 minute.
- 10 g of this mixture was weighed into a silicone cup and allowed to stand at a temperature of 62 ° C. for 3 hours, and then gently transferred onto a sieve having an opening of 74 ⁇ m, and a powder tester (“PT-E type” manufactured by Hosokawa Micron Corporation) was vibrated. I set it on the table. After setting the amplitude of the sieve to 1.0 mm and vibrating for 30 seconds, the mass of the mixture remaining on the sieve was measured. The smaller this value, the better the storage stability of the toner.
- the suction time was 3 minutes, the suction pressure was 4.0 kPa, and a screen of 32 ⁇ m mesh was used for the screen used for separating the simulated toner and the carrier.
- a toner external additive excellent in storage stability and chargeability is provided. Further, silica fine powder suitable for addition to the toner external additive is provided.
- the silica fine powder of the present invention is used as an external additive for electrophotographic toners used in copying machines and laser printers.
Abstract
Description
(1)球状シリカ微粉末をヘキサメチルジシラザンで表面処理した疎水化球状シリカ微粉末であり、比表面積が15m2/g以上90m2/g以下、緩め嵩密度が0.09g/cm3以上0.18g/cm3以下、カーボン量が0.25wt%以上0.90wt%以下、疎水化度が60%以上75%以下であることを特徴とする疎水化球状シリカ微粉末。
(2)表面処理前の球状シリカ微粉末の緩め嵩密度(B)に対する表面処理後の疎水化球状シリカ微粉末の緩め嵩密度(A)の比(A)/(B)が1.05以上1.60以下であることを特徴とする前記(1)に記載の疎水化球状シリカ微粉末。
(3)球状シリカ微粉末が、金属シリコンと酸素を反応させて得られた球状シリカ微粉末であることを特徴とする前記(1)又は(2)に記載の疎水化球状シリカ微粉末。
(4)前記(1)から(3)のいずれか1項に記載の疎水化球状シリカ微粉末を含有することを特徴とする静電荷像現像用トナー外添剤。
(5)比表面積が15m2/g以上90m2/g以下、緩め嵩密度が0.09g/cm3以上0.18g/cm3以下、カーボン量が0.25wt%以上0.90wt%以下、疎水化度が60%以上75%以下であるシリカ微粉末。
(6)平均球形度が0.80以上である(5)に記載のシリカ微粉末。
(7)表面にアルキル基を有する(5)又は(6)に記載のシリカ微粉末。
(8)表面にトリメチルシリル基を有する(5)又は(6)に記載のシリカ微粉末。
(9)含水率が0.03wt%以上0.50wt%以下である(5)から(8)のいずれか1項に記載のシリカ微粉末。
(10)(5)から(9)のいずれか1項に記載のシリカ微粉末を含有する静電荷像現像用トナー外添剤。
(11)(4)又は(10)に記載の静電荷像現像用トナー外添剤を含有する静電荷像現像用トナー。
本発明のシリカ微粉末は、比表面積が15m2/g以上90m2/g以下であることが必要である。比表面積が15m2/g未満であると、シリカ微粉末自体の帯電量が小さくなり、トナー外添剤に使用した際の帯電性が不十分となる。一方、比表面積が90m2/gを超えると、トナー同士のブロッキング防止に寄与しないサイズのシリカ微粉末が多くなり、トナー外添剤に使用した際に、保存性を向上させることが出来ない。好ましい比表面積は20m2/g以上75m2/g以下、より好ましくは25m2/g以上60m2/g以下である。
実施例1~14 比較例1~10
球状シリカ微粉末は、燃焼炉の頂部に内炎と外炎が形成できる二重管構造のLPG-酸素混合型バーナーが設置され、下部に捕集系ラインが直結されてなる装置を用いて製造した。上記バーナーの中心部には更にスラリー噴霧用の二流体ノズルが設置され、その中心部から、金属シリコン粉末(平均粒径10.5μm)と水からなるスラリー(金属シリコン濃度:10~70質量%)を2~30L/Hrのフィード量で噴射した。周囲からは酸素を供給した。火炎の形成は二重管バーナーの出口に数十個の細孔を設け、そこからLPGと酸素の混合ガスを噴射することによって行った。二流体ノズルから噴射され火炎を通過して生成した球状シリカ微粉末は、ブロワによって捕集ライン中を空気輸送し、バグフィルターで捕集した。なお、球状シリカ微粉末の比表面積の調整は、スラリー濃度、スラリーフィード量、及びLPG量の調整により行った。具体的には、比表面積を小さくする場合は、スラリー濃度、スラリーフィード量、及びLPG量を増加させることで調整した。一方、比表面積を大きくする場合は、スラリー濃度、スラリーフィード量、及びLPG量を低下させることで調整した。
また、比較例として、上記ステンレス製円筒容器を常温とし、容器上部から水を液噴霧し、水噴霧5分後にヘキサメチルジシラザンを液噴霧して10分間流動後、粉末を回収し、疎水化球状シリカ微粉末V~Xを得た。水、及びヘキサメチルジシラザンの液噴霧速度はそれぞれ2.0g/秒とした。
また、水の噴霧量を球状シリカ微粉末1m2あたり、0.6mg~1.2mg、ヘキサメチルジシラザンの噴霧量を球状シリカ微粉末1m2あたり、1.0mg~2.0mgと調整することで、緩め嵩密度、カーボン量、及び疎水化度を調整した。
得られた疎水化球状シリカ微粉末の比表面積、緩め嵩密度、カーボン量、疎水化度、表面処理前の球状シリカ微粉末の緩め嵩密度(B)に対する表面処理後の疎水化球状シリカ微粉末の緩め嵩密度(A)の比(A)/(B)を表1、表2に示す。なお、得られた疎水化球状シリカ微粉末A~Xの平均球形度は、いずれも0.85以上であり、含水率は0.05wt%以上0.40wt%以下の範囲であった。
疎水化球状シリカ微粉末A~X15gと、ガラス転移点62℃のポリエステル樹脂をジェットミルで平均粒径が7.5μmになるように粉砕調整した樹脂粉485gをヘンシェルミキサー(三井三池化工機社製「FM-10B型」)に入れ、1000rpmで1分間混合した。この混合物10gをシリコーンカップに計り取り、温度62℃の条件下で3時間静置した後、目開き74μmの篩の上に静かに移し、パウダテスタ(ホソカワミクロン社製「PT-E型」)の振動台にセットした。篩の振幅を1.0mmに設定して、30秒間振動した後、篩上に残った混合物の質量を測定した。この値が小さいほど、トナーの保存性が良いことを表す。
疎水化球状シリカ微粉末A~X30gと、平均粒子径5μmの架橋スチレン樹脂粉(綜研化学社製商品名「SX-500H」)970gをヘンシェルミキサー(三井三池化工機社製「FM-10B型」)に入れ、1000rpmで1分間混合し疑似トナーを作製した。この疑似トナーを、温度25℃、相対湿度55%の条件下で24時間静置した後、ブローオフ帯電量を以下の手法で測定した。模擬トナー0.20gと、キャリアとして負帯電極性トナー用標準キャリア(日本画像学会より頒布「N-01」)3.80gを100mlポリエチレン製容器に入れて容器の蓋を閉め、容器を上下にして手に持ち、約30cmのストロークにて2回/秒の速度で200回振とうさせた。振とう3分後、この模擬トナーとキャリアの混合物0.30gを用いて吸引分離式帯電量測定器(三協パイオテク社製「セパソフトSTC-1」)により、ブローオフ帯電量を測定した。吸引時間は3分間、吸引圧力は4.0kPaとし、模擬トナーとキャリアの分離に用いるスクリーンには目開き32μmの金網を使用した。このブローオフ帯電量のマイナスの値が大きいほど、トナーの帯電性が良いことを表す。
Claims (11)
- 球状シリカ微粉末をヘキサメチルジシラザンで表面処理した疎水化球状シリカ微粉末であり、比表面積が15m2/g以上90m2/g以下、緩め嵩密度が0.09g/cm3以上0.18g/cm3以下、カーボン量が0.25wt%以上0.90wt%以下、疎水化度が60%以上75%以下であることを特徴とする疎水化球状シリカ微粉末。
- 表面処理前の球状シリカ微粉末の緩め嵩密度(B)に対する表面処理後の疎水化球状シリカ微粉末の緩め嵩密度(A)の比(A)/(B)が1.05以上1.60以下であることを特徴とする請求項1に記載の疎水化球状シリカ微粉末。
- 球状シリカ微粉末が、金属シリコンと酸素を反応させて得られた球状シリカ微粉末であることを特徴とする請求項1又は2に記載の疎水化球状シリカ微粉末。
- 請求項1から3のいずれか1項に記載の疎水化球状シリカ微粉末を含有することを特徴とする静電荷像現像用トナー外添剤。
- 比表面積が15m2/g以上90m2/g以下、緩め嵩密度が0.09g/cm3以上0.18g/cm3以下、カーボン量が0.25wt%以上0.90wt%以下、疎水化度が60%以上75%以下であるシリカ微粉末。
- 平均球形度が0.80以上である請求項5に記載のシリカ微粉末。
- 表面にアルキル基を有する請求項5又は6に記載のシリカ微粉末。
- 表面にトリメチルシリル基を有する請求項5又は6に記載のシリカ微粉末。
- 含水率が0.03wt%以上0.50wt%以下である請求項5から8のいずれか1項に記載のシリカ微粉末。
- 請求項5から9のいずれか1項に記載のシリカ微粉末を含有する静電荷像現像用トナー外添剤。
- 請求項4又は10に記載の静電荷像現像用トナー外添剤を含有する静電荷像現像用トナー。
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