WO2007142047A1 - 乾式シリカ微粒子 - Google Patents
乾式シリカ微粒子 Download PDFInfo
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- WO2007142047A1 WO2007142047A1 PCT/JP2007/060757 JP2007060757W WO2007142047A1 WO 2007142047 A1 WO2007142047 A1 WO 2007142047A1 JP 2007060757 W JP2007060757 W JP 2007060757W WO 2007142047 A1 WO2007142047 A1 WO 2007142047A1
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- gas
- fine particles
- particles
- oxygen
- dry
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C01B33/181—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to a novel dry silica fine particle which can be suitably used as a filler for a resin composition used as a semiconductor sealing material, a liquid crystal sealing material, a laminated substrate insulating material or the like, or as an external additive for an electrophotographic toner.
- dry silica fine particles for example, fumed silicon force produced by flame hydrolysis of silane silane (generally called dry silica) is known (patent) Reference 1).
- force fumed silica has the effect of imparting high viscosity just by adding a small amount to a resin in the liquid state (molten state or solution state).
- the resin resin composition
- the fumed shear force has the disadvantage of causing corrosion of metal wiring and the like because it contains chlorine derived from chlorosilane as a raw material.
- spherical silica with an average particle diameter of about 1; / m as the filler. In this case, it is possible to suppress the increase in the viscosity of the resin and increase the filling rate of the filler.
- This spherical silica contains not only a lot of coarse particles of several jum or more due to the production method, but also contains a lot of agglomerated particles that are highly cohesive and difficult to disperse in the resin. As a result, such a resin composition to which a large amount of spherical silica is added has poor gap permeability, and is clogged between wirings, thereby reducing the reliability of equipment to which the resin composition is applied.
- the fumed silica described above is used as an external additive for toners used in electrophotographic technology such as copying machines and laser printers for the purpose of imparting fluidity and controlling the amount of charge. (See Patent Document 2).
- fumed silica fine particles used as an external toner additive have a branched structure in which primary particles are fused, and it is difficult to obtain a fluidity-imparting effect compared to independent spherical particles. Since the primary particle size is small, silica particles are buried from the surface of the toner resin particles due to external stress such as stirring, so that the anti-blocking function is not fulfilled for a long time, and the fluidity of the toner gradually decreases. It becomes difficult to scrape the residual toner with the cleaning blade, and if the transfer rate is lowered during image formation, it causes problems such as image quality deterioration due to filming.
- toner external additives are also required to have a charge control function for toner particles.
- the external additive has a broad particle size distribution, dispersibility and adhesion to toner resin particles will be uneven. For this reason, problems arise in charging control, which causes a reduction in image quality.
- a metal such as iron or sodium or chlorine is contained as an impurity, recharge control with a low charge amount becomes difficult.
- the raw material does not contain a halogen compound, but in order to control the average particle diameter of the silica obtained, it is necessary to control the concentration of the raw material silicon in the flame.
- the raw material Sicon powder
- the supply rate can be increased, but it is difficult to obtain a stable quantitative supply. Therefore, the silica source concentration varies in the flame due to fluctuations in the supply of raw materials, and it is impossible to obtain silli force fine particles having a sharp particle size distribution without including coarse particles.
- silica particles with a sharp particle size distribution that do not contain coarse particles are easily obtained due to the particle size distribution derived from the raw material powder and the uneven distribution of the raw material in the flame. It is not possible.
- the raw material used is liquid (liquid siloxane), which is easy in terms of stable supply of the raw material, but the size of the droplets when sprayed is kept constant. It is difficult, and there must be a place where a droplet exists and a place where it does not exist As a result, the silica source concentration in the flame varies, and it is impossible to obtain silica fine particles having a sharp particle size distribution without containing coarse particles.
- the methods (1) to (4) are not suitable as a method for obtaining silica particles having the characteristics (a) to (c) described above.
- siloxane containing no halogen in the molecule is vaporized and fed quantitatively to the PANA to produce silica in the flame. Introduced into carrier with nitrogen or other carrier gas and diffused and mixed with combustion-supporting gas (oxygen, air, outside air, etc.) introduced separately into the analyzer at the outlet of the analyzer.
- the mixed state of the siloxane gas and the combustion-supporting gas has a significant effect on the combustion state of the siloxane and, in turn, the formation of silica fine particles. Therefore, there is a problem that it is difficult to control the particle size distribution of the resultant silica fine particles.
- the siloxane burns incompletely, carbon soot is generated, and silica fine particles cannot be obtained.
- silica fine particles contain coarse particles
- a method of removing coarse particles by classification operation is considered, but the technology for removing particles of about 3 to 5 m by dry classification methods such as cyclist air classification not exist. Therefore, the classification of the silica fine particles must be carried out by a wet classification method such as wet sieving or elutriation. This means that a fine particle drying process is required, and particles are strongly aggregated during drying, resulting in generation of coarse particles.
- the particle size distribution is controlled by classification. The fact is that we cannot do it.
- Patent Document 2 Japanese Patent Application Laid-Open No. 2 00 1- 1 1 6 5 7 5
- Patent Document 3 Japanese Patent Laid-Open No. 4 1 2 1 5 1 5
- Patent Document 4 Japanese Patent Application Laid-Open No. 2 00 3-2 13
- Patent Document 5 Japanese Patent Application Laid-Open No. Sho 60-255-5602
- Patent Document 6 Japanese Patent Laid-Open No. 2 00 2-6 0 2 14
- Patent Document 7 Japanese Patent Application Laid-Open No. 2 0 0 2- 1 1 4 5 10
- an object of the present invention is to provide dry silica fine particles that are excellent in dispersibility in a resin, can suppress an increase in viscosity when the resin is highly filled, and can provide sufficient strength to the resin, and the production thereof. It is to provide a method.
- the object of the present invention can further prevent deterioration of resin gap permeability and clogging between wirings caused by coarse particles or agglomerated particles of several meters or more when blended in a resin.
- An object of the present invention is to provide a dry silica fine particle that does not cause problems such as a decrease in reliability of equipment to which a resin is applied, and a method for producing the same.
- Another object of the present invention is to provide excellent fluidity when used as an external additive for toner particles for electrophotography, and maintain good fluidity by suppressing the embedding in toner resin particles even for long-term use. To provide dry-shear force fine particles and a method for producing the same.
- the inventors of the present invention are informed about the relationship between the combustion conditions of a siloxane compound containing no halogen in the molecule and the performance of the resulting dry silica fine particle resin filler as a toner external additive.
- the siloxane compound By adjusting the combustion conditions to a specific range, the present inventors have succeeded in obtaining dry silica fine particles that have achieved the above object, and have completed the present invention.
- the following formula (1) shows the absorbance of the aqueous suspension contained at a concentration of% by weight with respect to light having a wavelength of 700 nm.
- S is a dry silica fine particle force ⁇ provided by satisfying the following: BET specific surface area (m 2 Zg) of dry silica fine particles.
- the remaining amount on the screen by the wet sieving method using an electroformed sieve with a mesh size of 5 m is 10 ppm or less
- r-methacryloxypropyl trimethoxysilane glycidoxy propyl pyrimethoxysilane, glycidoxypropylmethyldimethoxysilane, mercaptopropyl trimethoxysilane, ⁇ -aminopropyl trimethoxysilane, r With at least one silylating agent selected from the group consisting of aminopropyltriethoxysilane, r- (2-aminoethyl) aminopropyl trimethoxysilane, and r- (2-aminoethyl) aminopropylmethyldimethoxysilane.
- Surface treatment Is preferred.
- a burner having a multi-tube structure having a central tube and a first annular tube formed on the outer periphery thereof is used, and a gas of siloxane compound not containing halogen in the molecule and oxygen gas are used.
- the dry mixed silica is supplied by supplying the mixed gas containing the gas to the center pipe of the panner and supplying the auxiliary fuel gas containing hydrogen gas or hydrocarbon gas as a combustible component to the first annular pipe of the panner for combustion.
- a method for producing fine particles, wherein the mixed gas has the following formula (2) :
- A is the amount of oxygen in the mixed gas
- B is the amount of oxygen necessary for complete combustion of the siloxane compound in the mixed gas
- R 0 is 0, 3-1.
- R 0 is 0, 3-1.
- the auxiliary fuel gas has the following formula (3):
- c is the amount of oxygen necessary to completely burn the combustible component in the auxiliary fuel gas discharged from the first annular pipe
- B ′ is the amount of oxygen necessary for complete combustion of the siloxane compound in the mixed gas discharged from the central tube.
- the mixed gas contains a siloxane compound gas and an oxygen gas at a ratio such that the oxygen ratio R 0 is 1.0 to 1.5.
- a resin composition containing the dry silica fine particles and an electrophotographic toner external additive comprising the dry silica fine particles.
- the dry silica fine particles of the present invention are excellent in dispersibility in a resin or the like, and can suppress an increase in viscosity when, for example, a large amount is dispersed and blended in a resin, and can impart sufficient strength to a resin composition. . Further, such silica fine particles do not contain coarse particles or agglomerated particles, and as a result, the resin composition containing the silica fine particles exhibits good gap permeability and clogs between wirings. In addition, there is no problem that the reliability of equipment to which such a resin composition is applied is lowered.
- the dry silica fine particles of the present invention are useful as a filler for resin, and the resin composition containing the dry silica fine particles is used as a semiconductor sealing material, a liquid crystal sealing material, or an insulating material for a laminated substrate. Very useful for applications.
- the dry silica fine particles of the present invention are excellent in the early fluidity-imparting effect because they are quickly dispersed on the surface of the toner resin particles even when they are mixed with the toner resin particles by means of a method of weak dispersion called dry mixing.
- dry mixing even when used for a long period of time, it is not buried in the toner resin particles, so that excellent fluidity can be imparted to the toner particles over a long period of time.
- due to poor scraping of the cleaning blade It has a particle size suitable for preventing filming phenomenon, and furthermore, the particle size distribution is sharp and variation in the toner charge amount is suppressed, and further, the durability of the photoreceptor drum due to wear is effectively reduced. Can be suppressed.
- FIG. 1 is a diagram showing a schematic cross-sectional structure of a panner suitably used for producing the dry silica fine particles of the present invention.
- the dry silica fine particles of the present invention have a BET specific surface area of 20 to 55 m 2 / g ,
- the specific surface area exceeds 55 m 2 Zg, for example, when adding an amount necessary for providing efficient heat dissipation or approximating the thermal expansion coefficient to the semiconductor element, the viscosity increases. It becomes difficult to achieve the object of the present invention to suppress the increase in viscosity.
- the specific surface area is 2 Om z less, when added to the resin to cure the resin, for the surface area of the silica fine particles that interact with the resin is small, a sufficient strength to the resulting cured product grant I can't do it.
- BET specific surface area (m 2 Zg) of dry silica fine particles In general, the smaller the primary particle diameter of silica in the water suspension, that is, the higher the specific surface area, the smaller the absorbance.
- fumed silica when several to several tens of primary particles form a group (secondary particles) that are relatively strongly bonded, and they have an agglomerated structure that is further bonded to other secondary particles. Has a large absorbance. Therefore, in the silica having the same specific surface area, the low absorbance value means that the primary particles themselves are small and do not form fused secondary particles, and exist as independent small primary particles.
- the particles do not have an agglomerated structure, do not contain coarse particles, and the primary particle size distribution is narrow (shows a sharp particle size distribution).
- the silica particles having a smaller absorbance value are silica particles that have inherently good dispersibility in the resin and have characteristics.
- the dry silica fine particles of the present invention have a specific surface area exhibiting the above-mentioned characteristics and at the same time the absorbance satisfies the condition of the formula (1).
- Resin has almost no secondary particles, no agglomeration structure, no coarse particles, sharp particle size distribution, and such particle characteristics. And dispersibility with respect to toner particles is very good.
- the method for measuring the absorbance ⁇ will be described in the examples below.
- the dispersibility in the resin is poor and the thermal expansion coefficient of the resin composition is not uniform.
- the particle size distribution becomes broad and dispersed in the resin, the gap permeability of the resin composition deteriorates and clogging between the wirings tends to occur.
- the dispersibility with respect to the toner particles becomes unsatisfactory, the effect of imparting early fluidity to the toner particles cannot be obtained, the adhesion to the toner particles and the charging characteristics become non-uniform, When image formation is performed, image deterioration such as streaks, capri, and blurring is likely to occur.
- the dry silica fine particles of the present invention have a screen residual amount of 10 ppm or less by a wet sieving method using an electroformed sieve having an aperture of 5 / m, more preferably an electroformed sieve having an aperture of 3 im. There is Is preferred.
- the residual amount on the screen by the wet sieving method using an electroformed sieve with such openings is
- the gap permeability of the resin composition deteriorates due to coarse particles, or clogging between wirings tends to occur, and the reliability of equipment to which the resin composition is applied decreases. It is because it becomes easy to produce the problem of. In addition, wear due to coarse particles becomes prominent, and when used as an external additive for toner, the durability of the photosensitive drum due to wear or the image quality due to deterioration of the characteristics of the photosensitive drum are likely to be reduced. .
- the method for quantifying the content of coarse particles will be described later, but it must be a wet sieving method using an electroforming sieve.
- a particle size distribution measurement method using a laser diffraction / scattering method is conceivable.
- such a method has a detection level of about a percent as described later, and the detection sensitivity is very poor. It is not suitable for measuring the particle size distribution of silica fine particles.
- the dry silica particles of the present invention have less than 2 O ppm iron, less than 5 ppm aluminum, less than 5 ppm nickel, less than 5 pp rr> chromium, less than 3 ppm sodium, and less than 3 ppm chlorine. It is preferable because it can reduce the short circuit between metal wires and the corrosion of metal wires caused by silica fine particles, and it is also preferable in terms of ensuring the chargeability of toner particles when used as an external additive for toner.
- the dry silica particles of the present invention have less than 2 O ppm iron, less than 5 ppm aluminum, less than 5 ppm nickel, less than 5 pp rr> chromium, less than 3 ppm sodium, and less than 3 ppm chlorine. It is preferable because it can reduce the short circuit between metal wires and the corrosion of metal wires caused by silica fine particles, and it is also preferable in terms of ensuring the chargeability of toner particles when used as an external additive for toner.
- the above-described dry silica fine particles of the present invention are produced using, for example, a panner having a multi-tube structure as shown in FIG.
- This panner has a central tube 1, a first annular tube 3 is formed on the outer periphery of the central tube 1, and a second tube is provided around the first annular tube 3 if necessary.
- An annular tube 5 is formed.
- a siloxane compound containing no halogen in the molecule is used as a silica source, and a mixed gas containing a gas of this siloxane compound and an oxygen gas is connected to the center tube of the PANA 1
- the dry silica fine particles of the present invention are produced by supplying an auxiliary fuel gas containing hydrogen gas or hydrocarbon gas as a combustible component to the first annular pipe 3 of the above-mentioned burner for combustion. To do.
- the siloxane compound used as the silica source of silica must be free of halogen atoms.
- a molecule containing a halogen atom such as chlorosilane
- the halogen atom remains in the resulting silica, which causes metal corrosion and the like. This is because the use of silica is limited.
- a sufficient flame temperature cannot be secured during combustion, silica particle growth is suppressed, and silica particles having a particle size suitable for the use of a resin filler or a toner external additive can be obtained. There is also the inconvenience that it becomes difficult.
- siloxanes having a ratio (CZS i) of the number of carbon atoms to the number of carbon atoms contained in the molecule of 2 or less that is, cyclic siloxanes are preferable.
- silica fine particles obtained will have a high content of iron and the like.
- the above siloxane compound must be supplied to the PANA in a gas state. However, this can be easily performed by heating and vaporizing the siloxane compound. In this case, since a siloxane compound having a low boiling point is more easily vaporized by heating, among the above siloxane compounds, those having a boiling point of 100 to 25 ° C., such as hexamethylcyclosiloxane and octamethyl. Cyclotetrasiloxane is most preferred.
- a carrier gas can also be used when a siloxane compound containing no halogen in the molecule is vaporized and supplied to the PANA.
- a carrier gas nitrogen, helium, argon or the like is suitable.
- the above siloxane compound gas is supplied to the above-described center pipe 1 of the above-mentioned gas in the form of a mixed gas with oxygen, and at the same time, an auxiliary fuel gas containing hydrogen gas or hydrocarbon gas as a combustible component. Then, the first annular pipe 3 surrounding the central pipe 1 is supplied and combusted, and the silitri force fine particles are obtained by the combustion.
- the characteristics of the silica fine particles obtained reflect the history of the silica fine particles in the flame.
- the characteristics of silica fine particles are very strongly influenced by the flame structure during combustion. Therefore, in order to obtain fine particle silica having the specific surface area and absorbance described above, the mixed gas supplied to the central tube 1 and the auxiliary fuel gas supplied to the first annular tube must satisfy the following conditions: .
- the mixed gas supplied to the central tube 1 is represented by the following formula ( 2 ):
- A is the amount of oxygen in the mixed gas
- B is the amount of oxygen necessary for complete combustion of the siloxane compound in the mixed gas
- oxygen ratio R 0 is 0, 3-1 defined. 5, preferably from 1.0 to 1. Require der be 5 to become percentage are those which contain a gas and oxygen gas of the siloxane compound The That is, when octamethylcyclotetrasiloxane is used as the siloxane compound, this combustion formula is represented by the following formula.
- the oxygen ratio R is in the mixed gas. Therefore, it is necessary to contain oxygen gas in an amount of 4.8 to 24 mol, particularly 16 to 24 mol, per mol of siloxane compound (octamethylcyclotetrasiloxane) so that the above-mentioned range is satisfied. is there.
- the oxygen ratio R 0 when the oxygen ratio R 0 is smaller than 0.3, the amount of oxygen in the mixed gas is small, so oxygen and air introduced from other than the center tube 1 of the panner, or oxygen and panner contained in the atmosphere. Since the proportion of the siloxane compound mixed and reacted at the outlet increases too much, the uniformity of the flame related to the generation and growth of silica particles is lost, the particle size distribution of the resulting silica particles becomes broad, and the absorbance is high. Natsume no longer satisfies equation (1). For this reason, the oxygen ratio R 0 must be 0.3 or more. However, in order to sufficiently maintain the uniformity of the flame involved in the generation and growth of silica fine particles, the oxygen ratio should be 1.0 or more. More preferred.
- the absorbance of the silica fine particles obtained is adjusted by adjusting the siloxane compound and oxygen gas concentrations in the mixed gas so that the oxygen ratio R 0 is in the range of 0.3 to 1.5.
- the above formula ( 1 ) is satisfied and the specific surface area can be within the above-mentioned range, formation of silica fine particles ⁇ Uniform flame associated with growth
- the oxygen ratio is preferably set to 1.0 to 1.5.
- the mixed gas may contain the above-described carrier gas.
- the siloxane compound and the oxygen gas concentration in the mixed gas have an oxygen ratio Ro within the above range. It must be adjusted so that
- the above mixed gas is supplied to the central pipe 1 of the burner, and at the same time, the auxiliary fuel gas is supplied to the first annular pipe 3 to burn it ⁇
- a flammable gas containing hydrogen gas or hydrocarbon gas is used.
- hydrogen alone gas, hydrocarbon alone gas, mixed gas of hydrogen and hydrocarbon, gas obtained by diluting these combustible gases with nitrogen, etc. can be used, but hydrocarbon is incomplete. Since carbon soot is generated when burned, it is preferable to use a gas not containing hydrocarbons as an auxiliary fuel gas.
- the auxiliary fuel gas has the following formula (3) :
- C is the amount of oxygen necessary to completely burn the combustible component in the auxiliary fuel gas discharged from the first annular pipe
- B ′ is the amount of oxygen necessary for complete combustion of the siloxane compound in the mixed gas discharged from the central tube.
- auxiliary fuel ratio R SFL defined by is between 0.003 and 0.3.
- the siloxane compound when octamethylcyclotetrasiloxane is used as the siloxane compound, if this siloxane compound is discharged from the central tube 1a in an amount of 1 mole per unit time, it is completely burned. Since the amount of oxygen required for this is 16 moles per unit time, the auxiliary fuel gas at this time includes combustible gas that is completely burned by an amount of 0.048-4.8 moles of oxygen per unit time. It must be something.
- hydrogen when hydrogen is used as the combustible gas, its combustion formula 2007/060757
- the auxiliary fuel gas must be supplied to the Parner so that an amount of 0.096 to 9.6 mol of hydrogen is discharged per unit time.
- the auxiliary fuel ratio R SF 1 _ is greater than 0.3, the amount of oxygen that is mixed with the siloxane gas in advance and reacts with the combustible component in the auxiliary fuel gas is excessively increased. Formation of silica fine particles ⁇ The uniformity of the flame associated with the growth is lost, the particle size distribution of the resulting silica fine particles becomes broad, and the absorbance is high, so the formula (1) is not satisfied. Also, if the auxiliary fuel ratio R SF is less than 0.003, no flame is formed, or even if a flame is formed, the flame is not stable, and as a result, the uniformity of the flame is lost, The particle size distribution becomes broad, and the absorbance does not satisfy the condition of the above formula (1).
- combustion is performed by discharging the auxiliary fuel gas from the first annular pipe so that the auxiliary fuel ratio R s F falls within the above range according to the discharge amount of the siloxane compound in the mixed gas.
- the present invention in the case where lysic force fine particles are produced by combustion by discharging the mixed gas from the central tube 1 and discharging the auxiliary fuel gas from the first annular tube 3 as described above, It is sufficient to use a panner having a double pipe structure consisting of the pipe 1 and the first annular pipe 3.
- the second annular pipe 5 is further provided outside the first annular pipe 3.
- a panner having a triple pipe structure provided with oxygen gas from the second annular pipe 5 as a combustion-supporting gas. That is, by supplying such a combustion-supporting gas (oxygen gas) from the outside of the auxiliary fuel gas, it is possible to suppress the auxiliary fuel from reacting with oxygen contained in the mixed gas.
- Silica fine particles can be generated well.
- the flame temperature is prevented from lowering due to the reaction between the auxiliary fuel and the air outside the flame (outside air), and the increase in fused particles is avoided, resulting in poor dispersibility. It is also preferable to prevent generation of large silica fine particles.
- combustion-supporting gas oxygen gas
- D is the amount of oxygen discharged from the second annular tube
- the combustion-supporting oxygen ratio R cmb ts defined by the above is supplied so as to be 0.1 to 2.0 . That is, the combustion-supporting oxygen ratio R cmb ts is set in the same manner as the auxiliary fuel ratio R SF ! _, So that the combustion-supporting oxygen ratio R cmbts is larger than the above range.
- the oxygen gas power is supplied from the second annular pipe 5, there is no particular effect, and the amount of silica fine particles produced is small compared to the amount of gas used, which is economically disadvantageous.
- the dry-shearing fine particles of the present invention obtained as described above are suitably used as an external additive for a resin filler or an electrophotographic toner.
- a resin composition in which silica fine particles are blended as a filler is particularly suitable for use as a semiconductor sealing material, a liquid crystal sealing material, or an insulating material for a laminated substrate.
- the dry silica fine particles of the present invention are usually externally added in an amount of 0.1 to 5 parts by weight per 100 parts by weight of toner resin particles.
- dry silica fine particles of the present invention can be directly blended into a resin or externally added to toner resin particles, but can also be used after being surface-treated with a surface treatment agent.
- Examples of such surface treatment agents include silylating agents, silicone oils, various siloxanes, and various fatty acids, which contain halogens. It is necessary not to be. This is because, when a surface treatment agent containing halogen is used, the advantage of the dry silica fine particles of the present invention that it is substantially free of halogen is impaired.
- silylating agent examples include tetramethoxysilane, methyltrimethoxysilane, dimethyldimethyloxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, o-methylphenyltrimethoxysilane, p_methylphenyltrisilane.
- Silicone oils include dimethyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, alkyl-modified silicone oil, carboxylic acid-modified silicone oil, fatty acid-modified silicone oil, polyether-modified silicone oil, alkoxy-modified silicone oil, and carbino. Silicone modified silicone oil, amino modified silicone oil, terminal reactive silicone For example, oil.
- siloxanes examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane, and the like.
- fatty acids long chain such as undecyl acid, lauric acid, tridecyl acid, dodecyl acid, myristic acid, valmitic acid, pentadecyl acid, stearic acid, heptadecyl acid, araquinic acid, montanic acid, oleic acid, linoleic acid, arachidonic acid, etc.
- fl Fatty acids can be exemplified.
- the dry silica fine particles of the present invention have one advantage that the content of metal impurities such as iron is low.
- metal impurities such as iron
- the above-mentioned metal of fatty acid is used.
- a salt for example, a salt with a metal such as zinc, iron, magnesium, aluminum, calcium, sodium, or lithium
- a metal alkoxide can also be used as a surface treatment agent.
- Such metal alkoxides include: trimethoxyaluminum, triethoxyaluminum, tree i-propoxyaluminum, tree n-butoxyaluminum, trie s-butoxyaluminum, tri-t-butoxyaluminum, mono-s-butoxydi-i Propylaluminum, Tetramethoxytitanium, Tetraethoxytitanium, Tetra-i-propoxytitanium, Tetra-n-propoxytitanium, Tetra-n-butoxytitanium, Tetra-s-butoxytitanium, Tetra-t-butoxytitanium, Tetraethoxyzirconium, Tetra-i —Propoxy diol, tetra n-butoxy zirconium, dimethyl tin, gypoxy tin, di-n-butoxy tin, tetraethoxy tin, tetra-i-propoxy tin
- dry silica fine particles of the present invention As an external additive for toner, Such as hexamethylsilazane, dimethyl silicone oil, r-aminopropyltriethoxysilane, r- (2-aminoethyl) aminopropylmethyldimethoxysilane, etc. It is good.
- a surface treatment method using a surface treatment agent a known method can be used without any limitation. For example, a method of spraying a surface treatment agent with dry silica fine particles while stirring or contacting with a vapor is common.
- the amount of the surface treatment with the surface treatment agent described above may be an appropriate amount depending on the application, but when used as an external additive for toner, 1 to 80 parts by weight per 100 parts by weight of dry silica fine particles. The range of is appropriate.
- dry silica fine particles of the present invention are limited to the above-described use as a resin composition for semiconductor sealing, liquid crystal sealing or insulating layer formation of a laminated substrate, and as an external additive for toner. It can be used for other purposes either alone or in combination with other particles.
- quartz crucibles quartz glass members such as optical fibers, polishing materials such as CMP, adhesives such as photoreactive adhesives, cosmetics, precision resin molded material fillers, dental material fillers, LED sealants, Carrier tape film for IC tape automated bonding, IC lead frame fixing tape, ink jet paper coating layer, electrophotographic photosensitive member protective layer, electrophotographic photosensitive member cleaning material, various resin films, paints It can also be suitably used for applications such as paint additives such as decoloring agents, antiblocking agents, hard coat agents, and raw materials for reflection molded articles.
- SA-1000 specific surface area measuring device manufactured by Shibata Rikagaku Co., Ltd.
- the nitrogen adsorption BET one-point method was used.
- the absorbance of an aqueous suspension having a silica concentration of 1.5% by weight with respect to light having a wavelength of 700 nm was measured using a spectrophotometer (V-530) manufactured by Enomoto Spectroscopy.
- the measurement sample cell is a synthetic quartz cell manufactured by Tokyo Glass Instruments Co., Ltd.
- a water suspension with a silica concentration of 1.5% by weight was prepared as follows.
- a predetermined amount of monodispersed spherical silica particles having a particle size of 7 ⁇ 2 soil 0.1 j! M were added as coarse particles to the silica fine particles prepared in Example 1 to be described later.
- Coarse particle content was quantified with a wet sieve using jWm electroformed sieve.
- the measurement is performed with a water dispersion medium using a laser diffraction scattering type particle size distribution measuring device (LA-920) manufactured by Horiba, The content of coarse particles of 5 m or more was quantified.
- the particle size distribution measurement method by the laser diffraction scattering method has low detection sensitivity of coarse particles, and quantification of coarse particles at the p pm level Is impossible.
- An epoxy resin composition was prepared as described below, and the characteristics of the resin composition were evaluated (viscosity characteristics, gap penetration, presence of voids).
- a glass plate and polyimide tape formed with a width of 1 Omm, a length of 50 mm, and a gap size of 50 // m After maintaining a gap of 90 m at a temperature of 90 ° C, the epoxy resin composition was dropped into one opening and left for 5 minutes. The distance permeated with was measured.
- the elements of iron, aluminum, chromium, nickel, sodium and chlorine were quantified by ICP emission spectrophotometry, atomic absorption spectrophotometry and ion chromatography.
- Silica fine particles were produced by burning octamethylcyclotetrasiloxane in a triple pipe furnace as follows.
- Table 2 shows the characteristics of the resin composition (viscosity, gap penetration, presence of voids) as the absorbance of the suspension.
- Table 3 shows the results of impurity analysis.
- R SFL Auxiliary Fuel Ratio
- Rcmb ts Combustion Oxygen Ratio
- F (S) 24 OS— 14 — 0. 07
- silica fine particles obtained in the above examples and comparative examples were evaluated for characteristics (image characteristics, cleaning properties) as an electrophotographic toner external additive by the following method.
- each silica fine particle obtained in Examples and Comparative Examples was placed in a mixer, stirred, and replaced with a nitrogen atmosphere and simultaneously heated to 250 ° C. Thereafter, the mixer was closed, 20 parts by weight of hexamethyldisilazane was sprayed onto 100 parts by weight of the silica fine particles, and the mixture was stirred as it was for 30 minutes to carry out a hydrophobic treatment.
- the silica particles thus hydrophobized were evaluated for image characteristics and cleaning properties, and the results are shown in Table 4.
- Toner resin particles having an average particle diameter of 7 m were added with 1% by weight of the hydrophobic particle sample hydrophobized as described above, and mixed by stirring to prepare a toner composition.
- This toner composition 30,000 copies were made with a commercially available copying machine (using an organic photosensitive drum), and the image density, presence or absence of capri, etc. were visually observed and evaluated.
- the evaluation criteria are as follows.
- Image density is low, capri is generated, or image is uneven.
- Residual toner is considerably large, and vertical stripe-like image defects occur.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silicon Compounds (AREA)
- Developing Agents For Electrophotography (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Description
Claims
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KR1020087029912A KR101206685B1 (ko) | 2006-06-09 | 2007-05-22 | 건식 실리카 미립자 |
US12/303,535 US7803341B2 (en) | 2006-06-09 | 2007-05-22 | Fine dry silica particles |
EP07744191.3A EP2028158B1 (en) | 2006-06-09 | 2007-05-22 | Dry-process for the preparation of silica particles |
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EP (1) | EP2028158B1 (ja) |
KR (1) | KR101206685B1 (ja) |
CN (1) | CN104649282B (ja) |
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TWI492339B (zh) * | 2009-06-01 | 2015-07-11 | Shinetsu Chemical Co | A dam material composition for a bottom layer filler material for a multilayer semiconductor device, and a manufacturing method of a multilayer semiconductor device using the dam material composition |
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TW201731782A (zh) | 2015-12-18 | 2017-09-16 | 何瑞斯廓格拉斯公司 | 在多腔式爐中製備石英玻璃體 |
KR20180095622A (ko) | 2015-12-18 | 2018-08-27 | 헤래우스 크바르츠글라스 게엠베하 & 컴파니 케이지 | 내화성 금속으로 제조된 용융 도가니에서 실리카 유리 제품의 제조 |
EP3390304B1 (de) | 2015-12-18 | 2023-09-13 | Heraeus Quarzglas GmbH & Co. KG | Sprühgranulieren von siliziumdioxid bei der herstellung von quarzglas |
WO2017103153A1 (de) | 2015-12-18 | 2017-06-22 | Heraeus Quarzglas Gmbh & Co. Kg | Glasfasern und vorformen aus quarzglas mit geringem oh-, cl- und al-gehalt |
JP6881776B2 (ja) | 2015-12-18 | 2021-06-02 | ヘレウス クワルツグラス ゲーエムベーハー ウント コンパニー カーゲー | 不透明石英ガラス体の調製 |
JP6881777B2 (ja) | 2015-12-18 | 2021-06-02 | ヘレウス クワルツグラス ゲーエムベーハー ウント コンパニー カーゲー | 合成石英ガラス粒の調製 |
CN108698888A (zh) | 2015-12-18 | 2018-10-23 | 贺利氏石英玻璃有限两合公司 | 在石英玻璃制备中作为中间物的经碳掺杂的二氧化硅颗粒的制备 |
EP3390303B1 (de) | 2015-12-18 | 2024-02-07 | Heraeus Quarzglas GmbH & Co. KG | Herstellung von quarzglaskörpern mit taupunktkontrolle im schmelzofen |
JP6727803B2 (ja) * | 2015-12-21 | 2020-07-22 | キヤノン株式会社 | トナーおよびトナーの製造方法 |
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JP7013662B2 (ja) | 2017-03-23 | 2022-02-01 | 富士フイルムビジネスイノベーション株式会社 | シリカ複合粒子及びその製造方法 |
CN113604182B (zh) * | 2021-08-16 | 2022-11-29 | 广东生益科技股份有限公司 | 一种树脂组合物及其应用 |
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- 2007-05-22 KR KR1020087029912A patent/KR101206685B1/ko active IP Right Grant
- 2007-05-22 WO PCT/JP2007/060757 patent/WO2007142047A1/ja active Application Filing
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TW200804186A (en) | 2008-01-16 |
EP2028158B1 (en) | 2017-01-18 |
US7803341B2 (en) | 2010-09-28 |
TWI395712B (zh) | 2013-05-11 |
CN104649282B (zh) | 2017-06-13 |
CN104649282A (zh) | 2015-05-27 |
EP2028158A4 (en) | 2012-03-28 |
EP2028158A1 (en) | 2009-02-25 |
KR20090018102A (ko) | 2009-02-19 |
US20090253851A1 (en) | 2009-10-08 |
KR101206685B1 (ko) | 2012-11-29 |
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