WO2018184486A1 - 硅油处理的热解法二氧化硅、其制造方法及应用 - Google Patents

硅油处理的热解法二氧化硅、其制造方法及应用 Download PDF

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WO2018184486A1
WO2018184486A1 PCT/CN2018/080614 CN2018080614W WO2018184486A1 WO 2018184486 A1 WO2018184486 A1 WO 2018184486A1 CN 2018080614 W CN2018080614 W CN 2018080614W WO 2018184486 A1 WO2018184486 A1 WO 2018184486A1
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silicone oil
fumed silica
treated fumed
polyetheramine
treated
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PCT/CN2018/080614
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English (en)
French (fr)
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前原孝之
周庆涛
戴建璋
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株式会社德山
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Priority to US16/495,191 priority Critical patent/US11254821B2/en
Priority to EP18781493.4A priority patent/EP3608381A4/en
Priority to KR1020197026139A priority patent/KR102319929B1/ko
Priority to JP2019548391A priority patent/JP6982627B2/ja
Publication of WO2018184486A1 publication Critical patent/WO2018184486A1/zh

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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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4085—Curing agents not provided for by the groups C08G59/42 - C08G59/66 silicon containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5026—Amines cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • 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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • 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.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y10T428/2995—Silane, siloxane or silicone coating

Definitions

  • the invention relates to the technical field of silica, in particular to the technical field of fumed silica, in particular to a silicone oil treated fumed silica, a manufacturing method thereof and an application thereof.
  • Epoxy resin is the most common type of adhesive in the adhesive.
  • the main component of the epoxy resin is the main component and the main component is the curing agent of the polyether amine compound (hereinafter referred to as polyether amine curing agent).
  • Cooperate used as a two-component epoxy system adhesive. From the construction point of view, the adhesive needs to have good thickening and anti-sagging properties. From the viewpoint of handling properties when mixed with an epoxy resin, the polyether amine curing agent also needs to have the above properties, so a rheological agent needs to be added in the polyether amine curing agent.
  • Silica is often used as a rheological agent, the most common of which is the silica produced by the combustion decomposition process, so-called fumed silica.
  • the surface of the fumed silica is hydrophobized to reduce the density of the surface silanol groups and increase the thickening property.
  • the most suitable surface treatment agent is silicone oil (for example, see JP-A-2004-99690).
  • the surface silicone oil-treated product of the fumed silica mentioned above is obtained by first spraying a fumed silica with a silicone oil at a high temperature and then performing heat treatment for a certain period of time.
  • a fumed silica with a silicone oil at a high temperature
  • heat treatment for a certain period of time.
  • the silicone oil spray treatment of the fumed silica the silicone oil which is not combined with the fumed silica is excessively heated, and the silicone oil is oxidized and decomposed to be largely volatilized, and is easily flammable.
  • the above-described spray treatment is carried out under an inert gas atmosphere such as nitrogen, and the above heat treatment is also carried out under the same inert gas atmosphere, which is a general method (see Chinese Patent Application Publication No. CN101755017A). And Chinese invention patent application publication specification CN103435056A).
  • the series of surface treatments described above can be carried out at relatively low temperatures below 150 °C. (Please refer to Japanese Patent Laid-Open No. 7-271087 (paragraph 0067)).
  • a silicone oil-treated fumed silica which has good thickening property and thickening stability when mixed with a polyetheramine compound, and It can be used in polyether amine compositions for two-component epoxy system adhesives, suitable for large-scale popularization applications.
  • Another object of the present invention is to provide a method for preparing a silicone oil-treated fumed silica, which is simple in preparation, low in cost, and suitable for large-scale popularization and application.
  • Another object of the present invention is to provide a silicone oil-treated fumed silica which has good thickening and thickening stability when used for mixing with a polyetheramine compound, and can be used for
  • the polyether amine composition of the two-liquid epoxy system adhesive is suitable for large-scale popularization and application.
  • a silicone oil-treated fumed silica characterized in that the silicone oil-treated fumed silica has the following physical properties of A) to C):
  • the degree of hydrophobicity is 68% by volume or more
  • the silicone oil immobilization rate is 60% by mass to 95% by mass
  • the silicone oil-treated fumed silica has a specific surface area of 50 to 130 m 2 /g.
  • the total carbon content of the silicone oil-treated fumed silica is 5% by mass to 8% by mass.
  • the metal impurities of the silicone oil-treated fumed silica include Na, K, Ca, Mg, Fe, and Al, and the content of the metal impurities is 0.1 ppm or less.
  • the silicone oil-treated fumed silica further has physical properties: D) using a polyetheramine composition prepared by the same method as described in the above C), and measuring thixotropic properties after measuring at 25 ° C for 1 hour ( TI) is above 4.8.
  • the silicone oil-treated fumed silica further has physical properties: D') is calculated using the polyetheramine composition prepared by the same method as the above C), and the TI residual ratio in the following formula is 45%. the above:
  • TI residual ratio (%) TI x 100 after the polyetheramine composition was subjected to a constant temperature of 25 ° C for 31 hours, and the polyetheramine composition was heated at 25 ° C for 1 hour.
  • the silicone oil-treated fumed silica further has physical properties: C') is calculated using the polyetheramine composition prepared by the same method as the above C), and the viscosity residual ratio in the following formula is 70%. the above:
  • Viscosity residual ratio (%) viscosity of the polyetheramine composition after being kept at a constant temperature of 31 ° C for 31 hours ⁇ viscosity of the polyetheramine composition after thermosetting at 25 ° C for 1 hour ⁇ 100.
  • the polyetheramine composition is a polyetheramine curing agent for an adhesive.
  • the adhesive is a two-part epoxy system adhesive.
  • the silicone oil-treated fumed silica is prepared by adhering a surface of a fumed silica to a silicone oil under an inert gas atmosphere of 150 ° C to 300 ° C, and then at 150 ° C. High temperature treatment in an oxygen environment of ⁇ 300 °C.
  • the oxygen environment has an oxygen concentration of 12% by volume or more.
  • the inert gas environment is a nitrogen atmosphere.
  • the fumed silica has a specific surface area of from 30 m 2 /g to 420 m 2 /g.
  • the fumed silica has a bulk density of from 20 g/L to 70 g/L.
  • the silicone oil is dimethyl silicone oil.
  • the silicone oil has a viscosity at 25 ° C of 20 cSt to 500 cSt.
  • the polyetheramine system composition is used as a curing agent in a two-part epoxy system adhesive.
  • a method for preparing a silicone oil-treated fumed silica characterized in that the method for preparing the silicone oil-treated fumed silica comprises the following steps: at 150 ° C - The surface of the fumed silica is adhered to the silicone oil in an inert gas atmosphere at 300 ° C, and then subjected to a high temperature treatment in an oxygen atmosphere at 150 ° C to 300 ° C to obtain a silicone oil-treated fumed silica.
  • the oxygen environment has an oxygen concentration of more than 12% by volume.
  • the inert gas environment is a nitrogen atmosphere.
  • the fumed silica has a specific surface area of from 30 m 2 /g to 420 m 2 /g.
  • the fumed silica has a bulk density of from 20 g/L to 70 g/L.
  • the silicone oil is dimethyl silicone oil.
  • the viscosity of the silicone oil at 25 ° C is from 20 cSt to 500 cSt.
  • the silicone oil-treated fumed silica has the following physical properties of A) to C):
  • the degree of hydrophobicity is 68% by volume or more
  • the silicone oil immobilization rate is 60% by mass to 95% by mass
  • the silicone oil-treated fumed silica has a specific surface area of from 15 m 2 /g to 210 m 2 /g.
  • the total carbon content of the silicone oil-treated fumed silica is 5% by mass to 8% by mass.
  • the metal impurities Na, K, Ca, Mg, Fe, and Al of the silicone oil-treated fumed silica are each 0.1 ppm or less.
  • the silicone oil-treated fumed silica further has physical properties: D) the thixotropy after measuring at 25 ° C for 1 hour using a polyether amine composition prepared by the same method as described in C) (TI) ) is above 4.8.
  • silicone oil-treated fumed silica further has physical properties: D') is calculated using the polyetheramine composition prepared by the same method as the above C), and the TI residual ratio in the following formula is 45. %the above:
  • TI residual ratio (%) TI x 100 after the polyetheramine composition was subjected to a constant temperature of 25 ° C for 31 hours, and the polyetheramine composition was heated at 25 ° C for 1 hour.
  • the silicone oil-treated fumed silica further has physical properties: C') is calculated using the polyetheramine composition prepared by the same method as the above C), and the viscosity residual ratio in the following formula is 70. %the above:
  • Viscosity residual ratio (%) viscosity of the polyetheramine composition after being kept at a constant temperature of 31 ° C for 31 hours ⁇ viscosity of the polyetheramine composition after thermosetting at 25 ° C for 1 hour ⁇ 100.
  • the polyetheramine composition is a polyetheramine curing agent for an adhesive.
  • the adhesive is a two-component epoxy system adhesive.
  • a silicone oil-treated fumed silica which is prepared by the above-described method for preparing a silicone oil-treated fumed silica.
  • the silicone oil-treated fumed silica of the present invention has the following physical properties of A) to C): A) a hydrophobicity of 68% by volume or more; B) a silicone oil immobilization ratio of 60% by mass to 95% by mass; and C) at 100 6 parts by mass of the silicone oil-treated fumed silica is added to the parts by mass of the polyetheramine composition, and the polyether amine composition includes trimethylolpropane polyoxypropyleneamine and 1,3 cyclohexane
  • the amine, the mass ratio of the trimethylolpropane polyoxypropylene amine to the 1,3 cyclohexanedimethylamine is 95:5, and the viscosity of the obtained polyetheramine composition after standing at 25 ° C for 1 hour is 4000mPa ⁇ s or more, therefore, it has good thickening property and thickening stability when mixed with polyetheramine compound, and can be used in polyether amine composition for epoxy resin, suitable for large-scale popularization. application.
  • the preparation method of the silicone oil-treated fumed silica of the present invention comprises the steps of: adhering the surface of the fumed silica to the silicone oil under an inert gas atmosphere of 150 ° C to 300 ° C, and then at 150 ° C -
  • the high temperature treatment is carried out in an oxygen environment of 300 ° C. Therefore, the preparation is simple and the cost is low, and it is suitable for large-scale popularization and application.
  • the silicone oil-treated fumed silica of the present invention can be contained in a polyether amine curing agent for a two-component epoxy system adhesive, and can be used for preparing a two-component epoxy resin adhesive.
  • a polyetheramine curing agent which can be used as a rheological agent in a polyetheramine curing agent for a two-component epoxy system adhesive, and therefore has a good increase in mixing with a polyetheramine compound. It has thickness and thickening stability, and can be used in polyetheramine compositions for epoxy resins, and is suitable for large-scale popularization applications.
  • the present invention relates to a fumed silica which is surface-treated by silicone oil and which satisfies the physical properties of the following A) to C):
  • the degree of hydrophobicity is 68% by volume or more
  • the silicone oil immobilization rate is 60 to 95% by mass
  • the present invention also relates to a method for producing the above-mentioned silicone oil heat treatment after the silicone oil is adhered to the surface of the fumed silica in an inert gas atmosphere of 150-300 ° C, and then switched to an oxygen gas atmosphere containing 150-300 ° C for high-temperature treatment.
  • a method for producing a fumed silica by a silicone oil treatment of silica is also referred to a method for producing the above-mentioned silicone oil heat treatment after the silicone oil is adhered to the surface of the fumed silica in an inert gas atmosphere of 150-300 ° C, and then switched to an oxygen gas atmosphere containing 150-300 ° C for high-temperature treatment.
  • a further invention is a curing agent for a two-component epoxy system adhesive containing a polyether amine compound and the above-mentioned silicone oil-treated fumed silica, which is used in a two-component epoxy resin adhesive.
  • Silicone oil treats fumed silica, because silica as a raw powder requires very low water content and metal impurities, and has good fluidity, so it is made by using fumed silica, that is, by combustion decomposition method.
  • the resulting silica refers to a method of producing a silica particle by burning a silicon compound or metal silicon in an oxyhydrogen flame.
  • a silicon compound such as silicon tetrachloride is generally used.
  • fumed silica is also called fumed silica or fumed silica.
  • the specific surface area measured by the BET1 point method is from 30 to 420 m 2 /g, preferably from 100 to 350 m 2 /g, more preferably from 120 to 250 m 2 /g.
  • the bulk density of the fumed silica is 20 to 70 g/L, preferably 25 to 50 g/L.
  • the above bulk density was calculated by placing a weighed fumed silica in a 1 L graduated cylinder and placing it for 30 minutes.
  • the fumed silica used as the raw powder is hydrophilic because it has a silanol group on the surface before being treated with the silicone oil, and does not contain carbon, and generally has a degree of hydrophobicity of zero.
  • the silicone oil used for the surface treatment is not particularly limited, and is, for example, dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, carboxyl modified silicone oil, polyether modified silicone oil, alkyl modified silicone oil, fluorine modified silicone oil. Wait. The most desirable is dimethicone.
  • the viscosity of the above silicone oil is preferably measured at 25 ° C and is preferably from 20 to 500 cSt.
  • the viscosity of the above silicone oil is preferably measured at 25 ° C and is preferably from 20 to 500 cSt.
  • the silicone oil volatilizes and the surface treatment cannot be sufficiently performed; when it exceeds 500 cSt, the viscosity is too high and the uniformity of the treatment is deteriorated.
  • the most preferable viscosity range is 50 to 200 cSt. Silicone oil can also be used in combination of two or more.
  • the silicone oil-treated fumed silica of the present embodiment is obtained by surface-treating the fumed silica with the above-mentioned silicone oil, and satisfies the physical properties of the following A) to C).
  • the degree of hydrophobicity is 68% by volume or more
  • the silicone oil immobilization rate is 60 to 95% by mass
  • the degree of hydrophobicity is 68% by volume or more, and most preferably 70% by volume or more.
  • the high degree of hydrophobicity indicates that the surface of the fumed silica is sufficiently treated with silicone oil, which is very important to improve the dispersibility of the silicone oil treated fumed silica in various polyether amine system compositions.
  • Silicone-treated fumed silica has a lower degree of hydrophobicity and a lower viscosity in the polyetheramine system composition, which is not particularly desirable.
  • the upper limit of the degree of hydrophobicity is not particularly specified, but is generally 80% by volume or less, preferably 75% by volume or less. .
  • the A) degree of hydrophobicity in the silicone oil-treated fumed silica of the present embodiment is obtained by adding 0.2 g of silicone oil-treated fumed silica to a 250 mL beaker having 50 mL of water, followed by slowly adding methanol.
  • the silicone oil-treated fumed silica powder is wetted by the solution in the beaker, the measurement is performed, and the methanol volume % in the methanol-water mixed solution at the end point is determined.
  • the silicone oil immobilization ratio is 60 to 95% by mass, preferably 70 to 95% by mass, more preferably 70 to 90% by mass.
  • the silicone oil present on the surface of the fumed silica particles treated with silicone oil has two forms, one is "immobilized silicone oil” combined with the surface of fumed silica, and the other is physically adsorbed on fumed silica.
  • the surface of the "free silicone oil.” Therefore, even if the surface of the fumed silica is coated with a large amount of silicone oil by surface treatment, and the above hydrophobicity is very high, if the above-mentioned free silicone oil accounts for a large portion, it is actually mixed into the polyetheramine system composition.
  • the silicone oil immobilization rate of the above silicone oil-treated fumed silica needs to be maintained within the above-mentioned high range.
  • the "silicone oil immobilization rate FR [%]" is as shown in the following formula.
  • F(OIL) represents the amount of immobilized silicone oil [g]
  • T(OIL) represents the amount of silicone oil [g] equivalent to the total carbon content.
  • the amount of silicone oil T (OIL) equivalent to the total carbon content represented by the formula (1) and the amount of immobilized silicone oil F (OIL) can be obtained by the following method.
  • T (Oil) T (carbon) ⁇ molecular weight of the silicone oil used / carbon content in one molecule of the silicone oil used.
  • the molecular weight of the silicone oil used and the carbon content of one molecule of the silicone oil used can be calculated as the value per unit structure of the silicone oil main chain.
  • the same formula (3) is the same.
  • the solid was dried under reduced pressure (120 ° C, 12 hours) to obtain a dry powder, and the weight was measured, and the total weight [g] of the silica in which only the immobilized silicone oil remained was detected.
  • 0.1 g of the silica in which the immobilized silicone oil remained, and the carbon content was measured by a combustion method using a carbon content detecting device (SUMIGRAPH NC-2 2F manufactured by Sumitomo Chemical Co., Ltd.) to obtain an immobilized silicone oil.
  • Carbon content F (Carbon) [g] is calculated according to the following formula (3).
  • F (Oil) F (carbon) ⁇ molecular weight of the silicone oil used / carbon content in one molecule of the silicone oil used ⁇ total weight of silica in which only the immobilized silicone oil remains [g] / 0.1g[g] ⁇ 0.1[g]/0.5[g]
  • the liquid phase obtained by centrifugal separation contains free silicone oil physically adsorbed on the surface.
  • the free silicone oil amount I(Oil) [g] is represented by the following formula (4).
  • Mb represents a value obtained by subtracting the amount of silicone oil T(Oil) [g] equivalent to the total carbon content from the mass (0.1 g) of the silica oil treated by the combustion method (the silicone oil for processing) The mass of the silica particle body [g] after removal of the silicone oil in 0.1 g of silicon oxide.
  • S represents the specific surface area [m 2 /g] of the raw material fumed silica used for the production of silicone oil for the detection of silica.
  • the specific surface area S of the raw material fumed silica is not known, it can be obtained by the following method. First, the silicone oil-treated silica is heated at 650 ° C or higher for 2 hours or more to thermally decompose the immobilized silicone oil and the free silicone oil. The bulk of the silica particles (i.e., the raw material fumed silica) from which the silicone oil of the surface is removed can be obtained. Next, the main body of the obtained silica particles is subjected to heat treatment, and the specific surface area of the raw material fumed silica is obtained by detecting the specific surface area by the BET1 point method.
  • the silicone oil-treated fumed silica of the present invention preferably has a carbon content of from 3 to 8% by mass, more preferably from 5 to 8% by mass, from the viewpoint of sufficient degree of hydrophobicity.
  • silicone oil-treated fumed silica of the present invention has the following characteristics:
  • the fumed silica was treated by adding 6 parts by mass of a silicone oil, and the viscosity of the obtained polyetheramine composition after standing at 25 ° C for 1 hour was 4,000 mPa ⁇ s or more, and most preferably 4,000 to 10,000 mPa ⁇ s.
  • the polyetheramine composition is a typical form used as a curing agent for a two-component epoxy resin adhesive (for example, see JP-A-2015-524875).
  • the silicone oil-treated fumed silica having the above-mentioned A) hydrophobicity and B) silicone oil immobilization rate cannot be completely satisfied, so the silicone oil-treated fumed silica of the present embodiment is used as a poly
  • the silicone oil-treated fumed silica of the present embodiment is used as a poly
  • the polyetheramine composition shown in C) used in the etheramine curing agent is mixed, the viscosity can be increased.
  • the silicone oil-treated fumed silica of the present embodiment can be more uniformly used to immobilize the surface by using a silicone oil than a conventional technique by using a special production method or the like, and it is presumed that not only the above A) hydrophobicity and B) The silicone oil immobilization rate, the viscosity when mixed to the polyetheramine composition shown in C) should also be greatly improved. Further, it is presumed that various polyetheramine system compositions other than the polyetheramine composition shown in C) have the above-described work effects.
  • the measuring method of C) is specifically as follows. First, in 190 parts by mass of trimethylolpropane polyoxypropylene amine (CAS No.: 39423-51-36) (kinetic viscosity at 25 ° C is 72 cSt) and 10 parts by mass of 1,3-cyclohexanedimethylamine
  • the polyetheramine composition (CAS No.: 2579-20-6) was treated with 12 parts by mass of silicone oil to treat fumed silica. Thereafter, it was dispersed for 10 minutes using a high speed disperser at 4000 rpm.
  • the viscosity of the polyetheramine composition was calculated based on the measured value (mPa ⁇ s) of a BL type viscometer at 60 rpm.
  • the silicone oil-treated fumed silica of the present embodiment has the following physical properties: D) Thixotropy (TI) after constant temperature at 25 ° C for 1 hour by measuring the polyetheramine composition by the same method as the above C) It is preferably at least 4.8. The most ideal is between 4.8 and 6.0. TI can be calculated by the following formula. When the value is close to 1, it is Newtonian fluid. The higher the value, the better the thickening is, the better the anti-sagging is.
  • Viscosity at TI 6 rpm Viscosity at 60 rpm ⁇ 10
  • the B) silicone oil has a high immobilization rate, a good thickening stability, and the following physical properties:
  • the polyetheramine composition is obtained by the same method as the above C), and the viscosity residual ratio in the following formula is preferably 70% or more, and most preferably 72% or more.
  • Viscosity residual ratio (%) viscosity at 25 ° C for 31 hours at a constant temperature ⁇ viscosity at 25 ° C for 1 hour at a constant temperature ⁇ 100.
  • silicone oil-treated fumed silica of the present embodiment has the following physical properties:
  • the polyetheramine composition is obtained by the same method as the above C), and the TI residual ratio in the following formula is preferably 45% or more, and most preferably 46% or more.
  • TI residual ratio (%) TI ⁇ 100 after 1 hour after the start of the constant temperature of 25 ° C after 31 hours of constant temperature start.
  • the specific surface area of the silicone oil-treated fumed silica of the present embodiment is changed depending on the specific surface area of the fumed silica as the raw powder and the amount of the silicone oil to be used, and therefore cannot be determined. It is usually 15 to 210 m 2 /g, preferably 40 to 180 m 2 /g, and most preferably 50 to 130 m 2 /g.
  • the silicone oil-treated fumed silica of the present embodiment has very few metal impurities as compared with the precipitated silica synthesized in the solution, and is used in combination. It is very advantageous if the polyetheramine compound is a polyetheramine curing agent used in an epoxy resin adhesive such as an electronic material.
  • the general metal impurities, Na, K, Ca, Mg, Fe, and Al are each 0.1 ppm or less.
  • the silicone oil-treated fumed silica of the present embodiment is a fumed silica surface-treated with a silicone oil, and can satisfy the physical properties of the above A) to C), and can be produced by any method, but is optimal.
  • the manufacturing method is exemplified as follows: a method in which a surface of a fumed silica is adhered to a silicone oil in an inert gas atmosphere of 150 to 300 ° C, and then switched to an oxygen atmosphere of 150 to 300 ° C to carry out a high temperature treatment.
  • the high temperature treatment is carried out in an oxygen atmosphere.
  • the uniformity of the immobilization of the silicone oil on the surface of the fumed silica is remarkably improved, not only the above A) hydrophobicity and B) the increase in the immobilization rate of the silicone oil, but also the polyetheramine composition shown in C).
  • the viscosity is also high.
  • the most common method is that the high-temperature treatment after the adhesion of the silicone oil is carried out under a nitrogen atmosphere. At this time, the immobilization of the free silicone oil present on the surface of the fumed silica does not sufficiently function. As a result, the surface treatment of the silicone oil is not uniform, and the physical properties of the prepared silicone oil-treated fumed silica cannot satisfy the physical properties of the above C).
  • the silicone oil adhesion treatment on the surface of the fumed silica needs to be carried out in an inert gas atmosphere such as nitrogen gas, and the high temperature treatment after the silicone oil adhesion treatment needs to be switched to After the oxygen environment, proceed. That is, if it is desired that the silicone oil adhesion treatment effect on the surface of the fumed silica is more uniform, it is preferably carried out at a high temperature of 150 to 300 ° C as described above.
  • the silicone oil spray treatment of the fumed silica the amount of the silicone oil which cannot be combined with the fumed silica is overheated, and the silicone oil oxidizes and decomposes a large amount of volatilization, and is easy to generate a flammable substance. Therefore, from the viewpoint of safety, the above-described spray treatment needs to be carried out in an inert gas atmosphere such as nitrogen.
  • the temperature of the silicone oil adhering treatment on the surface of the fumed silica and the subsequent high temperature treatment are preferably 200 to 300 °C.
  • the above treatment temperature is lower than 150 ° C, the silicone oil cannot be uniformly surface-treated, and the obtained silicone oil-treated fumed silica cannot satisfy the viscosity when the polyether amine composition shown in C) is mixed.
  • the specified value of the present invention cannot be achieved.
  • the amount of adhesion of the silicone oil of the fumed silica varies depending on the specific surface area of the fumed silica used as the raw material, and therefore cannot be generalized, but from the viewpoint of producing the silicone oil-treated silica of the present embodiment. It is preferably from 3 to 50 parts by mass, more preferably from 10 to 30 parts by mass, per 100 parts by mass of the raw material fumed silica.
  • the inert gas used in the silicone oil adhesion treatment is preferably nitrogen gas, but may be an inert gas such as argon gas or helium gas.
  • the high-temperature treatment of the fumed silica after the adhesion of the silicone oil is switched from the inert gas atmosphere to the oxygen gas atmosphere, it is preferably carried out while stirring as in the case of the silicone oil spray.
  • this high-temperature treatment more than half of the already sprayed silicone oil has been combined with the surface of the fumed silica, so that it is the same as the silicone oil adhesion treatment, and the risk of ignition is small, and the stirring treatment can be performed.
  • the oxygen concentration of the oxygen gas is not particularly limited as long as it is sufficient to promote the volatilization of the free silicone oil on the surface of the fumed silica, but is preferably 12% by volume or more, preferably 18% by volume or more. In consideration of safety, the oxygen concentration is preferably 30% by volume or less.
  • the oxygen gas may be a gas component other than oxygen, and may be an inert gas or the like as described above.
  • the oxygen gas may have an oxygen concentration of 21% by volume, so air may also be used.
  • the high temperature treatment after the adhesion of the silicone oil is preferably carried out for 30 minutes or longer, preferably 60 to 180 minutes.
  • the silicone oil-treated fumed silica of the present embodiment is a kind of hydrophobic silica, and is used in various applications such as electronic materials and building materials, and can also be used in combination with functional materials. In consideration of the superior thickening effect in the above polyetheramine compound, it is preferably used in combination with an additive for a polyetheramine system composition containing a polyetheramine compound (main component). It is preferable to use the silicone oil-treated silica of the present embodiment as an additive for a polyether amine curing agent formulation of an epoxy resin (especially for a two-component epoxy resin adhesive for use in electronic materials, etc.). The use of the silicone oil-treated fumed silica of the present embodiment is highly advantageous because it has high viscosity and is anti-sagging, and has excellent workability.
  • the polyether amine curing agent of the two-liquid epoxy resin adhesive, the silicone oil-treated fumed silica in the present embodiment is selected as a typical state in C) which defines its good thickening property.
  • the above C) trimethylolpropane polyoxypropylene amine (kinetic viscosity at 25 ° C is 72 cSt): 1,3-cyclohexanedimethylamine 95:5 mass ratio is the best.
  • the polyetheramine curing agent containing a polyetheramine compound as a main component any known component can be a formulation target of the silicone oil-treated fumed silica of the present embodiment, and is not limited.
  • the silicone oil-treated silica of the present embodiment can be applied to a polyetheramine system composition which can be used in various applications other than the polyether amine curing agent of the two-component epoxy resin adhesive.
  • polyetheramine curing agent of the various polyetheramine compounds such as aminoethylpiperazine and 1,3-cyclohexanedimethylamine, or the polyetheramine curing agent
  • a polyetheramine system composition used in various applications.
  • the polyetheramine system composition in addition to the above amine compound, other pigments, dyes and the like may be added.
  • the polyetheramine system composition particularly in the polyether amine curing agent, the formulation amount of the silicone oil-treated fumed silica of the present embodiment is generally 2 to 15 mass in 100 parts by mass of the polyetheramine compound. Share.
  • the viscosity after leaving at 25 ° C for 1 hour is 4,000 mPa ⁇ s or more, preferably 4,500 to 10,000 mPa ⁇ s.
  • the silicone oil-treated fumed silica of the present embodiment has a good thickening effect in the polyetheramine system composition, and it is only necessary to add 2 to 10 masses to 100 parts by mass of the polyetheramine compound. In part, it is possible to achieve various uses, in particular the viscosity desired for the use of polyetheramine curing agents.
  • the silicone oil-treated fumed silica of the present embodiment can be used not only in the polyetheramine curing agent but also in the main component containing the epoxy resin (main component) used in combination with the polyetheramine curing agent. .
  • the silicone oil-treated fumed silica of the present embodiment has good thickening property, and has good mixing property when used in combination with a polyether amine curing agent.
  • the resulting mixed composition has high viscosity, is difficult to sag, and has good handleability.
  • the specific surface area of fumed silica and silicone oil-treated fumed silica was measured by a BET1 point method based on the amount of nitrogen adsorption by using a specific surface area measuring device SA-1000 manufactured by Shibata Scientific Instruments.
  • 0.2 g of silicone oil-treated silica was added to a 250 mL beaker containing 50 mL of water and stirred with a magnetic stirrer. Thereafter, methanol was added thereto by using a burette, and the silica treated with the powdery silicone oil was all wetted by the solvent in the beaker to the end point for measurement. In order to prevent the methanol from directly contacting the silicone oil treated silica, a hose is added to the solution. The volume % of methanol in the methanol-water mixed solution at the end point is the degree of hydrophobicity.
  • F(OIL) represents the amount of immobilized silicone oil [g]
  • T(OIL) represents the amount of silicone oil [g] equivalent to the total carbon content.
  • F(OIL) and T(OIL) were obtained by the following methods.
  • the amount of silicone oil T (OIL) equivalent to the total carbon content expressed in the formula (1) and the amount of immobilized silicone oil F (OIL) can be obtained by the following method.
  • T(Oil) T(carbon) ⁇ molecular weight of the silicone oil used / carbon content in one molecule of the silicone oil used
  • the molecular weight of the silicone oil used and the carbon content of one molecule of the silicone oil used can be calculated as the value per unit structure of the silicone oil main chain.
  • the silicone oil treated on the surface of the silica is a silicone oil having dimethylsiloxane as a main chain, so the unit structural formula is: -(Si(CH3)2-O)-, Can be obtained by the following formula.
  • T(Oil) T(carbon) ⁇ (Si[28]+C[12] ⁇ 2+H[1] ⁇ 6+O[16]) ⁇ (C[12] ⁇ 2)
  • the solid was dried under reduced pressure (120 ° C, 12 hours) to obtain a dry powder, and the weight was measured, and the total weight [g] of the silica in which only the immobilized silicone oil remained was detected.
  • 0.1 g of the silica in which the immobilized silicone oil remains is used, and the carbon content is detected by a combustion method using a carbon content detecting device (SUMIGRAPHNC-22F, manufactured by Sumitomo Chemical Co., Ltd.) to determine the carbon content of the immobilized silicone oil.
  • F(Carbon)[g] the amount of immobilized silicone oil F(Oil) [g] is calculated according to the following formula (3).
  • F (Oil) F (carbon) ⁇ molecular weight of the silicone oil used / carbon content in one molecule of the silicone oil used ⁇ total weight of silica in which only the immobilized silicone oil remains [g] / 0.1g[g] ⁇ 0.1[g]/0.5[g] ⁇ stack density measurement>
  • the viscosity is a measured value (mPa ⁇ s) at 60 rpm of a BL type viscometer, and the formula for calculating TI is as follows.
  • the viscosity at TI 6 rpm ⁇ 60 rpm viscosity ⁇ 10.
  • the calculation formula of the viscosity residual ratio and the TI residual ratio is as follows.
  • the constant temperature means 25 °C.
  • Viscosity residual ratio (%) viscosity after 31 hours from the start of the constant temperature ⁇ viscosity after one hour from the start of the constant temperature ⁇ 100.
  • TI residual ratio (%) TI ⁇ 100 after one hour after the start of the constant temperature of TI 31 31 hours after the start of the constant temperature.
  • the fumed silica was treated with 53 g of silicone oil in 1 kg of epoxy resin (EPIKOTE 828, manufactured by HEXION Specialty Chemicals, Inc.), and the silicone oil-treated silica was dispersed by stirring for about 1 hour.
  • 53 g of silicone oil was added to 1 kg of a polyetheramine curing agent (JEFAMIN T-403 manufactured by HUNTSMAN Co., Ltd.) to treat fumed silica, and the silica was dispersed by stirring for about 1 hour.
  • the adjusted epoxy resin and the polyetheramine curing agent were mixed in a volume ratio of 1:1, and 30 cm was applied horizontally from left to right on the wall using a spray gun to confirm the sag.
  • the anti-sagging effect will be drooped by gravity, and the anti-sagging effect will be good. It will not sag and can maintain the state just after coating.
  • a closed triple tube head having an inner tube inner diameter of 100 mm is placed in a closed reactor, and silicon tetrachloride (STC) as a material gas and hydrogen gas, and air as a combustion-supporting gas are previously mixed, and the mixed gas is supplied to In the center tube. Hydrogen and air are supplied to the first annular tube to form an ignition flame. Air is circulated through the second annular tube to prevent adhesion of fumed silica particles to the base.
  • STC silicon tetrachloride
  • Air is circulated through the second annular tube to prevent adhesion of fumed silica particles to the base.
  • the desired specific surface area can be obtained by adjusting the amount of the raw material gas supplied to the central pipe and the amount of the combustion-supporting gas.
  • the viscosity of the silicone oil used and the specific surface area of the fumed silica were changed as shown in Table 1, and the method was the same as in the first embodiment.
  • the properties of the prepared silicone oil-treated silica were as shown in Table 1 and Table 2, and the metal impurity contents are shown in Table 3.
  • the operation was the same as that of the case 1 except that the replacement in the container of the embodiment 1 was changed to an oxygen concentration of 15% by volume.
  • the physical properties of the obtained silicone oil-treated silica and the like are shown in Table 1 and Table 2, and the metal impurity contents are shown in Table 3.
  • the operation was the same as in the first embodiment except that the air was not replaced after the silicone oil was sprayed, and after the spray was maintained at 260 ° C for 1 hour and then at 260 ° C for 1 hour in a nitrogen atmosphere.
  • the physical properties of the obtained silicone oil-treated silica and the like are shown in Table 1 and Table 2, and the metal impurity contents are shown in Table 3.
  • the specific surface area of the fumed silica was changed as shown in Table 1, and the silicone oil-treated silica was obtained by the same method as in the case of Example 1.
  • the physical properties of the obtained silicone oil-treated silica and the like are shown in Table 1 and Table 2, and the metal impurity contents are shown in Table 3.
  • Viscosity and TI time are the time after the detection liquid is placed at a constant temperature of 25 °C.
  • the present invention provides a silicone oil-treated fumed silica which can impart a higher thickening effect than a prior art in a resin composition using an epoxy resin and a polyetheramine curing agent.
  • a silicone oil-treated fumed silica which can impart a higher thickening effect than a prior art in a resin composition using an epoxy resin and a polyetheramine curing agent.
  • the silicone oil-treated fumed silica of the invention has high hydrophobicity and high silicone oil immobilization rate, and can impart a good thickening effect to the polyetheramine compound, and has good thickening stability.
  • the silicone oil-treated fumed silica of the present invention is suitable for a polyetheramine curing agent for an epoxy resin, and has characteristics of high viscosity, sag resistance, and easy handling.
  • Fumed silica which is a raw powder, generally has very few metallic impurities, and is therefore particularly suitable for epoxy resin adhesives for use in electronic materials and the like.
  • the silicone oil-treated fumed silica of the present invention has good thickening property and thickening stability when mixed with a polyether amine compound, and can be used in a polyether amine combination for an epoxy resin.
  • the preparation is simple, the cost is low, and it is suitable for large-scale popularization and application.

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Abstract

本发明提供一种硅油处理热解法二氧化硅，其具有以下A)～C)的物性：A)疏水度68体积％以上；B)硅油固定化率60质量％～95质量％；C)在三羟甲基丙烷聚氧丙烯胺和所述1,3环己二甲胺的质量比为95：5的100质量份的聚醚胺组成物中，添加6质量份的所述硅油处理热解法二氧化硅，所得到的聚醚胺组合物在25℃放置1小时后的粘度在4000mPa·s以上。较佳地，其是在150℃～300℃的惰性气体环境下，使热解法二氧化硅的表面粘附硅油，然后在150℃～300℃的氧气环境下，进行高温处理获得。还提供了相关的制备方法和应用。本发明的硅油处理热解法二氧化硅在和聚醚胺化合物混合时有良好的增稠性以及增稠稳定性，且可以用在用于二液型环氧体系胶黏剂的聚醚胺组合物中，制备简单，成本低，适于大规模推广应用。

Description

硅油处理的热解法二氧化硅、其制造方法及应用 技术领域
本发明涉及二氧化硅技术领域，特别涉及热解法二氧化硅技术领域，具体是指一种硅油处理的热解法二氧化硅、其制造方法及应用。
背景技术
胶黏剂在电子材料和建筑材料等中被广泛使用。在胶黏剂中环氧树脂胶黏剂是最常见的一类，一般会将主要成分是环氧树脂的主剂和主要成分是聚醚胺化合物的固化剂(以下简称聚醚胺固化剂)配合，作为二液型环氧体系胶黏剂使用。从施工方面考虑，胶黏剂需要有良好的增稠和防流挂等性能。从与环氧树脂混合时的操作性考虑，聚醚胺固化剂也需要拥有上述性能，所以在聚醚胺固化剂中需要添加流变剂。二氧化硅常被作为流变剂使用，其中最常见的是燃烧分解法所制得的二氧化硅，即所谓的热解法二氧化硅。
但是，热解法二氧化硅表面存在很多亲水性的硅醇基团，如果直接和聚醚胺固化剂混合，易和亲水性强的聚醚胺固化剂溶合，以至于达不到上述良好的增稠效果以及防流挂效果。因此会对热解法二氧化硅的表面进行疏水化处理，减少其表面硅醇基团的密度，提高增稠性。最合适的表面处理剂是硅油(例如：请参见日本特开2004-99690号公报)。
以往所提到的热解法二氧化硅的表面硅油处理品，是在高温下先对热解法二氧化硅进行硅油喷雾，再进行一定时间的加热处理后制得的。(请参见中国发明专利申请公开说明书CN101755017A、中国发明专利申请公开说明书CN103435056A以及日本特开平7-271087号公报)。上述热解法二氧化硅的硅油喷雾处理中，对于未与热解法二氧化硅结合的硅油会产生加热过剩，以及上述硅油会氧化分解大量挥发，且易副生易燃性物质。因此，从安全方面考虑，上述喷雾处理会在氮气等的惰性气体环境下进行，上述加热处理也会在相同的惰性气体环境下实施，这是一般的方法(请参见中国发明专利申请公开说明书CN101755017A和中国发明专利申请公开说明书CN103435056A)。另外，如果不在惰性气体环境下实施，上述一连串的 表面处理会在150℃以下的相对较低的温度下进行。(请参见日本特开平7-271087号公报(第0067段))。
但是，即使使用上述以往技术中所制得的硅油处理热解法二氧化硅，对于上述聚醚胺固化剂的分散性改善效果也是不充分的，如果想达到一定的增稠性以及防流挂性，在制备硅油处理热解法二氧化硅时需要添加大量的硅油。另外，即使在和聚醚胺固化剂的混合初期有较高的增稠性，随着时间的推移粘度也会慢慢降低，最好是能改善硅油处理热解法二氧化硅的增稠稳定性。
发明内容
为了克服上述现有技术中的缺点，本发明的一个目的在于提供一种硅油处理热解法二氧化硅，其在和聚醚胺化合物混合时有良好的增稠性以及增稠稳定性，且可以用在用于二液型环氧体系胶黏剂的聚醚胺组合物中，适于大规模推广应用。
本发明的另一个目的在于提供一种硅油处理热解法二氧化硅的制备方法，其制备简单，成本低，适于大规模推广应用。
本发明的另一个目的在于提供一种硅油处理热解法二氧化硅的应用，其在用于和聚醚胺化合物混合时有良好的增稠性以及增稠稳定性，且可以用在用于二液型环氧体系胶黏剂的聚醚胺组合物中，适于大规模推广应用。
为达到以上目的，在本发明的第一方面，提供一种硅油处理热解法二氧化硅，其特点是，所述硅油处理热解法二氧化硅具有以下A)～C)的物性：
A)疏水度68体积％以上；
B)硅油固定化率60质量％～95质量％；
C)在100质量份的聚醚胺组成物中添加6质量份的所述硅油处理热解法二氧化硅，所述聚醚胺组成物包括三羟甲基丙烷聚氧丙烯胺和1,3环己二甲胺，所述三羟甲基丙烷聚氧丙烯胺和所述1,3环己二甲胺的质量比为95：5，所得到的聚醚胺组合物在25℃放置1小时后的粘度在4000mPa·s以上。
较佳地，所述硅油处理热解法二氧化硅的比表面积是50～130m 2/g。
较佳地，所述硅油处理热解法二氧化硅的总碳含量是5质量％～8质量％。
较佳地，所述硅油处理热解法二氧化硅的金属杂质包括Na、K、Ca、Mg、Fe、Al，所述金属杂质的含量分别在0.1ppm以下。
较佳地，所述硅油处理热解法二氧化硅还具有物性：D)使用通过所述C)相同的方法制得的聚醚胺组合物，进行测量25℃恒温1小时后的触变(TI)在4.8以上。
更佳地，所述硅油处理热解法二氧化硅还具有物性：D’)使用通过所述C)相同方法制得的聚醚胺组合物进行计算，以下公式中的TI残存率在45％以上：
TI残存率(％)＝所述聚醚胺组合物在25℃恒温开始31小时后的TI÷所述聚醚胺组合物在25℃恒温开始1小时后的TI×100。
较佳地，所述硅油处理热解法二氧化硅还具有物性：C’)使用通过所述C)相同方法制得的聚醚胺组合物进行计算，以下公式中的粘度残存率在70％以上：
粘度残存率(％)＝所述聚醚胺组合物在25℃恒温31小时后的粘度÷所述聚醚胺组合物在25℃恒温1小时后的粘度×100。
较佳地，所述聚醚胺组成物是用于胶黏剂的聚醚胺固化剂。
更佳地，所述胶黏剂是二液型环氧体系胶黏剂。
较佳地，所述硅油处理热解法二氧化硅通过以下方法制备而成：在150℃～300℃的惰性气体环境下，使热解法二氧化硅的表面粘附硅油，然后在150℃～300℃的氧气环境下，进行高温处理。
更佳地，所述氧气环境的氧气浓度在12体积％以上。
更佳地，所述惰性气体环境是氮气环境。
更佳地，所述热解法二氧化硅的比表面积为30m 2/g～420m 2/g。
更佳地，所述热解法二氧化硅的堆积密度是20g/L～70g/L。
更佳地，所述硅油是二甲基硅油。
更佳地，所述硅油在25℃的粘度是20cSt～500cSt。
在本发明的第二方面，提供了上述的硅油处理热解法二氧化硅在在作为添加剂制备含有聚醚胺化合物的聚醚胺体系组合物的应用。
较佳地，所述聚醚胺体系组合物是作为二液型环氧体系胶黏剂中的固化剂使用。
在本发明的第三方面，提供了一种硅油处理热解法二氧化硅的制备方 法，其特点是，所述的硅油处理热解法二氧化硅的制备方法包括以下步骤：在150℃～300℃的惰性气体环境下，使热解法二氧化硅的表面粘附硅油，然后在150℃～300℃的氧气环境下，进行高温处理，从而获得硅油处理热解法二氧化硅。
较佳地，所述氧气环境的氧气浓度在12体积％以上。
较佳地，所述惰性气体环境是氮气环境。
较佳地，所述热解法二氧化硅的比表面积为30m 2/g～420m 2/g。
较佳地，所述热解法二氧化硅的堆积密度是20g/L～70g/L。
较佳地，所述硅油是二甲基硅油。
较佳地，所述硅油在25℃的粘度是20cSt～500cSt。
较佳地，所述硅油处理热解法二氧化硅具有以下A)～C)的物性：
A)疏水度68体积％以上；
B)硅油固定化率60质量％～95质量％；
C)在100质量份的聚醚胺组成物中添加6质量份的所述硅油处理热解法二氧化硅，所述聚醚胺组成物包括三羟甲基丙烷聚氧丙烯胺和1,3环己二甲胺，所述三羟甲基丙烷聚氧丙烯胺和所述1,3环己二甲胺的质量比为95：5，所得到的聚醚胺组合物在25℃放置1小时后的粘度在4000mPa·s以上。
更佳地，所述硅油处理热解法二氧化硅的比表面积是15m 2/g～210m 2/g。
更佳地，所述硅油处理热解法二氧化硅的总碳含量是5质量％～8质量％。
更佳地，所述硅油处理热解法二氧化硅的金属杂质Na、K、Ca、Mg、Fe、Al分别在0.1ppm以下。
更佳地，所述硅油处理热解法二氧化硅还具有物性：D)使用通过所述C)相同的方法制得的聚醚胺组合物进行测量25℃恒温1小时后的触变(TI)在4.8以上。
更进一步地，所述硅油处理热解法二氧化硅还具有物性：D’)使用通过所述C)相同的方法制得的聚醚胺组合物进行计算，以下公式中的TI残存率在45％以上：
TI残存率(％)＝所述聚醚胺组合物在25℃恒温开始31小时后的TI÷所述聚醚胺组合物在25℃恒温开始1小时后的TI×100。
更佳地，所述硅油处理热解法二氧化硅还具有物性：C’)使用通过所述C)相同的方法制得的聚醚胺组合物进行计算，以下公式中的粘度残存率在70％以上：
粘度残存率(％)＝所述聚醚胺组合物在25℃恒温31小时后的粘度÷所述聚醚胺组合物在25℃恒温1小时后的粘度×100。
更佳地，所述聚醚胺组成物是用于胶黏剂的聚醚胺固化剂。
更进一步地，所述胶黏剂是二液型环氧体系胶黏剂。
在本发明的第四方面，提供了一种硅油处理热解法二氧化硅，其特点是，采用上述的硅油处理热解法二氧化硅的制备方法制备而成。
在本发明的第五方面，提供了上述的硅油处理热解法二氧化硅在作为固化剂制备含聚醚胺化合物的二液型环氧体系胶粘剂的应用。
本发明的有益效果主要在于：
1、本发明的硅油处理热解法二氧化硅具有以下A)～C)的物性：A)疏水度68体积％以上；B)硅油固定化率60质量％～95质量％；C)在100质量份的聚醚胺组成物中添加6质量份的所述硅油处理热解法二氧化硅，所述聚醚胺组成物包括三羟甲基丙烷聚氧丙烯胺和1,3环己二甲胺，所述三羟甲基丙烷聚氧丙烯胺和所述1,3环己二甲胺的质量比为95：5，所得到的聚醚胺组合物在25℃放置1小时后的粘度在4000mPa·s以上，因此，其在和聚醚胺化合物混合时有良好的增稠性以及增稠稳定性，且可以用在用于环氧树脂的聚醚胺组合物中，适于大规模推广应用。
2、本发明的硅油处理热解法二氧化硅的制备方法包括以下步骤：在150℃～300℃的惰性气体环境下，使热解法二氧化硅的表面粘附硅油，然后在150℃～300℃的氧气环境下，进行高温处理，因此，其制备简单，成本低，适于大规模推广应用。
3、本发明的硅油处理热解法二氧化硅可以包含在用于二液型环氧体系胶黏剂的聚醚胺固化剂中，可以用于制备用于二液型环氧体系胶黏剂的聚醚胺固化剂，可以在用于二液型环氧体系胶黏剂的聚醚胺固化剂中用作流变剂，因此，其在用于和聚醚胺化合物混合时有良好的增稠性以及增稠稳定性，且可以用在用于环氧树脂的聚醚胺组合物中，适于大规模推广应用。
本发明的这些和其它目的、特点和优势，通过下述的详细说明和权利要求得以充分体现，并可通过所附权利要求中特地指出的手段、装置和它们的 组合得以实现。
具体实施方式
本发明人员通过很多次探讨和试验，其结果是成功地开发出了拥有高疏水度以及高硅油固定化率，且和聚醚胺固化剂混合时有良好的增稠性能的特殊的硅油处理热解法二氧化硅。
本发明涉及通过硅油进行表面处理的热解法二氧化硅，且满足以下A)～C)的物性的硅油处理热解法二氧化硅：
A)疏水度68体积％以上；
B)硅油固定化率60～95质量％；
C)在三羟甲基丙烷聚氧丙烯胺(25℃下的动粘度为72cSt)：1,3环己二甲胺＝95：5质量比所组成的聚醚胺组成物的100质量份中，添加6质量份的上述硅油处理热解法二氧化硅，所得聚醚胺组合物在25℃放置1小时后的粘度在4000mPa·s以上。
另外，本发明还涉及一种在150-300℃的惰性气体环境下，热解法二氧化硅表面附着硅油后，切换成含有150-300℃的氧气气体环境进行高温处理的生产上述硅油处理热解法二氧化硅的硅油处理热解法二氧化硅制造方法。
进一步的发明是，被使用在二液型环氧体系胶黏剂中，含有聚醚胺化合物和上述硅油处理热解法二氧化硅的二液型环氧体系胶黏剂用固化剂。
的硅油处理热解法二氧化硅，因为作为原粉的二氧化硅需要含水率以及金属杂质非常少，且具有很好的流动性，所以使用热解法二氧化硅，即燃烧分解法所制得的二氧化硅。所谓燃烧分解法，是指将硅化合物或金属硅在氢氧火焰中燃烧，制造二氧化硅粒子的方法。一般会使用四氯化硅等的硅化合物。为了和沉淀法二氧化硅等的用沉淀法制造的二氧化硅做区分，热解法二氧化硅也叫气相二氧化硅或是气相法二氧化硅。
在上述热解法二氧化硅中，如果比表面积太小，达到一定的增稠效果需要添加大量的硅油处理热解法二氧化硅；如果比表面积太大，在树脂中的分散性会变差。因此用BET1点法测量的比表面积在30～420m 2/g，较好的是100～350m 2/g，最好是120～250m 2/g。
为了有效地发挥增稠效果，热解法二氧化硅的堆积密度是20～70g/L，最好是在25～50g/L。上述堆积密度是在1L的量筒中放入已称重的热解法二 氧化硅，放置30分钟后，通过体积计算出来的。
像这种作为原粉使用的热解法二氧化硅，在用硅油处理前，因为表面还有硅醇基团，所以是亲水性的，不含有碳，一般疏水度为0。
表面处理所使用的硅油，没有特殊限定，例如二甲基硅油、甲基苯基硅油、甲基含氢硅油、羧基改性硅油、聚醚改性硅油、烷基改性硅油、氟改性硅油等。最理想的是二甲基硅油。
上述硅油的粘度在25℃下的测量值，最好是在20～500cSt。低于20cSt时，硅油会挥发，不能充分地进行表面处理；超过500cSt时，粘度太高处理均匀性会变差。另外，为了能同时满足高硅油固定化率和高粘度，最理想的粘度范围是50～200cSt。硅油还可以两种以上混合使用。
本实施形态的硅油处理热解法二氧化硅通过上述硅油对热解法二氧化硅进行表面处理获得，且满足以下A)～C)的物性。
A)疏水度68体积％以上；
B)硅油固定化率60～95质量％；
C)在三羟甲基丙烷聚氧丙烯胺(25℃下的动粘度为72cSt)：1,3环己二甲胺＝95：5质量比所组成的聚醚胺组成物的100质量份中，添加6质量份的本实施形态的硅油处理热解法二氧化硅，所得聚醚胺组合物在25℃放置1小时后的粘度在4000mPa·s以上。
A)疏水度68体积％以上，最理想是70体积％以上。拥有高的疏水度，说明热解法二氧化硅表面充分地被硅油进行了处理，对提高硅油处理热解法二氧化硅在各种聚醚胺体系组合物中的分散性是非常重要的。硅油处理热解法二氧化硅的疏水度较低，聚醚胺体系组合物中的粘度也会降低，不是特别理想。疏水度的上限没有特殊规定，但一般在80体积％以下，最好是在75体积％以下。。
本实施形态的硅油处理热解法二氧化硅中的A)疏水度是通过将0.2g硅油处理热解法二氧化硅加入到有50mL的水的250mL的烧杯中进行搅拌，之后慢慢加入甲醇，等硅油处理热解法二氧化硅粉末全部被烧杯内的溶液润湿时作为终点，来进行测量的，求得该终点的甲醇-水混合溶液中的甲醇体积％。
B)硅油固定化率是60～95质量％，较佳是70～95质量％，最好是70～90质量％。存在于被硅油处理的热解法二氧化硅粒子表面的硅油有两种形式，一是和热解法二氧化硅表面结合的“固定化硅油”，二是物理吸附在热解法二 氧化硅表面的“游离硅油”。因此，即使通过表面处理，热解法二氧化硅表面披覆了大量硅油，且上述疏水度也非常高，但如果上述游离硅油占了很大一部分时，实际混合到聚醚胺体系组合物中时，会产生大量游离硅油，不能达到预期的增稠性或是增稠稳定性。因此，上述硅油处理热解法二氧化硅的硅油固定化率需要维持在上述的高范围内。
本发明中，「硅油固定化率FR[％]」如以下公式所示。
公式(1)：FR＝100×F(OIL)/T(OIL)
公式(1)中，F(OIL)表示固定化硅油量[g]，T(OIL)表示总碳含量相当的硅油量[g]。
公式(1)中所表示的总碳含量相当的硅油量T(OIL)以及固定化硅油量F(OIL)可以通过以下方法求得。
＜总碳含量相当的硅油量T(Oil)＞
首先将0.1g硅油处理二氧化硅，利用碳含量检测装置(株式会社住化分析中心产SUMIGRAPHNC－22F)通过燃烧法来求得硅油总碳含量T(Carbon)〔g〕。接着通过以下公式(2)来求得总碳含量相当的硅油量T(Oil)[g]。
公式(2)：T(Oil)＝T(carbon)×所使用的硅油的分子量/所使用硅油的1分子中的碳含量。
所使用的硅油的分子量以及所使用硅油的1分子中的碳含量，可以作为硅油主链的每单位构造的值来进行计算。以下公式(3)也是一样的。
当硅油总碳含量T用〔wt％〕表示时，该值表示的是相对于0.1g硅油处理二氧化硅的硅油总碳含量T〔g〕的质量比率。
＜固定化硅油量F(Oil)＞
首先在容量50mL的离心管中，加入0.5g硅油处理二氧化硅和32mL正己烷，用超声波清洗器(例如大和科学产超声波清洗器1510HMTH)90W的强度下超声波清洗30分钟，得到悬浊液。将所得悬浊液进行离心分离，分离回收固体。所回收的固体中添加32mL正己烷，重复3次超声波处理以及离心分离得到固体(表面只残留结合的固定化硅油的二氧化硅)。接着将该固体进行减压干燥(120℃、12小时)得到干燥粉末，检测该重量，检测上述只残留有固定化硅油的二氧化硅的全重量[g]。从该只残留有固定化硅油的二氧化硅中取0.1g，利用碳含量检测装置(株式会社住化分析中心产SUMIGRAPH NC－2 2F)通过燃烧法来检测其碳含量，求得固定化硅油碳含量F(Carbon)[g]。接着根据以下公式(3)来计算固定化硅油量F(Oil)[g]。
公式(3)：F(Oil)＝F(carbon)×所使用的硅油的分子量/所使用的硅油1分子中的碳含量×只残留有固定化硅油的二氧化硅的全重量[g]/0.1g[g]×0.1[g]/0.5[g]
上述公式(3)中，前段的「F(carbon)×所使用的硅油分子量/所使用的硅油的1分子中的碳含量」中，可以计算出相对于0.1g的只残留有固定化硅油的二氧化硅的固定化硅油量(暂定F(Oil))。但该值是上述的相对于「0.1g的只残留有固定化硅油的二氧化硅」的固定化硅油量，所以相对于「0.1g硅油处理二氧化硅」的固定化硅油量还需要补正。所以公式(3)的后段有提到在上述计算出来的暂定F(Oil)上，通过公式「只残留有固定化硅油的二氧化硅的全重量[g]/0.1g[g]×0.1[g]/0.5[g]」，可以算出所需要的固定化硅油量F(Oil)。
另外作为参考，离心分离所得到的液相中含有物理吸附在表面的游离硅油。游离硅油量I(Oil)[g]用以下公式(4)来表示。
公式(4)：I(Oil)＝T(Oil)－F(Oil)
公式(1)～(4)中所显示的数值参数：T(Oil)、F(Oil)、I(Oil)、T(carbon)、F(carbon)，是燃烧法检测中所使用的每0.1g硅油处理二氧化硅所相当的值[g]。
将这些数值参数的值[g]换算成检测时所使用的硅油处理二氧化硅的生产原料热解法二氧化硅的每单位表面积的值[g/m 2]时，只需要除以以下公式(5)中的换算系数C[m 2]。另外，将值换算成[mg/m 2]时，只需要在[g/m 2]的数值上乘以1000。该换算系数C表示每0.1g燃烧法检测用硅油处理二氧化硅中的热解法二氧化硅粒子本体的表面积。
公式(5)：C＝Mb×S
公式(5)中，Mb表示从燃烧法检测用硅油处理二氧化硅的质量(0.1g)中减去了总碳含量相当的硅油量T(Oil)[g]的值(检测用硅油处理二氧化硅0.1g中除去硅油之后的二氧化硅粒子本体的质量)[g]。S表示生产检测用硅油处理二氧化硅说使用的原料热解法二氧化硅的比表面积[m 2/g]。
如果不知道原料热解法二氧化硅的比表面积S时，可以通过以下方法求得。首先将硅油处理二氧化硅在650℃以上加热2小时以上，使固定化硅油以及 游离硅油加热分解。就可以得到去除了表面的硅油的二氧化硅粒子本体(即原料热解法二氧化硅)。接着将加热处理所得的二氧化硅粒子本体，通过BET1点法来检测其比表面积，就可以得到原料热解法二氧化硅的比表面积S。
本发明的硅油处理热解法二氧化硅，从充分的疏水度的观点考虑，上述碳含量较佳是在3～8质量％的范围内，最好是5～8质量％。
进一步地，本发明的硅油处理热解法二氧化硅，拥有以下特征：
C)在三羟甲基丙烷聚氧丙烯胺(25℃下的动粘度为72cSt)：1,3环己二甲胺＝95：5质量比所组成的聚醚胺组成物的100质量份中，添加6质量份硅油处理热解法二氧化硅，所得聚醚胺组合物在25℃放置1小时后的粘度在4000mPa·s以上，最理想是在4000～10000mPa·s。
上述聚醚胺组合物，是作为二液型环氧体系胶黏剂用固化剂被使用的典型的形态(例如，请参见日本特表2015-524875号公报)。
因此，和C)中所示的聚醚胺组合物混合能达到高粘度的性能，说明本实施形态的硅油处理热解法二氧化硅适用于用于二液型环氧体系胶黏剂用固化剂的聚醚胺固化剂。
具体地，为了拥有上述A)高疏水度和B)高硅油固定化率，只要是用硅油进行表面处理的热解法二氧化硅，对于聚醚胺固化剂都具有一定的良好的分散性，有一定的增稠效果。但电子材料等用途中使用的环氧树脂所需要的作业精密性在不断提高，对于聚醚胺固化剂的增稠性要求也更高。从上述观点考虑，提高了上述A)疏水度和B)硅油固定化率的硅油处理热解法二氧化硅不能完全满足，因此本实施形态的硅油处理热解法二氧化硅，在和作为聚醚胺固化剂使用的C)中所示的聚醚胺组合物进行混合时，可以提高粘度。
在硅油处理热解法二氧化硅中，即使A)疏水度和B)硅油固定化率都很高，C)中所示的聚醚胺组合物的粘度不能充分提高的理由也不是一定的，推测和热解法二氧化硅粒子表面处理均匀性有关。即在硅油的表面处理中，如果观察每个粒子，处理程度是有波动的。因此，整体粒子在经过处理后能拥有上述高疏水度以及硅油固定化率，但也存在一小部分固定化处理不到位的粒子，这些粒子会阻碍C)中所示的聚醚胺组合物的分散，控制上述粘度的提高。
因此，本实施形态的硅油处理热解法二氧化硅通过采用特殊的制造方法等，跟以往技术相比能够更均匀地使用硅油对表面进行固定化处理，推测不 仅仅是上述A)疏水度和B)硅油固定化率，混合到C)中所示的聚醚胺组合物时的粘度应该也会有很大的改善。另外，推测除了C)中所示的聚醚胺组合物以外的各种聚醚胺体系组合物都会具有上述说明的作业效果。
本发明中，C)的测量方法具体如下。首先，在190质量份的三羟甲基丙烷聚氧丙烯胺(CAS号：39423-51-36)(25℃下的动粘度是72cSt)和10质量份的1,3－环己二甲胺(CAS号：2579-20-6)的聚醚胺组合物中，加入12质量份的硅油处理热解法二氧化硅。之后，使用高速分散机4000rpm，分散10分钟。将得到的聚醚胺组合物在25℃下恒温1小时后，用BL型粘度计(例如:东机产业社产的VISCOMERER BL)测量粘度。聚醚胺组合物的粘度根据BL型粘度计60rpm下的测量值(mPa·s)来进行计算。
本实施形态的硅油处理热解法二氧化硅还具有以下物性：D)通过和上述C)相同的方法制得聚醚胺组合物进行测量的在25℃恒温1小时后的触变(TI)较好是在4.8以上。最理想是在4.8～6.0。通过以下公式可以计算TI，值接近1时就是牛顿流体，值越高说明增稠性越好防流挂越好。
TI＝6rpm下的粘度÷60rpm下的粘度×10
上述计算TI的公式中，6rpm以及60rpm下的各粘度，是通过上述BL型粘度计来检测的。
进一步地，本实施形态的硅油处理热解法二氧化硅，上述B)硅油固定化率高，增稠稳定性好，还具有以下物性：
C’)通过和上述C)相同的方法制得聚醚胺组合物进行计算，以下公式中的粘度残存率较佳在70％以上，最理想是在72％以上。
粘度残存率(％)＝25℃恒温31小时后的粘度÷25℃恒温1小时后的粘度×100。
上述计算粘度残存率的公式中，25℃恒温31小时后以及25℃恒温1小时后的各粘度，是通过上述BL型粘度计来检测的。
同样地，本实施形态的硅油处理热解法二氧化硅，还具有以下物性：
D’)通过和上述C)相同方法制得聚醚胺组合物进行计算，以下公式中的TI残存率较佳在45％以上，最理想是在46％以上。
TI残存率(％)＝25℃恒温开始31小时后的TI÷25℃恒温开始1小时后的TI×100。
上述计算粘度残存率的公式中，25℃恒温31小时后以及25℃恒温1小 时后的各粘度，是通过上述BL型粘度计来检测的。
本实施形态的硅油处理热解法二氧化硅的比表面积，根据作为原粉的热解法二氧化硅的比表面积，以及使用的硅油的量而改变，所以不能一概而定。一般在15～210m 2/g，较好在40～180m 2/g，最理想是在50～130m 2/g。
如上所述，使用的原粉是热解法二氧化硅，所以本实施形态的硅油处理热解法二氧化硅和在溶液中合成的沉淀二氧化硅相比，金属杂质非常少，所配合使用的聚醚胺化合物如果是作为电子材料等的环氧树脂胶黏剂中用的聚醚胺固化剂时，那是非常有利的。一般的金属杂质，Na、K、Ca、Mg、Fe，Al的含量分别在0.1ppm以下。
接下来，对拥有以上特征的本实施形态的硅油处理热解法二氧化硅的制造方法进行说明。本实施形态的硅油处理热解法二氧化硅，是用硅油进行表面处理的热解法二氧化硅，如能满足上述A)～C)的物性，使用任何方法都能生产，但对于最佳的制造方法，举例做如下说明：150～300℃的惰性气体环境下，使热解法二氧化硅的表面粘附硅油后，切换成150～300℃的氧气环境，进行高温处理的方法。
上述方法中，热解法二氧化硅的表面粘附硅油后，上述高温处理是在氧气环境下实施的。这样热解法二氧化硅表面的硅油固定化的均匀性会明显提高，不仅仅是上述A)疏水度和B)硅油固定化率提高了，而且C)中所示的聚醚胺组合物使用时的粘度也很高。具体理由如下：
在硅油附着后的高温环境下的固定化处理中，存在于热解法二氧化硅粉体表层的游离状态的硅油有一部分会挥发离解。所挥发的部分中还会有一部分再次与热解法二氧化硅表面发生固定化反应，即与残留的硅醇基结合、固定。上述反应是在氧气氛围内实施的，故而硅油与硅醇基的固定化会更活泼。其结果就是热解法二氧化硅粉体表面不同位置的硅醇基与硅油固定结合的概率增大了，这可能就是得到上述C)的物性提高的硅油处理热解法二氧化硅的原因。
如上述的以往的硅油处理热解法二氧化硅的制造中，最常见的方法是硅油附着后的高温处理在氮气环境下进行。此时热解法二氧化硅表面所存在的游离硅油挥发后的固定化不能充分的发挥作用。其结果是硅油表面处理还是不均匀，所制得的硅油处理热解法二氧化硅的物性也是不能满足上述C)的物性要求的。
另外，在上述制造方法中，在上述高温处理前，热解法二氧化硅表面的硅油粘附处理需要在氮气等的惰性气体环境下进行，在硅油粘附处理之后的高温处理，需要切换成氧气环境后再进行。即如果希望热解法二氧化硅表面的硅油粘附处理效果更均匀，最好在上述150～300℃的高温下实施。
但如上所述进行喷雾，或是在较强的搅拌下等进行该表面处理操作时，在高温下实施有着火的危险。即热解法二氧化硅的硅油喷雾处理，不能和热解法二氧化硅结合的硅油量会过加热，以及该硅油会氧化分解大量挥发，且易副生成着火性物质。因此，从安全面考虑，上述喷雾处理需要在氮气等的惰性气体环境下实施。
上述热解法二氧化硅表面的硅油附着处理，以及之后的高温处理的温度，分别最好是在200～300℃。上述处理温度低于150℃时，硅油不能进行均匀的表面处理，所制得的硅油处理热解法二氧化硅，不能满足混合在C)中所示的聚醚胺组合物中时的粘度，不能达到本发明的规定值。
热解法二氧化硅表面的硅油附着处理的具体方法可以列举如下。在搅拌机或流动层中边混合边对热解法二氧化硅粒子进行硅油喷雾的方法，或使硅油溶解在甲苯等的溶剂中，然后将热解法二氧化硅粒子分散到上述溶液，蒸发溶剂的方法等，但从成本面、安全面、环境面考虑，前者的喷雾方法较好。在喷雾处理中的搅拌机的搅拌中，为了使热解法二氧化硅粒子流动，且具有稳定的搅拌状态，最好选定搅拌转数以及搅拌桨的形状。通过上述方法使热解法二氧化硅粒子和硅油接触后，在搅拌机或流动层中的混合，最好在上述惰性气体环境下进行30～180分钟。
热解法二氧化硅的硅油的附着处理量会根据作为原料使用的热解法二氧化硅的比表面积而发生变化，所以不能一概而论，但从制造本实施形态的硅油处理二氧化硅的观点考虑，相对于100质量份的原料热解法二氧化硅，较好是3～50质量份，最好是10～30质量份。
使用在硅油附着处理中的惰性气体最好是氮气，但也可以是氩气、氦气等惰性气体。
硅油附着后的热解法二氧化硅的高温处理，从上述惰性气体环境切换成氧气气体环境后，最好是和硅油喷雾时相同，边搅拌边进行。在此高温处理中，已经喷雾的硅油的一半以上已经和热解法二氧化硅表面结合，所以和硅油附着处理时相同，着火的危险性很小，可以进行搅拌处理。
氧气气体的氧气浓度，只要能足够促进挥发的游离硅油在热解法二氧化硅表面固定化，没有特殊限制，但较好是12体积％以上，最好是18体积％以上。考虑安全，氧气浓度最好在30体积％以下。
氧气气体，除了氧气以外的气体成分，也可以是如上述的惰性气体等。该氧气气体的氧气浓度可以是21体积％，所以也可以使用空气。
硅油附着后的高温处理，较好是进行30分钟以上，最好是60～180分钟。
本实施形态的硅油处理热解法二氧化硅，是一种疏水性二氧化硅，电子材料用和建筑材料等用途多样化，也可以配合功能材料使用。如果考虑上述聚醚胺化合物中的优越的增稠效果，那么较好是配合使用在含有聚醚胺化合物(主要成分)的聚醚胺体系组合物的添加剂用途中。最好是作为环氧树脂(特别是电子材料用途等的二液型环氧体系胶黏剂用)的聚醚胺固化剂配方用添加剂来使用本实施形态的硅油处理二氧化硅，在此用途中使用本实施形态的硅油处理热解法二氧化硅，高粘度且防流挂，同时具有很好的操作性，是非常有利的。
二液型环氧体系胶黏剂的聚醚胺固化剂，本实施形态中的硅油处理热解法二氧化硅在规定了其良好的增稠性的C)中，作为其典型状态所选择的，上述C)三羟甲基丙烷聚氧丙烯胺(25℃下的动粘度是72cSt)：1,3－环己二甲胺＝95：5质量比是最好的。另外，以聚醚胺化合物为主成分的聚醚胺固化剂，任何公知的成分都可以成为本实施形态的硅油处理热解法二氧化硅的配方对象，不受限制。另外，除了二液型环氧体系胶黏剂的聚醚胺固化剂以外的可以在各种用途中使用的聚醚胺体系组合物，都可以适用本实施形态的硅油处理二氧化硅。
具体地，可以是乙二胺，1,2－丙二胺、二乙烯三胺、三乙烯四胺、多乙烯多胺、己二胺、聚乙二胺、三羟甲基丙烷聚氧丙烯胺、氨乙基哌嗪、1,3－环己二甲胺等的各种聚醚胺化合物中的至少含有1种以上的聚醚胺固化剂，或是也包括该聚醚胺固化剂的在各种用途中被使用的聚醚胺体系组合物。在这些聚醚胺体系组合物中，除了上述胺化合物外，还可以添加其他的颜料和染料等。
聚醚胺体系组合物，特别是在聚醚胺固化剂中，本实施形态的硅油处理热解法二氧化硅的配方量，一般是在100质量份的聚醚胺化合物中添加2～ 15质量份。25℃放置1小时后的粘度是4000mPa·s以上，最好是4500～10000mPa·s。从上述观点看，本实施形态的硅油处理热解法二氧化硅，在聚醚胺体系组合物中具有良好的增稠效果，只需在100质量份的聚醚胺化合物中添加2～10质量份，就可以达到各种用途，特别是聚醚胺固化剂用途所期望的粘度。
本实施形态的硅油处理热解法二氧化硅，不仅仅可以使用在聚醚胺固化剂中，也可以使用在与聚醚胺固化剂混合使用的含有环氧树脂(主要成分)的主剂中。拥有良好的疏水性，本实施形态的硅油处理热解法二氧化硅，原本在上述环氧树脂中也有良好的增稠性，且和聚醚胺固化剂混合使用时，具有良好的混合性，所制得的混合组合物，具有高粘度、难流挂，且具有良好的操作性。
为了能够更清楚地理解本发明的技术内容，以下利用实施案例以及对比案例对本发明进行详细说明，但本发明不限于这些实施案例。
＜比表面积的测量＞
热解法二氧化硅以及硅油处理热解法二氧化硅的比表面积使用柴田科学器械工业产的比表面积测量装置SA-1000，根据氮气吸附量通过BET1点法来测量。
＜疏水度测量＞
将0.2g硅油处理二氧化硅添加到装有50mL水的250mL烧杯中，用磁力搅拌机搅拌。之后使用滴定管往里面加甲醇，以粉末状的硅油处理二氧化硅全部被烧杯内的溶剂润湿为终点来进行测量。为了不让甲醇直接和硅油处理二氧化硅接触，使用软管添加至溶液中。终点的甲醇-水混合溶液中的甲醇的体积％就是疏水度。
＜硅油固定化率FR[％]的检测＞
作为以下公式(1)中所表示的值进行了计算。
公式(1)：FR＝100×F(Oil)/T(Oil)
公式(1)中，F(OIL)表示固定化硅油量[g]，T(OIL)表示总碳含量相当的硅油量[g]。F(OIL)和T(OIL)通过以下方法来求得。
公式(1)中所表示的总碳含量相当的硅油量T(OIL)以及固定化 硅油量F(OIL)可以通过以下方法求得。
＜总碳含量相当的硅油量T(Oil)＞
首先将0.1g硅油处理二氧化硅，利用碳含量检测装置(株式会社住化分析中心产SUMIGRAPHNC－22F)通过燃烧法来求得硅油总碳含量T(Carbon)〔g〕。接着通过以下公式(2)来求得总碳含量相当的硅油量T(Oil)[g]。
公式(2)：T(Oil)＝T(carbon)×所使用的硅油的分子量/所使用硅油的1分子中的碳含量
所使用的硅油的分子量以及所使用硅油的1分子中的碳含量，可以作为硅油主链的每单位构造的值来进行计算。具体的，在各实施案例中，使用在二氧化硅表面处理的硅油是以二甲基硅氧烷作为主链的硅油，所以单位构造式是：－(Si(CH3)2－O)－，可以通过以下公式求得。
T(Oil)＝T(carbon)×(Si〔28〕+C〔12〕×2+H〔1〕×6+O〔16〕)÷(C〔12〕×2)
＜固定化硅油量F(Oil)＞
首先在容量50mL的离心管中，加入0.5g硅油处理二氧化硅和32mL正己烷，用超声波清洗器(例如大和科学产超声波清洗器1510HMTH)90W的强度下超声波清洗30分钟，得到悬浊液。将所得悬浊液进行离心分离，分离回收固体。所回收的固体中添加32mL正己烷，重复3次超声波处理以及离心分离得到固体(表面只残留结合的固定化硅油的二氧化硅)。接着将该固体进行减压干燥(120℃、12小时)得到干燥粉末，检测该重量，检测上述只残留有固定化硅油的二氧化硅的全重量[g]。从该只残留有固定化硅油的二氧化硅中取0.1g，利用碳含量检测装置(株式会社住化分析中心产SUMIGRAPHNC－22F)通过燃烧法来检测其碳含量，求得固定化硅油碳含量F(Carbon)[g]。接着根据以下公式(3)来计算固定化硅油量F(Oil)[g]。
公式(3)：F(Oil)＝F(carbon)×所使用的硅油的分子量/所使用的硅油1分子中的碳含量×只残留有固定化硅油的二氧化硅的全重量[g]/0.1g[g]×0.1[g]/0.5[g]＜堆积密度测量＞
在1L的塑料量筒加入热解法二氧化硅，注意不要满出来，静置30分钟 后确认容积。通过所加入的热解法二氧化硅的重量和容积来计算堆积密度。
＜粘度、TI测量＞
在190重量份的三羟甲基丙烷聚氧丙烯胺(HUNTSMAN社产JEFAMIN T-403、25℃下的动粘度72cSt)和10重量份的1,3－环己二甲胺(三菱瓦斯化学社产)(质量比95:5)的聚醚胺组合物中，加入12重量份的硅油处理热解法二氧化硅(100质量％的聚醚胺组合物中添加6质量％)，用玻璃棒混合，放置3分钟。之后用高速分散机(PREMIX社HOMODISPER MODEL2.5、分散盘直径40mm)4000rpm搅拌分散10分钟。25℃下恒温1小时后，用BL型粘度计(东机产业社产VISCOMERER BL)测量粘度。恒温开始31小时后也进行测量。粘度是BL型粘度计60rpm下的测量值(mPa·s)，计算TI的公式如下。
TI＝6rpm下的粘度÷60rpm下的粘度×10。
粘度残存率、TI残存率的计算公式如下。恒温是指25℃。
粘度残存率(％)＝恒温开始31小时后的粘度÷恒温开始1小时后的粘度×100。
TI残存率(％)＝恒温开始31小时后的TI÷恒温开始1小时后的TI×100。
＜流挂试验＞
在1kg环氧树脂(HEXION Specialty Chemicals,Inc.社产EPIKOTE828)中添加53g硅油处理热解法二氧化硅，约搅拌1小时使硅油处理二氧化硅分散。在1kg聚醚胺固化剂(HUNTSMAN社产JEFAMIN T-403)中添加53g硅油处理热解法二氧化硅，约搅拌1小时使二氧化硅分散。将调整后的环氧树脂和聚醚胺固化剂以1：1的体积比混合，使用喷射枪在墙上从左到右水平方向涂布30cm，确认流挂情况。防流挂效果差的会受重力影响下垂，防流挂效果好的，不会下垂可以保持刚涂布时的状态。
＜金属杂质含量测量＞
称取2g硅油处理热解法二氧化硅在白金容器中，添加10mL浓硝酸和10mL氟酸。在200℃的加热板上加热，蒸发液体。再加2mL浓硝酸，200℃加热3分钟后，冷却，加入超纯水稀释至25mL。将此作为试料，用ICP发光分析装置(VARIAN社产、型号[715-ES Radial])测量金属杂质含量。
实施案例1
＜热解法二氧化硅合成＞
将中心管内径为100mm的密闭式三重管灯头设置在密闭式反应器中，将作为原料气体的四氯化硅(STC)和氢气，以及作为助燃气体的空气事先混合，将上述混合气体供应到中心管中。第一环状管中供应氢气和空气，形成引燃火炎。第二环状管中流通空气，防止灯头上有热解法二氧化硅粒子粘附。通过调整供应到中心管中的原料气的量和助燃气体的量，可以得到想要的比表面积。
＜硅油处理＞
在容量为35L的搅拌机中，加入400g上述热解法二氧化硅，进行搅拌，切换至氮气环境的同时，加热至260℃。然后喷雾80g(相对于热解法二氧化硅100质量份的添加量来说，添加20质量份)的作为硅油的粘度为50cSt的聚二甲基硅氧烷。260℃保持1小时后，容器内置换成空气，氧气浓度调到20.5体积％。之后再进行260℃保持1小时，就能得到硅油处理热解法二氧化硅。制得的硅油处理热解法二氧化硅和其生成用的热解法二氧化硅以及硅油的物性如表1及表2，制得的硅油处理热解法二氧化硅的金属杂质含量如表3。
实施案例2～4
在实施案例1中，所使用的硅油粘度以及热解法二氧化硅的比表面积，如表1做变更以外，方法和实施案例1相同。制得的硅油处理二氧化硅物性如表1以及表2，金属杂质含量如表3。
实施案例5
除了将在实施案例1的容器内的置换换成氧气浓度15体积％以外，操作和实施案例1相同。制得的硅油处理二氧化硅等的物性如表1以及表2，金属杂质含量如表3。
对比案例1
和实施案例1相比，除了硅油喷雾后不进行空气置换，喷雾后，260℃下保持1小时后，在氮气环境下260℃保持1小时以外，操作和实施案例1相同。制得的硅油处理二氧化硅等的物性如表1以及表2，金属杂质含量如 表3。
对比案例2
除了将对比案例1中的表面处理所使用的硅油量变更为160g(相对于热解法二氧化硅100质量份来说40质量份)以外，操作和对比案例1相同。制得的硅油处理二氧化硅等的物性如表1以及表2，金属杂质含量如表3。
对比案例3
和对比案例1相比，除了硅油喷雾后260℃下保持1小时后，氮气环境下的高温处理变更为310℃2小时以外，操作和对比案例1相同。制得的硅油处理二氧化硅等的物性如表1以及表2，金属杂质含量如表3。
对比案例4
在实施案例1中，热解法二氧化硅的比表面积，如表1做变更以外，通过和实施案例1相同的方法可以制得硅油处理二氧化硅。制得的硅油处理二氧化硅等的物性如表1及表2，金属杂质含量如表3。
通过上述的实施案例以及对比案例，在生产硅油处理热解法二氧化硅时，通过硅油处理后，在氧气共存下进行加热处理，疏水度会上升，聚醚胺体系组合物中的粘度、TI也会上升，且保持稳定性也很好。通过对比案例3可知，想要在聚醚胺体系组合物中有增稠效果以及稳定性，最好是在氧气环境下进行加热处理。
Figure PCTCN2018080614-appb-000001
Figure PCTCN2018080614-appb-000002
Figure PCTCN2018080614-appb-000003
※粘度、TI的时间是将检测液体放在25℃下恒温开始后的时间。
※流挂试验A：无流挂、B：有流挂。
Figure PCTCN2018080614-appb-000004
从而，本发明提供了一种在使用了环氧树脂以及聚醚胺固化剂的树脂组合物中，跟以往技术相比能赋予更高的增稠效果的硅油处理热解法二氧化硅。在用硅油对亲水热解法二氧化硅进行处理时，通过在氧气共存的环境下进行处理，能得到增稠效果非常好的硅油处理热解法二氧化硅。
本发明的有益效果主要在于：
本发明的硅油处理热解法二氧化硅，具有高疏水度以及高硅油固定化率，而且可以赋予聚醚胺化合物良好的增稠效果，同时具有良好的增稠稳定性。
因此，本发明的硅油处理热解法二氧化硅，适用于用于环氧树脂的聚醚胺固化剂，具有高粘度、防流挂、易操作的特征。作为原粉的热解法二氧化硅，一般金属杂质是非常少的，所以特别适用于电子材料等用途的环氧树脂胶黏剂。
综上所述，本发明的硅油处理热解法二氧化硅在和聚醚胺化合物混合时有良好的增稠性以及增稠稳定性，且可以用在用于环氧树脂的聚醚胺组合物中，制备简单，成本低，适于大规模推广应用。
本领域的技术人员应理解，上述描述所示的本发明的实施例只作为举例而并不限制本发明。
由此可见，本发明的目的已经完整并有效的予以实现。本发明的功能及结构原理已在实施例中予以展示和说明，在不背离所述原理下，实施方式可作任意修改。所以，本发明包括了基于权利要求精神及权利要求范围 的所有变形实施方式。

Claims (13)

  1. 一种硅油处理热解法二氧化硅，其特征在于，所述硅油处理热解法二氧化硅具有以下A)～C)的物性：
    A)疏水度为68体积％以上；
    B)硅油固定化率为60～95质量％；
    C)在100质量份的聚醚胺组成物中添加6质量份的所述硅油处理热解法二氧化硅，所述聚醚胺组成物包括三羟甲基丙烷聚氧丙烯胺和1,3环己二甲胺，所述三羟甲基丙烷聚氧丙烯胺和所述1,3环己二甲胺的质量比为95：5，所得到的聚醚胺组合物在25℃放置1小时后的粘度在4000mPa·s以上。
  2. 根据权利要求1所述的硅油处理热解法二氧化硅，其特征在于：
    所述硅油处理热解法二氧化硅的比表面积为50～130m 2/g。
  3. 根据权利要求1或2所述的硅油处理热解法二氧化硅，其特征在于：
    所述硅油处理热解法二氧化硅的总碳含量为5～8质量％。
  4. 根据权利要求1至3中任一权利要求所述的硅油处理热解法二氧化硅，其特征在于：
    所述硅油处理热解法二氧化硅的金属杂质包括Na、K、Ca、Mg、Fe、Al，所述金属杂质的含量分别在0.1ppm以下。
  5. 根据权利要求1至4中任一权利要求所述的硅油处理热解法二氧化硅，其特征在于：
    所述硅油处理热解法二氧化硅还具有物性：D)使用通过所述C)相同的方法制得的聚醚胺组合物，进行测量25℃恒温1小时后的触变(TI)在4.8以上。
  6. 根据权利要求1至5中任一权利要求所述的硅油处理热解法二氧化硅，其特征在于：
    所述硅油处理热解法二氧化硅还具有物性：C’)使用通过所述C)相同 的方法制得的聚醚胺组合物进行计算，以下公式中的粘度残存率在70％以上：
    粘度残存率(％)＝所述聚醚胺组合物在25℃恒温31小时后的粘度÷所述聚醚胺组合物在25℃恒温1小时后的粘度×100。
  7. 根据权利要求1至6中任一权利要求所述的硅油处理热解法二氧化硅，其特征在于：
    所述硅油处理热解法二氧化硅还具有物性：D’)使用通过所述C)相同的方法制得的聚醚胺组合物进行计算，以下公式中的TI残存率在45％以上：
    TI残存率(％)＝所述聚醚胺组合物在25℃恒温开始31小时后的TI÷所述聚醚胺组合物在25℃恒温开始1小时后的TI×100。
  8. 根据权利要求1至7中任一权利要求所述的硅油处理热解法二氧化硅在作为添加剂制备含有聚醚胺化合物的聚醚胺体系组合物的应用。
  9. 根据权利要求8所述的硅油处理的热解法二氧化硅，其特征在于：
    所述聚醚胺体系组合物是作为二液型环氧体系胶粘剂中的固化剂使用。
  10. 一种根据权利要求1至9中任一权利要求所述的硅油处理热解法二氧化硅的制造方法，其特征在于，所述的硅油处理热解法二氧化硅的制备方法包括以下步骤：
    在150℃～300℃的惰性气体环境下，使热解法二氧化硅的表面粘附硅油，然后在150℃～300℃的氧气环境下，进行高温处理，从而获得硅油处理热解法二氧化硅。
  11. 根据权利要求10所述的硅油处理热解法二氧化硅的制造方法，其特征在于：
    所述氧气气体的氧气浓度在12体积％以上。
  12. 一种根据权利要求1至9中任一权利要求所述的硅油处理热解法二 氧化硅，其特征在于：
    采用根据权利要求10或11所述的硅油处理热解法二氧化硅的制造方法进行生产。
  13. 根据权利要求1至9中任一权利要求所述的硅油处理热解法二氧化硅在作为固化剂制备含聚醚胺化合物的二液型环氧体系胶粘剂的应用。
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CN108467692B (zh) 2020-10-13
JP2020515489A (ja) 2020-05-28
US20210115262A1 (en) 2021-04-22
KR102319929B1 (ko) 2021-10-29

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