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  • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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  • C01—INORGANIC CHEMISTRY
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  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
  • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
  • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08K9/00—Use of pretreated ingredients
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  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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  • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
  • C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
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  • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/12—Surface area
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  • C01—INORGANIC CHEMISTRY
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  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability

Definitions

• the present invention relates to a dispersion of silica-containing inorganic oxide particles whose surface is silane-treated and a method for producing the same.
• a dispersion of silica-containing inorganic oxide particles, particularly a silica sol, is a liquid in which silica particles are dispersed in a dispersion medium.
• One of the methods is to modify the surface of silica particles with a silane coupling agent having a cationic or anionic functional group when the dispersion medium is an aqueous solution, or to modify the surface of the silica particles when the dispersion medium is an organic solvent.
• There is a method of modifying the surface of silica particles with a silane coupling agent having an organic group There is a method of modifying the surface of silica particles with a silane coupling agent having an organic group.
• a method for producing an organic solvent-dispersed silica sol comprises the steps of adding an alkoxide for surface treatment and replacing the dispersion medium with a non-alcoholic organic solvent in the presence of a primary alcohol having 3 to 12 carbon atoms. (See Patent Document 1).
• the present invention provides a dispersion of silica-containing inorganic oxide particles, particularly a dispersion of silica particles, which has high dispersion stability even at high temperature and high salinity.
• the dispersion containing the silica-containing inorganic oxide particles are silica particles having an average particle diameter of 5 nm to 100 nm, or at least one selected from the group consisting of silica and alumina, tin oxide, zirconium oxide, titanium oxide, and antimony oxide.
• the hydrolyzable silane has formulas (1) to (3):
• R 3 is an alkyl group, a halogenated alkyl group, an alkenyl group, or an organic group having an epoxy group, (meth)acryloyl group, mercapto group, amino group, ureido group, or cyano group, and Si is bonded to a silicon atom by a —C bond
• R 4 represents an alkoxy group, an acyloxy group, or a halogen group
• a represents an integer of 1 to 3
• R 5 and R 7 are alkyl groups having 1 to 3 carbon atoms and are bonded to silicon atoms via Si—C bonds
• the dispersion according to the first or second aspect which is at least one silane compound selected from the group consisting of
• a hydrolyzate of the hydrolyzable silane in the dispersion medium a hydrolyzate of a silane compound in which a in formula (1) is an integer of 1 is observed by Si-NMR to form a bridge between silicon atoms.
• (T2+T3)/(T0+T1 ) has a specific value (2 to 15), or the (T1+T2+T3)/(T0) ratio contains a silane compound having a specific value (5 to 100),
• a hydrolyzate of a silane compound in which a in formula (1) is an integer of 2 is observed by Si-NMR to form a bridge between silicon atoms.
• the dispersion according to the third aspect comprising a silane compound having a (D2)/(D0+D1) ratio of 0.01 to 10;
• the value obtained by dividing the water vapor adsorption amount to the silica-containing inorganic oxide particles by the nitrogen gas adsorption amount (specific surface area calculated from the water vapor adsorption amount) / (specific surface area calculated from the nitrogen gas adsorption amount) is 0.15 to 0.95 compared to the silica particles before the addition of the silane compound, the dispersion according to any one of the first to fifth aspects,
• Silica-containing inorganic oxide particles especially inorganic particle dispersion liquids such as silica, ensure dispersion stability due to the repulsive force between particles.
• silica particles silanol groups are present on the surface of the silica particles, and repulsion between the particles occurs due to the negative charge possessed by the silanol groups.
• the magnitude of the absolute value of electric charge varies depending on the pH and salts in the dispersion. There are surface-treated particles that are less affected by pH and salts.
• the surface of the silica particles is treated with a hydrolyzable silane compound having a cationic functional group with a positive charge, or the surface is treated with a hydrolyzable silane compound having an anionic functional group with a negative charge.
• a hydrolyzable silane compound having a cationic functional group with a positive charge or the surface is treated with a hydrolyzable silane compound having an anionic functional group with a negative charge.
• There are methods of processing. Each of these has a repulsive force between particles due to the electrical repulsive force between cationic or anionic functional groups.
• silane compound having a functional group added to the silica particle dispersion liquid is dissolved in the dispersion medium without bonding to the silane (bonded silane) having a functional group bonded to the silica particle surface.
• silanes with functional groups hereinafter referred to as free silanes.
• the silane having a functional group in the dispersion medium exists between the silica particles, and since it has the same functional group, a repulsive force is generated between the bound silane and the free silane. A repulsive force is generated between the particles, resulting in a dispersion with high dispersion stability.
• the ratio of (the number of moles of silicon atoms in the hydrolyzate of the hydrolyzable silane in the dispersion medium)/(the number of moles of silicon atoms of the silane bonded to the surface of the inorganic oxide particles) is a specific value (0.2 ⁇ 30) gives a dispersion of silica particles with high dispersion stability.
• the dispersion medium is an organic solvent
• the silica particles have hydrophilicity based on silanol, which is different from the liquid properties of organic solvents. and have high compatibility with the organic solvent.
• Silane with a hydrophobic functional group is difficult to modify with the above functional group over the entire particle, and compatibility is ensured with a silane monomer with a hydrophobic functional group in the part of the silica particle that is not modified with a hydrophobic functional group. By doing so, it is possible to obtain a highly dispersible liquid dispersion even in an organic solvent.
• the hydrolyzate of the hydrolyzable silane in the dispersion medium preferably exists in such a manner that the repulsive force between the silica particles and the silane monomer is delocalized throughout the dispersion medium. It is preferable not to proceed to For example, when using a silane having three hydrolyzable groups in the hydrolyzable silane, the hydrolyzed compound of the silane compound is observed by Si-NMR and the ratio of bridging oxygen between silicon atoms is For T0, T1, T2, and T3 structures representing 0/2, 1/2, 2/2, and 3/2, (T2+T3)/(T0+T1) has a specific value (2-15, preferably is 2 to 10), or the (T1+T2+T3)/(T0) ratio is a specific value (5 to 100, preferably 5 to 50).
• the hydrolyzed compound of the silane compound is observed by Si-NMR so that the ratio of bridging oxygen between silicon atoms is For D0, D1 and D2 structures showing 0/2, 1/2, and 2/2, the (D1+D2)/(D0) ratio is a specific value (0.1-10), or (D2)/( It is preferable that the D0+D1) ratio is a specific value (0.01 to 10). Either one of these may be satisfied, but it is more preferable to satisfy both.
• the value obtained by dividing the amount of water vapor adsorption to the silica particles by the amount of nitrogen gas adsorption is in the range of 0.15 to 0.95 compared to the silica particles before the addition of the silane compound, so that the inorganic oxide particles can be highly compatible particles over a wide range from aqueous media to organic solvents. .
• Silica particles filled with these bound silanes and free silanes are surface-modified by Q4, in which the number of bridging oxygens between the silicon atoms of the silica particles is 4/2 per silicon atom by Si-NMR observation. This is an increase from before. For example, their increasing ratio can be in the range of 1.01 to 1.5, or 1.01 to 1.15.
• the present invention is a dispersion containing silane-bonded silica-containing inorganic oxide particles surface-modified with a hydrolyzable silane as a dispersoid and using a liquid medium as a dispersion medium, wherein the dispersion medium is a hydrolyzate of the hydrolyzable silane.
• the ratio of (the number of moles of silicon atoms in the hydrolyzate of the hydrolyzable silane in the dispersion medium)/(the number of moles of silicon atoms of the silane bonded to the surface of the inorganic oxide particles) is 0.2 to 30, preferably is 0.2 to 15, and in Si-NMR observation, the number of bridging oxygens between silicon atoms of silica particles is 4/2 per silicon atom. It is the above dispersion containing the silica-containing inorganic oxide particles.
• the average particle size of inorganic substances such as aqueous silica sol refers to the specific surface area measured by the nitrogen adsorption method (BET method), unless otherwise specified.
• the silica-containing inorganic oxide particles are silica particles having an average particle size of 5 nm to 100 nm, preferably 5 to 60 nm, as measured by the BET method, or from the group consisting of silica and alumina, tin oxide, zirconium oxide, titanium oxide, and antimony oxide. At least one selected inorganic oxide particle, the silica-containing inorganic oxide particle being a silica particle, a composite metal oxide of silica and other metal oxides, or a core-shell of silica and other metal oxides Composite oxide particles having a structure may be mentioned.
• silica particles are preferably used as single metal oxides, and composite metal oxide particles of silica and alumina and composite metal oxide particles of tin oxide and silica are mentioned as composite metal oxides.
• composite oxide particles having a core-shell structure include composite oxide particles having a core-shell structure in which a core is titanium oxide or titanium oxide and zirconium oxide and a shell is tin oxide and silica.
• the silica-containing inorganic oxide particles are obtained as a dispersion having a concentration of, for example, 1 to 50 mass % in a dispersion medium.
• the dispersion of the present invention is prepared by the following steps (A) to (B): (A) step: obtaining an aqueous dispersion of the silica-containing inorganic oxide particles; Step (B): Add hydrolyzable silane at a pH of 2.0 to 6.5 to the aqueous dispersion of silica-containing inorganic oxide particles as a ratio of the number of silanes to the surface area of the particles, 0.3 to 100/ nm 2 range, the temperature is raised to within 50 to 99° C.
• the aqueous dispersion of silica-containing inorganic oxide particles obtained in step (A) is obtained as a dispersion having a concentration of, for example, 1 to 50% by mass of silica-containing inorganic oxide particles in an aqueous medium.
• the aqueous silica sol is prepared by using water glass as a starting material, a) cation-exchanging the water glass to obtain active silicic acid, and b) heating the active silicic acid to obtain silica particles. .
• a mineral acid for example, hydrochloric acid, nitric acid, or sulfuric acid
• metal impurities other than silica are eluted by cation exchange and anion exchange.
• Activated silicic acid from which unnecessary anions are removed can be used.
• an alkali component eg, NaOH, KOH
• a seed liquid and a feed liquid are prepared by adding an alkali to the active silicic acid obtained in step a), and the feed liquid is supplied while heating the seed liquid to increase the silica particle diameter.
• step (B) An aqueous silica sol having an arbitrary particle size can be obtained by increasing the .
• step (B) the pH of the aqueous dispersion of silica-containing inorganic oxide particles obtained in step (A) can be adjusted to 2.0 to 6.5, and hydrolyzable silane can be added. Acid or alkali can be used for pH adjustment.
• Acids include mineral acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, oxalic acid, citric acid, acetic acid, lactic acid, malic acid, succinic acid, tartaric acid, butyric acid, fumaric acid, propionic acid and ascorbic acid.
• alkalis include ammonia, amines, quaternary ammonium hydroxides, alkali metal hydroxides, alkali metal alkoxides, and alkali metal salts of aliphatic carboxylic acids.
• Amines include primary amines, secondary amines, and tertiary amines.
• Examples of primary amines include methylamine, ethylamine, n-propylamine and i-propylamine.
• Examples of secondary amines include ethyl n-propylamine, ethyl i-propylamine, dipropylamine, di-i-propylamine, ethylbutylamine, n-propylbutylamine, dibutylamine, ethylpentylamine, n-propylpentylamine, i-propylpentylamine. , dipentylamine, ethyloctylamine, i-propyloctylamine, butyloctylamine, dioctylamine and the like.
• tertiary amine examples include triethylamine, ethyldi-n-propylamine, diethyl-n-propylamine, tri-n-propylamine, tri-i-propylamine, ethyldibutylamine, diethylbutylamine, i-propyldibutylamine, di-i-propylbutylamine, tributylamine, Ethyldipentylamine, diethylpentylamine, tripentylamine, methyldioctylamine, dimethyloctylamine, ethyldioctylamine, diethyloctylamine, trioctylamine and the like.
• the quaternary ammonium hydroxide is preferably a tetraalkylammonium hydroxide having 4 to 40 carbon atoms in total. Examples thereof include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-i-propylammonium hydroxide, tetrabutylammonium hydroxide, and ethyltrimethylammonium hydroxide.
• Alkali metal hydroxides include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like.
• Alkali metal alkoxides include sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide and the like.
• Alkali metal salts of aliphatic carboxylic acids include alkali metal salts of saturated aliphatic carboxylic acids having 10 to 30 carbon atoms and alkali metal salts of unsaturated aliphatic carboxylic acids.
• Alkali metals include sodium and potassium.
• Examples of the saturated aliphatic carboxylic acid alkali metal salt include alkali metal laurate, alkali metal myristate, alkali metal palmitate, alkali metal stearate and the like.
• Examples of the unsaturated aliphatic carboxylic acid alkali metal salt include alkali metal oleate, alkali metal linoleate, alkali metal linolenate and the like.
• At least one silane compound selected from the group consisting of the above formulas (1) to (3) can be used as the hydrolyzable silane used in the step (B).
• R 3 is an alkyl group, a halogenated alkyl group, an alkenyl group, or an organic group having an epoxy group, (meth)acryloyl group, mercapto group, amino group, ureido group, or cyano group, and Si— C-bonded to a silicon atom
• R 4 represents an alkoxy group, an acyloxy group, or a halogen group
• a represents an integer of 1 to 3
• R 5 and R 7 are alkyl groups having 1 to 3 carbon atoms and are bonded to silicon atoms via Si—C bonds
• R 6 and R 7 are represents an alkoxy group, an acyloxy group, or a halogen group
• Y represents an alkylene group, an NH group, or an oxygen atom; and at least one of R 5 and R 7
• the above alkyl group is an alkyl group having 1 to 18 carbon atoms, such as methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group.
• the alkenyl group is an alkenyl group having 2 to 10 carbon atoms, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl and 3-butenyl.
• alkoxy group examples include alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t -butoxy group, n-pentyloxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2 -dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group and the like, but are not limited thereto.
• the acyloxy group having 2 to 10 carbon atoms is, for example, methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, i-propylcarbonyloxy group, n-butylcarbonyloxy group, i-butyl carbonyloxy group, s-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, 1-methyl-n-butylcarbonyloxy group, 2-methyl-n-butylcarbonyloxy group, 3-methyl -n-butylcarbonyloxy group, 1,1-dimethyl-n-propylcarbonyloxy group, 1,2-dimethyl-n-propylcarbonyloxy group, 2,2-dimethyl-n-propylcarbonyloxy group, 1-ethyl -n-propylcarbonyloxy group, n-hexylcarbonyloxy group, 1-methyl-n-
• halogen group examples include fluorine, chlorine, bromine and iodine.
• the (meth)acryloyl group means both an acryloyl group and a methacryloyl group.
• Formulas (2) and (3) above are preferably compounds capable of forming trimethylsilyl groups on the surfaces of silica particles. Examples of these compounds are given below.
• R12 is an alkoxy group such as a methoxy group and an ethoxy group.
• hydroxyl groups on the surfaces of silica particles for example, silanol groups in the case of silica particles, react with the silane compound to coat the surfaces of the silica particles with the silane compound through siloxane bonds.
• the reaction temperature can be in the range of 20°C to the boiling point of the dispersion medium, for example, in the range of 20°C to 100°C.
• the reaction time can be about 0.1 to 6 hours.
• Preferred functional groups include amino group, epoxy group, alkyl group, phenyl group and the like, such as aminopropyl group, aminoethylaminopropyl group, methyl group, phenyl group, glycidoxypropyl group, epoxycyclohexylethyl group, trifluoropropyl group. and the like.
• Silane compounds corresponding to them include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropylmethyldiethoxysilane.
• Silane Methyltrimethoxysilane, Methyltriethoxysilane, Phenyltrimethoxysilane, Phenyltriethoxysilane, Glycidoxypropyltrimethoxysilane, Glycidoxypropyltriethoxysilane, Epoxycyclohexylethyltrimethoxysilane, Epoxycyclohexylethyltriethoxysilane silane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, and the like.
• the silane compound is added to the silica sol in such a manner that the silica particle surface is covered with a silane compound corresponding to a coating amount in which the number of silicon atoms in the silane compound is 0.1/nm 2 to 4.0/nm 2 .
• the surface of silica particles can be coated. Water is necessary for the hydrolysis of the silane compound, and if it is a sol of an aqueous solvent, such an aqueous solvent is used. Also, the hydrolysis can be carried out with or without a catalyst. When the reaction is carried out without a catalyst, the surface of the silica particles serves as a catalyst, and a silica sol having a pH of 2.0 to 6.5 can be used.
• hydrolysis catalysts include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.
• Metal chelate compounds as hydrolysis catalysts include, for example, triethoxy-mono(acetylacetonato)titanium and triethoxy-mono(acetylacetonato)zirconium.
• Organic acids as hydrolysis catalysts include, for example, acetic acid and oxalic acid.
• Inorganic acids as hydrolysis catalysts include, for example, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
• Examples of organic bases as hydrolysis catalysts include pyridine, pyrrole, piperazine and quaternary ammonium salts.
• Inorganic bases as hydrolysis catalysts include, for example, ammonia, sodium hydroxide, and potassium hydroxide.
• a hydrolyzable silane is added to the aqueous dispersion of inorganic oxide particles obtained in the step (A), and the mixture is stirred at room temperature (for example, about 15 to 25° C.) for 0.01 to 2 hours. After that, the temperature is raised to a temperature within 50 to 99° C. and stirred for 0.01 to 14 hours, and the stirring time after raising the temperature to 50 to 99° C. is 1 to 100 times the stirring time at room temperature, or It is preferable to carry out within the range of 1 to 7 times.
• the hydrolyzate of the hydrolyzable silane is not sufficiently coated on the inorganic oxide particles (for example, silica particles), and the silane compound present in the dispersion medium is later locally coated. , uniform coverage cannot be achieved.
• the ratio of the T1, T2, T3, D1, and D2 structures decreases, which is not preferable in terms of the repulsive force of the particles.
• the state in which the hydrolyzate of the hydrolyzable silane is bonded to the silica particles and the state in which the hydrolyzate of the hydrolyzable silane exists in the dispersion medium coexist. Both of them have a ratio of (number of moles of silicon atoms in the hydrolyzate of the hydrolyzable silane in the dispersion medium) / (number of moles of silicon atoms of the silane bonded to the surface of the inorganic oxide particles) of 0.2 to 30. Occasionally contributes to the stability of inorganic oxide sol (silica sol).
• the silica particles When the hydrolyzate of the hydrolyzable silane of the present invention is bonded to the silica particles, the silica particles have a reduced amount of silanol. It is characteristic that Q4, which is 4/2 of the silane, is increased from before the surface modification of the silane.
• the silica particles are obtained by dividing the specific surface area calculated from the amount of water vapor adsorbed on the silica particles by the specific surface area calculated from the amount of nitrogen gas adsorbed.
• a certain (specific surface area calculated from water vapor adsorption amount)/(specific surface area calculated from nitrogen gas adsorption amount) is 0.15 to 0.95 compared to the silica particles before addition of the silane compound.
• the hydrolyzate of the hydrolyzable silane in the dispersion medium the hydrolyzate of the silane compound in which a in formula (1) is an integer of 1 is observed by Si-NMR, and the ratio of bridging oxygen between silicon atoms for T0, T1, T2, and T3 structures exhibiting 0/2, 1/2, 2/2, and 3/2 per silicon atom, the (T2+T3)/(T0+T1) ratio is It is characterized by containing a silane compound having a ratio of 2 to 10 or (T1+T2+T3)/(T0) of 5 to 100.
• the hydrolyzate of the hydrolyzable silane in the dispersion medium the hydrolyzate of the silane compound in which a in formula (1) is an integer of 2 is observed by Si-NMR, and the ratio of bridging oxygen between silicon atoms is 0/2, 1/2, 2/2 per silicon atom, the (D1+D2)/(D0) ratio is 0.1 to 10, or (D2 )/(D0+D1) ratio is 0.01-10. Either one of these may be satisfied, but it is more preferable to satisfy both.
• Organic solvents include organic solvents such as alcohols, ketones, ethers, esters, amides, and hydrocarbons.
• the alcohol is an alcohol having 1 to 10 carbon atoms, such as methanol, ethanol, i-propanol, n-propanol and butanol.
• Ketones are linear or cyclic aliphatic ketones having 3 to 30 carbon atoms, such as methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl amyl ketone and cyclohexanone.
• Ethers are linear or cyclic aliphatic ethers having 3 to 30 carbon atoms, such as diethyl ether and tetrahydrofuran.
• Esters are linear or cyclic esters having 2 to 30 carbon atoms, such as ethyl acetate, butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, n-propyl acetate, i-propyl acetate, ethyl lactate, lactic acid.
• Amide is an aliphatic amide having 3 to 30 carbon atoms, such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, N-ethylpyrrolidone and the like.
• Hydrocarbons are linear or cyclic aliphatic or aromatic hydrocarbons having 6 to 30 carbon atoms, such as hexane, heptane, octane, nonane, decane, benzene, toluene and xylene.
• the silica-containing inorganic oxide sol (for example, silica sol) of the present invention can be used as a high-salt dispersion medium sol, an adhesive, a release agent, a semiconductor encapsulant, an LED encapsulant, a paint, a film internal additive, a hard coating agent, a photo Used in resist materials, printing inks, detergents, cleaners, additives for various resins, insulating compositions, rust preventives, lubricating oils, metal working oils, coating agents for films, stripping agents, well treatment agents, etc. can be done.
• aqueous silica sol pH value, electrical conductivity, viscosity, DLS average particle size, amount of silane bonds
• sample analysis after room temperature salt resistance test or high temperature salt resistance test of sample prepared using the aqueous silica sol was carried out using the following equipment.
• DLS average particle size average particle size by dynamic light scattering method: A dynamic light scattering particle size measuring device, Zetasizer Nano (manufactured by Spectris Co., Ltd., Malvern Division) was used.
• - pH A pH meter (manufactured by Toa DKK Co., Ltd.) was used.
• the aqueous silica sol from which the free silane was removed was dried by heating at 100° C. and pulverized in a mortar to obtain a silica sol powder.
• the carbon content of the obtained silica sol powder was measured with an organic trace element metal analyzer, and the silane bond content was calculated by the following formula from the obtained carbon content.
• Amount of surface treatment (Cm/Cn/Sc x A)/(Ct x Cs)
• Cm is the carbon content
• Cn is the carbon molecular weight
• Sc is the number of carbon atoms in the silane
• A is Avogadro's number
• Ct is the silica particle mass
• Cs is the silica specific surface area.
• the unit of the amount of silane bonds obtained by measuring the amount of carbon is (number/nm 2 ).
• the amount of nitrogen in the aqueous silica sol from which free silane was removed was measured with a TN measurement device, and the amount of silane bond was calculated from the obtained nitrogen amount by the following equation.
• Amount of surface treatment (Nm/Nn/Sn x A)/(Ct x Cs) where Nm is the nitrogen content, Nn is the nitrogen molecular weight, Sn is the number of nitrogen atoms in the silane, A is Avogadro's number, Ct is the silica particle mass, and Cs is the silica specific surface area.
• the unit of the amount of silane bonds obtained by measuring the amount of nitrogen is (number/nm 2 ).
• the aqueous silica sol obtained by removing the free silane was dried on a hot plate at 80° C., and the resulting silica gel was pulverized in a mortar and then dried at 150° C. for 3 hours to obtain dry silica powder. Based on the BET theory, the specific surface area (m 2 /g) of this powder was measured by the nitrogen adsorption method (BET method, ie nitrogen gas BET method).
• A The ratio of the DLS average particle size after the salt tolerance test/the DLS average particle size before the test is 1.1 or less.
• B The ratio of the DLS average particle size after the salt tolerance test/the DLS average particle size before the test is 1.2 to 1.5.
• C The ratio of the DLS average particle size after the salt resistance test/the DLS average particle size before the test is 1.6 to 2.4.
• D The ratio of the DLS average particle size after the salt tolerance test/the DLS average particle size before the test is 2.5 to 20.0.
• E The ratio of the DLS average particle size after the salt resistance test/the DLS average particle size before the test was 20.1 or more, or clouded and solid-liquid separation occurred. Salt tolerance test results show that A is the most preferred, with B, C, D and E being the preferred results in that order.
• High temperature salt resistance evaluation -1 Put 65 g of the salt tolerance test sample in a 120 ml Teflon (registered trademark) container that can be sealed, and after sealing, place the Teflon (registered trademark) container in a dryer at 100 ° C. and hold at 100 ° C. for a predetermined time (10 hours ), the appearance, pH, electrical conductivity, and DLS average particle size of the aqueous silica sol (silica particles) in the sample were evaluated.
• the high-temperature salt tolerance was determined according to the same criteria as the determination of the salt tolerance in the room-temperature salt tolerance evaluation.
• High temperature salt resistance evaluation -2 High-temperature salt resistance was determined in the same manner as described above (high-temperature salt resistance evaluation-1), except that the temperature of the dryer was 120° C. and the holding time was 10 hours.
• Example 1 Aqueous silica sol (Snowtex (trade name) ST-O manufactured by Nissan Chemical Industries, Ltd., silica concentration: 20.5% by mass, average particle size by BET method: 11.7 nm, average particle size by DLS method) in a 2000 ml glass eggplant flask After adding 1000 g of a magnetic stirrer (diameter 18.6 nm) and stirring with a magnetic stirrer, 3-glycidide was added so that the silane compound was 0.5/nm 2 with respect to the surface area of silica in the aqueous silica sol.
• a magnetic stirrer diameter 18.6 nm
• the aqueous silica sol of Example 1 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method. (Evaluation of silane bond content) The silane bond content of the aqueous silica sol of Example 1 was evaluated.
• a salt tolerance test sample was prepared according to ⁇ Preparation of salt tolerance test sample>, and after holding at 20°C for 10 hours according to ⁇ Room temperature salt tolerance evaluation>, the sample was taken out and room temperature salt tolerance was evaluated.
• Example 2 For silica in the aqueous silica sol (Nissan Chemical Co., Ltd. Snowtex (trade name) ST-O, average particle size 11.7 nm by BET method, average particle size 18.6 nm by DLS method), Same as Example 1 except that 149.7 g of 3-glycidoxypropyltrimethoxysilane (Dynasylan GLYMO manufactured by Evonik) was added so that the number of silane compounds was 8.0/nm 2 with respect to the surface area of silica. The operation yielded 1149.7 g of aqueous sol.
• the aqueous silica sol of Example 2 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method. (Evaluation of silane bond content) The silane bond content of the aqueous silica sol of Example 2 was evaluated.
• a salt resistance test sample was prepared according to (Preparation of salt resistance test sample), and after holding at 100° C. for 10 hours according to (Evaluation of high temperature salt resistance-1), the sample was taken out and evaluated for high temperature salt resistance.
• Example 3 For silica in the aqueous silica sol (Nissan Chemical Co., Ltd. Snowtex (trade name) ST-O, average particle size 11.7 nm by BET method, average particle size 18.6 nm by DLS method), Same as Example 1 except that 576.2 g of 3-glycidoxypropyltrimethoxysilane (Dynasylan GLYMO manufactured by Evonik) was added so that the number of silane compounds was 30.8/nm 2 with respect to the surface area of silica. The operation yielded 1576.2 g of aqueous sol. The aqueous silica sol of Example 3 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method.
• silane bond content The silane bond content of the aqueous silica sol of Example 3 was evaluated.
• a salt resistance test sample was prepared according to (Preparation of salt resistance test sample), and after holding at 100° C. for 10 hours according to (Evaluation of high temperature salt resistance-1), the sample was taken out and evaluated for high temperature salt resistance.
• Example 4 For silica in the aqueous silica sol (Snowtex (trade name) ST-O manufactured by Nissan Chemical Industries, average particle size 11.7 nm by BET method, average particle size 18.6 nm by DLS method), Same as Example 1 except that 864.3 g of 3-glycidoxypropyltrimethoxysilane (Dynasylan GLYMO manufactured by Evonik) was added so that the number of silane compounds was 46.2/nm 2 with respect to the surface area of silica. The operation yielded 1864.3 g of aqueous sol. The aqueous silica sol of Example 4 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method.
• silane bond content The silane bond content of the aqueous silica sol of Example 4 was evaluated.
• a salt resistance test sample was prepared according to (Preparation of salt resistance test sample), and after holding at 100° C. for 10 hours according to (Evaluation of high temperature salt resistance-1), the sample was taken out and evaluated for high temperature salt resistance.
• Example 5 For silica in the aqueous silica sol (Nissan Chemical Co., Ltd. Snowtex (trade name) ST-O, average particle size 11.7 nm by BET method, average particle size 18.6 nm by DLS method), The same operation as in Example 1 was performed except that 5.4 g of methyltrimethoxysilane (KBM-13 manufactured by Shin-Etsu Chemical Co., Ltd.) was added so that the number of silane compounds was 0.5/nm 2 with respect to the surface area of silica. 1005.4 g of aqueous sol were obtained. The aqueous silica sol of Example 5 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method.
• KBM-13 methyltrimethoxysilane
• silane bond content The silane bond content of the aqueous silica sol of Example 5 was evaluated.
• a salt tolerance test sample was prepared according to (Preparation of salt tolerance test sample) and kept at 20°C for 10 hours according to (Evaluation of room temperature salt tolerance).
• Example 6 For silica in the aqueous silica sol (Nissan Chemical Co., Ltd. Snowtex (trade name) ST-O, average particle size 11.7 nm by BET method, average particle size 18.6 nm by DLS method), Aqueous solution was prepared in the same manner as in Example 1, except that 4.8 g of dimethyldimethoxysilane (KBM-22 manufactured by Shin-Etsu Chemical Co., Ltd.) was added so that the number of silane compounds was 0.5/nm 2 with respect to the surface area of silica. 1004.8 g of sol were obtained. The aqueous silica sol of Example 6 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method.
• KBM-22 dimethyldimethoxysilane
• silane bond content The silane bond content of the aqueous silica sol of Example 6 was evaluated.
• a salt tolerance test sample was prepared according to (Preparation of salt tolerance test sample) and kept at 20°C for 10 hours according to (Evaluation of room temperature salt tolerance).
• Example 7 For silica in the aqueous silica sol (Nissan Chemical Co., Ltd. Snowtex (trade name) ST-O, average particle size 11.7 nm by BET method, average particle size 18.6 nm by DLS method), 9.8 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.) was added so that the number of silane compounds was 0.5/nm 2 with respect to the surface area of silica. 1009.8 g of aqueous sol was obtained by the same operation as in Example 1 except for the above.
• KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.
• the aqueous silica sol of Example 7 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method. (Evaluation of silane bond content) The silane bond content of the aqueous silica sol of Example 7 was evaluated.
• a salt tolerance test sample was prepared according to (Preparation of salt tolerance test sample) and kept at 20°C for 10 hours according to (Evaluation of room temperature salt tolerance).
• Example 8 For silica in the aqueous silica sol (Nissan Chemical Co., Ltd. Snowtex (trade name) ST-O, average particle size 11.7 nm by BET method, average particle size 18.6 nm by DLS method), Same as Example 1 except that 8.6 g of trifluoropropyltrimethoxysilane (KBM-7103 manufactured by Shin-Etsu Chemical Co., Ltd.) was added so that the number of silane compounds was 0.5/nm 2 with respect to the surface area of silica. The operation yielded 1008.6 g of aqueous sol.
• KBM-7103 manufactured by Shin-Etsu Chemical Co., Ltd.
• the aqueous silica sol of Example 8 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method. (Evaluation of silane bond content) The silane bond content of the aqueous silica sol of Example 8 was evaluated.
• a salt tolerance test sample was prepared according to (Preparation of salt tolerance test sample) and kept at 20°C for 10 hours according to (Evaluation of room temperature salt tolerance).
• Example 9 For silica in the aqueous silica sol (Nissan Chemical Co., Ltd. Snowtex (trade name) ST-O, average particle size 11.7 nm by BET method, average particle size 18.6 nm by DLS method), 114.1 g of lactic acid and 140.2 g of aminopropyltriethoxysilane (KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed in advance such that the number of silane compounds per surface area of silica was 8.0/nm 2 . 1254.3 g of aqueous sol was obtained in the same manner as in Example 1 except that the liquid stirred for 30 minutes was added.
• the aqueous silica sol of Example 9 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method. (Evaluation of silane bond content) The silane bond content of the aqueous silica sol of Example 9 was evaluated.
• a salt tolerance test sample was prepared according to (Preparation of salt tolerance test sample) and kept at 20°C for 10 hours according to (Evaluation of room temperature salt tolerance).
• Example 10 Aqueous silica sol (Nissan Chemical Co., Ltd. Snowtex (trade name) ST-O, average particle size 11.7 nm by BET method, average particle size 18.6 nm by DLS method), 114.1 g of lactic acid and stirred with a magnetic stirrer, aminopropyltrimethoxysilane (KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.) so that the silane compound is 8.0/nm 2 with respect to the surface area of silica in the aqueous silica sol. 1227.7 g of aqueous sol was obtained by the same operation as in Example 1, except that 113.6 g of water sol was added.
• KBM-903 aminopropyltrimethoxysilane
• the aqueous silica sol of Example 10 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method. (Evaluation of silane bond content) The silane bond content of the aqueous silica sol of Example 10 was evaluated.
• a salt tolerance test sample was prepared according to (Preparation of salt tolerance test sample) and kept at 20°C for 10 hours according to (Evaluation of room temperature salt tolerance).
• Example 11 Aqueous silica sol (Nissan Chemical Co., Ltd. Snowtex (trade name) ST-O, average particle size 11.7 nm by BET method, average particle size 18.6 nm by DLS method), lactic acid 228.2 g was added and stirred with a magnetic stirrer, and aminoethylaminopropyltrimethoxysilane ( KBM- 1369.1 g of aqueous sol was obtained by the same procedure as in Example 1, except that 140.9 g of 603) was added.
• the aqueous silica sol of Example 11 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method.
• silane bond content The silane bond content of the aqueous silica sol of Example 11 was evaluated.
• a salt tolerance test sample was prepared according to (Preparation of salt tolerance test sample), and after holding at 120°C for 10 hours according to (Evaluation of high temperature salt tolerance-2), the sample was taken out and the room temperature salt tolerance was evaluated.
• Example 12 Aqueous silica sol (Nissan Chemical Co., Ltd. Snowtex (trade name) ST-O, average particle size 11.7 nm by BET method, average particle size 18.6 nm by DLS method), lactic acid 228.2 g was added and stirred with a magnetic stirrer, and aminoethylaminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd. KBM- 1358.9 g of aqueous sol was obtained by the same procedure as in Example 1, except that 130.7 g of 602) was added.
• the aqueous silica sol of Example 12 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method. (Evaluation of silane bond content) The silane bond content of the aqueous silica sol of Example 12 was evaluated.
• a salt tolerance test sample was prepared according to (Preparation of salt tolerance test sample), and after holding at 120°C for 10 hours according to (Evaluation of high temperature salt tolerance-2), the sample was taken out and the room temperature salt tolerance was evaluated.
• Example 13 Aqueous silica sol (Nissan Chemical Co., Ltd. Snowtex (trade name) ST-OXS, silica concentration 10.5% by mass, average particle size 5.0 nm by BET method, average particle size 8.1 nm by DLS method) in 179.4 g of 3-glycidoxypropyltrimethoxysilane (Dynasylan GLYMO manufactured by Evonik) was added to silica so that the number of silane compounds per surface area of silica in the aqueous silica sol was 8.0/nm 2 .
• Dynasylan GLYMO manufactured by Evonik 3-glycidoxypropyltrimethoxysilane
• aqueous sol 1179.4 g was obtained by the same operation as in Example 1 except that The aqueous silica sol of Example 13 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method. (Evaluation of silane bond content) The silane bond content of the aqueous silica sol of Example 13 was evaluated.
• a salt resistance test sample was prepared according to (Preparation of salt resistance test sample), and after holding at 100° C. for 10 hours according to (Evaluation of high temperature salt resistance-1), the sample was taken out and evaluated for high temperature salt resistance.
• Example 14 Aqueous silica sol (Snowtex (trade name) ST-OL manufactured by Nissan Chemical Industries, Ltd., silica concentration 20.5% by mass, average particle size 45.0 nm by BET method, average particle size 78.0 nm by DLS method) in 159.0 g of 3-glycidoxypropyltrimethoxysilane (Dynasylan GLYMO manufactured by Evonik) was added to silica so that the number of silane compounds per surface area of silica in the aqueous silica sol was 32.7/nm 2 .
• aqueous sol 1159.0 g was obtained by the same operation as in Example 1 except that The aqueous silica sol of Example 14 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method. (Evaluation of silane bond content) The silane bond content of the aqueous silica sol of Example 14 was evaluated.
• a salt resistance test sample was prepared according to (Preparation of salt resistance test sample), and after holding at 100° C. for 10 hours according to (Evaluation of high temperature salt resistance-1), the sample was taken out and evaluated for high temperature salt resistance.
• aqueous silica sol (Snowtex (trade name) ST-O manufactured by Nissan Chemical Industries, Ltd.) was used as an aqueous silica sol of Comparative Example 1.
• the pH, electrical conductivity, viscosity, and DLS average particle size of the aqueous silica sol (silica particles) of the aqueous silica sol of Comparative Example 1 were evaluated.
• the silane bond content of the aqueous silica sol of Comparative Example 1 was evaluated.
• a salt tolerance test sample was prepared according to (Preparation of salt tolerance test sample) and kept at 20°C for 10 hours according to (Evaluation of room temperature salt tolerance).
• Example 2 By the same operation as in Example 2, 1149.7 g of aqueous silica sol was obtained. 800 g of pure water was added to 200 g of the aqueous silica sol of Example 2, followed by ultrafiltration until 200 g was discharged. 200 g of silica sol were obtained. The aqueous silica sol of Comparative Example 2 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method. (Evaluation of silane bond content) The silane bond content of the aqueous silica sol of Comparative Example 2 was evaluated. A salt resistance test sample was prepared according to (Preparation of salt resistance test sample), and after holding at 100° C. for 10 hours according to (Evaluation of high temperature salt resistance-1), the sample was taken out and evaluated for high temperature salt resistance.
• Example 3 For silica in the aqueous silica sol (Nissan Chemical Co., Ltd. Snowtex (trade name) ST-O, average particle size 11.7 nm by BET method, average particle size 18.6 nm by DLS method), The same operation as in Example 1 was performed except that 35.1 g of methyltrimethoxysilane (KBM-13 manufactured by Shin-Etsu Chemical Co., Ltd.) was added so that the number of silane compounds was 2.0/nm 2 with respect to the surface area of silica. 1035.1 g of aqueous sol were obtained. The aqueous silica sol of Comparative Example 3 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method.
• KBM-13 methyltrimethoxysilane
• silane bond content The silane bond content of the aqueous silica sol of Comparative Example 3 was evaluated.
• a salt tolerance test sample was prepared according to (Preparation of salt tolerance test sample) and kept at 20°C for 10 hours according to (Evaluation of room temperature salt tolerance).
• aqueous silica sol of Comparative Example 4 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method. (Evaluation of silane bond content) The silane bond content of the aqueous silica sol of Comparative Example 4 was evaluated.
• a salt tolerance test sample was prepared according to (Preparation of salt tolerance test sample) and kept at 20°C for 10 hours according to (Evaluation of room temperature salt tolerance).
• Example 5 By the same operation as in Example 9, 1254.3 g of aqueous silica sol was obtained. 800 g of pure water was added to 200 g of the aqueous silica sol of Example 9, followed by ultrafiltration until 200 g was discharged. 200 g of silica sol were obtained. The aqueous silica sol of Comparative Example 5 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method. (Evaluation of silane bond content) The silane bond content of the aqueous silica sol of Comparative Example 5 was evaluated. A salt tolerance test sample was prepared according to (Preparation of salt tolerance test sample) and kept at 20°C for 10 hours according to (Evaluation of room temperature salt tolerance).
• Example 6 By the same operation as in Example 10, 1227.7 g of aqueous silica sol was obtained. 800 g of pure water was added to 200 g of the aqueous silica sol of Example 10, followed by ultrafiltration until 200 g was discharged. 200 g of silica sol were obtained. The aqueous silica sol of Comparative Example 6 was evaluated for pH, electrical conductivity, viscosity, and average particle size by the DLS method. (Evaluation of silane bond content) The silane bond content of the aqueous silica sol of Comparative Example 6 was evaluated.
• aqueous silica sol (Snowtex (trade name) ST-OXS manufactured by Nissan Chemical Industries, Ltd.) was used as an aqueous silica sol of Comparative Example 7.
• the pH, electrical conductivity, viscosity, and DLS average particle size of the aqueous silica sol (silica particles) of the aqueous silica sol of Comparative Example 7 were evaluated.
• evaluation of silane bond content The silane bond content of the aqueous silica sol of Comparative Example 7 was evaluated.
• a salt tolerance test sample was prepared according to (Preparation of salt tolerance test sample) and kept at 20°C for 10 hours according to (Evaluation of room temperature salt tolerance).
• aqueous silica sol (Snowtex (trade name) ST-OL manufactured by Nissan Chemical Industries, Ltd.) was used as an aqueous silica sol of Comparative Example 8.
• the pH, electrical conductivity, viscosity, and DLS average particle size of the aqueous silica sol (silica particles) of the aqueous silica sol of Comparative Example 8 were evaluated.
• evaluation of silane bond content The silane bond content of the aqueous silica sol of Comparative Example 8 was evaluated.
• a salt tolerance test sample was prepared according to (Preparation of salt tolerance test sample) and kept at 20°C for 10 hours according to (Evaluation of room temperature salt tolerance).
• a brine test sample was prepared according to (Preparation of salt tolerance test sample) and kept at 20° C. for 10 hours according to (Evaluation of room temperature salt tolerance), then the sample was taken out and evaluated for room temperature salt tolerance.
• Tables 1 to 6 show the compositions (component concentrations) and salt tolerance test results of the aqueous silica sols of Examples, and Tables 7 and 8 show the compositions (component concentrations) and salt tolerance test results of the aqueous silica sols of Comparative Examples.
• the types (codes) of the silane compounds in the table are as follows.
• ⁇ LTAC Lauryltrimethylammonium chloride “trade name Cathiogen TML”, active ingredient 30.0%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
• ⁇ GPS 3-glycidoxypropyltrimethoxysilane “trade name Dynasylan GLYMO”, Evonik ( Co., Ltd. MTMS: Methyltrimethoxysilane "trade name KBM-13", Shin-Etsu Chemical Co., Ltd.
• DMS Dimethyldimethoxysilane "trade name KBM-22", Shin-Etsu Chemical Co., Ltd.
• EPCHS ( 3,4-epoxycyclohexyl)ethyltrimethoxysilane "trade name KBM-303", manufactured by Shin-Etsu Chemical Co., Ltd.
• TFPS Trifluoropropyltrimethoxysilane "trade name KBM-7103", manufactured by Shin-Etsu Chemical Co., Ltd.
• APTES 3-aminopropyltriethoxysilane “trade name KBE-903”, manufactured by Shin-Etsu Chemical Co., Ltd.
• APTMS 3-aminopropyltrimethoxysilane “trade name KBM-903”, Shin-Etsu Chemical ( Co., Ltd.
• AEAPTMS N-2-(aminoethyl)-3-aminopropyltrimethoxysilane “trade name KBM-603”, Shin-Etsu Chemical Co., Ltd.
• AEAPMDMS N-2-(aminoethyl)-3 -Aminopropylmethyldimethoxysilane "trade name KBM-602", manufactured by Shin-Etsu Chemical Co., Ltd.
• the aqueous silica sol of the present invention can be expected to have an effect of improving the stability of silica particles depending on the form of the free silane contained.
• the form of free silane was obtained by putting 6 g of aqueous silica sol into a 15 ml centrifugal filter unit (trade name: Amicon Ultra 15 (Merck Co., Ltd.)), centrifuging at a centrifugal force of 2770 G for 20 minutes, and discharging free silane at the bottom of the unit.
• a liquid containing is analyzed by Si-NMR, and analyzed by calculating the content ratio of the T structure or D structure.
• the T structure was measured for Examples 2, 9, 10, 13 and 15, and Table 9 shows the measurement results.
• the D structure was measured for Example 12, and the measurement results are shown in Table 10.
• a part of the silane compound is bound to the surface of the silica particles, so that an effect of improving the stability of the silica particles can be expected.
• the form of bound silane was analyzed by analyzing the liquid obtained in (removal of free silane) by Si-NMR and calculating the ratio of the Q structure.
• the Q structure was measured for Examples 2, 5, 6, 7, 8, 9, 10, 11, 12, 13 and 14 and Comparative Examples 1, 7 and 8, and Table 11 shows the measurement results.
• the silanol group on the surface of the silica particles is replaced with a silane compound having a functional group, so an effect of improving the stability of the silica particles can be expected.
• the value obtained by dividing the specific surface area calculated from the amount of water vapor adsorption to the silica particles by the specific surface area calculated from the amount of nitrogen gas adsorption, (specific surface area calculated from the amount of water vapor adsorption) / (specific surface area calculated from the amount of nitrogen gas adsorption) is It shows that the silanol groups on the silica particle surface are replaced with a silane compound having a functional group.
• the amount of water vapor adsorption and the amount of nitrogen gas adsorption were analyzed according to the procedures of (measurement of water vapor adsorption amount) and (measurement of nitrogen gas adsorption amount).
• the water vapor adsorption amount and nitrogen gas adsorption amount were measured for Examples 1, 2, 5, 7, 8, 13, 14 and Comparative Examples 1, 3, 7, and 8, and (specific surface area calculated from the water vapor adsorption amount) / ( Table 12 shows the measurement results of the value obtained by dividing the value after the silane compound treatment by the value before the silane compound treatment (specific surface area calculated from the nitrogen gas adsorption amount).
• the present invention can provide a dispersion of inorganic oxide particles, particularly a dispersion of silica particles, which has high dispersion stability even under high temperature and high salinity.

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