CN101535182A - Silica-alumina composite sol and process for production thereof - Google Patents
Silica-alumina composite sol and process for production thereof Download PDFInfo
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- CN101535182A CN101535182A CNA2007800411702A CN200780041170A CN101535182A CN 101535182 A CN101535182 A CN 101535182A CN A2007800411702 A CNA2007800411702 A CN A2007800411702A CN 200780041170 A CN200780041170 A CN 200780041170A CN 101535182 A CN101535182 A CN 101535182A
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- hydrate particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0008—Sols of inorganic materials in water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/146—After-treatment of sols
- C01B33/149—Coating
Abstract
The present invention provides a silica-alumina composite sol having excellent transparency, film-forming property and water resistance, which comprises a composite colloid particle comprising a colloidal silica particle coated with a fine colloidal alumina hydrate particle and a colloidal alumina hydrate particle having a major axis diameter 10-fold or more greater than the diameter of a primary particle of the colloidal silica particle bound to each other; and a process for producing the silica-alumina composite sol. Disclosed is a silica-alumina composite sol which comprises a composite colloid particle comprising a colloidal silica particle coated with a fine colloidal alumina hydrate particle and a colloidal alumina hydrate particle bound to each other, wherein the colloidal alumina hydrate particle has a major axis diameter 10-fold or more greater than the diameter of a primary particle of the colloidal silica particle and a minor axis diameter of 2 to 10 nm. Also disclosed is a process for producing the silica-alumina composite sol.
Description
Technical field
The present invention relates to silica-alumina composite sol and manufacture method thereof, described silica-alumina composite sol contains the colloid silica particle that has been covered by small colloidal alumina hydrate particles and the composite gel particle of colloidal alumina hydrate particles be combined into.
Silica-alumina composite sol of the present invention has the feature of silicon dioxide gel and alumina sol, if dry on solid surface, then shows the excellent transparency, film-forming properties and water tolerance.In addition, because the composite gel particle positively charged that silica-alumina composite sol of the present invention contained, so with positively charged ion be that tensio-active agent, cationic colloid, positively charged ion are consistency, miscibility and the excellent dispersion of emulsion or cationic powder slurry etc., thereby can and use with these positively charged ion based materials.
Because silica-alumina composite sol of the present invention has high transparent and excellent film-forming properties, water tolerance, so can be at the electro-magnetic steel plate surface treatment agent, the additive of the anti-corrosion treating agent of the plated steel sheet of automobile, household electrical appliances, the employed zinc of building materials, aluminium etc., the soaker of refractory body, tackiness agent, the tackiness agent that fire-resistant coating agent is used, little filler that ink jet recording medium is used, the tackiness agent of various catalyzer, strengthening agent, use in the various fields such as antifogging agent that the tackiness agent that the ceramic fiber moulding is used, film for agricultural use are used.
Background technology
In general, use spin-coating method, pickling process to be coated on separately on sheet glass, the steel plate silicon dioxide gel and when dry, be difficult to obtain densification and level and smooth tunicle owing to generate small chapping, the shortage film-forming properties.In addition, the known alumina sol of people can obtain fine and close tunicle on sheet glass, steel plate, but because the alumina sol drying is being made under the situation of tunicle, powder, in case make it to contact with water, then become alumina sol once more again, thereby tunicle is destroyed, so lack water tolerance.
Therefore, in order to remedy silicon dioxide gel and alumina sol shortcoming separately, people have carried out silicon dioxide gel is mixed use with alumina sol, thereby or use, but do not satisfied film-forming properties and water-proof colloidal sol simultaneously with the silicon dioxide gel of basic aluminium salt lining silicon dioxide gel modulation positively charged.
As the manufacture method of the silicon dioxide gel of the positively charged that has been covered by basic aluminium salt, the someone discloses the method (referring to Patent Document 1,2) of adding alkaline aluminum water solution in acidic aqueous silicon dioxide gel.With being covered of obtaining of method by basic aluminium salt the silicon dioxide gel of positively charged, same with the silicon dioxide gel in the past that is not covered by basic aluminium salt, dry and lack film-forming properties when making tunicle on solid surface.
Like this in silicon dioxide gel, the alumina sol of silicon dioxide gel, positively charged or colloidal sol that they are mixed, on solid surface dry and tunicle have excellent film-forming properties and water tolerance and have the colloidal sol of high transparent not known as yet.
Patent documentation 1: No. 3007878 specification sheets of United States Patent (USP)
Patent documentation 2: special public clear 47-26959 communique
Summary of the invention
The purpose of this invention is to provide silica-alumina composite sol and manufacture method thereof, described silica-alumina composite sol has excellent film-forming properties and water tolerance, the composite gel particle that contains following colloid silica particle and following colloidal alumina hydrate particles be combined into, the colloid silica particle that described colloid silica particle has been covered by small colloidal alumina hydrate particles, described colloidal alumina hydrate particles is that major diameter is the colloidal alumina hydrate particles more than 10 times of the primary particle size of this colloid silica particle.
The present invention as first scheme is, a kind of silica-alumina composite sol, it contains the composite gel particle of following colloid silica particle and following colloidal alumina hydrate particles be combined into, the colloid silica particle that described colloid silica particle has been covered by small colloidal alumina hydrate particles, described colloidal alumina hydrate particles be major diameter be this colloid silica particle primary particle size more than 10 times and minor axis be the colloidal alumina hydrate particles of 2～10nm.
As alternative plan be, a kind of silica-alumina composite sol, it contains the composite gel particle that combines following colloidal alumina hydrate particles, described colloidal alumina hydrate particles be major diameter be this colloid silica particle primary particle size more than 10 times and minor axis be the following colloidal alumina hydrate particles of the primary particle size of this colloid silica, the silicon-dioxide (SiO in the described silica-alumina composite sol
2) solids component and aluminum oxide (Al
2O
3) the mass ratio SiO of conversion solids component
2: Al
2O
3Be 70:30～20:80.
As third party's case be, according to first scheme or the described silica-alumina composite sol of alternative plan, the primary particle size of the colloid silica that has been covered by small colloidal alumina hydrate particles is 2～13nm, and the major diameter of colloidal alumina hydrate particles is 50～500nm.
Be that the manufacture method of a kind of first scheme, alternative plan and the described silica-alumina composite sol of third party's case comprises following operation (A) and operation (B) as cubic case:
(A): with silicon-dioxide (SiO
2) solids component is that the primary particle size of 0.5～50 quality %, colloid silica particle is acidic aqueous silicon dioxide gel and the aluminum oxide (Al of 2～13nm
2O
3) the conversion solids component is the basic aluminium salt aqueous solution of 0.5～50 quality %, at silica solid composition and aluminum oxide (Al
2O
3) the mass ratio SiO of conversion solids component
2: Al
2O
3Mix in the scope for 70:30～20:80, thereby obtain containing the operation of the silicon dioxide gel of the colloid silica particle that has been covered by basic aluminium salt;
(B): with being covered of obtaining in the operation (A) by basic aluminium salt silicon dioxide gel carry out hydrothermal treatment consists at 103～250 ℃, thereby obtain the operation of silica-alumina composite sol, described silica-alumina composite sol contains the composite gel particle of following colloid silica particle and following colloidal alumina hydrate particles be combined into, the colloid silica particle that described colloid silica particle has been covered by small colloidal alumina hydrate particles, described colloidal alumina hydrate particles be major diameter be this colloid silica particle primary particle size more than 10 times and minor axis be the colloidal alumina hydrate particles of 2～10nm.
Be, to carry out hydrothermal treatment consists as the 5th scheme at 103～130 ℃ according to the manufacture method of the described silica-alumina composite sol of cubic case.
As the 6th scheme be, according to the manufacture method of the described silica-alumina composite sol of cubic case, basic aluminium salt is be selected from compound in basic aluminium chloride, alkaline aluminum nitrate, alkaline Aluctyl, alkaline al formate and the alkaline aluminum acetate at least a.
The feature of silica-alumina composite sol of the present invention is, and is dry and when making tunicle, show high transparent and excellent film-forming properties and water tolerance on solid surface.Because this silica-alumina composite sol has above-mentioned feature, so can in various uses, use, for example, can in fields such as the surface treatment agent of anticorrosive agent, ceramic fiber and the cationic fiber etc. of surface treatment agent that electro-magnetic steel plate is used, steel plate, papermaking material, paint adhesive, use.
In addition because silica-alumina composite sol positively charged of the present invention, so with positively charged ion be that tensio-active agent, cationic colloid, positively charged ion are consistency, miscibility and the excellent dispersion of emulsion, cationic powder slurry etc., so can and use with these positively charged ion based materials.
Embodiment
Silica-alumina composite sol of the present invention, be the colloidal sol that contains the composite gel particle of following colloid silica particle and following colloidal alumina hydrate particles be combined into, the colloid silica particle that described colloid silica particle has been covered by small colloidal alumina hydrate particles, described colloidal alumina hydrate particles is that major diameter is the colloidal alumina hydrate particles more than 10 times of the primary particle size of this colloid silica particle.
The primary particle size of the colloid silica particle that silicon dioxide gel contained that uses among the present invention is 2～13nm, is preferably 4～10nm.The primary particle size of colloid silica is to use Sears (シ ア-ズ) volumetry is tried to achieve among the present invention.The particle diameter of trying to achieve with the Sears volumetry is illustrated in analytical chemistry (Analytical Chemistry) the 28th volume (1956) the 1981st page, is the sphere conversion particle diameter that calculates by the specific surface area with titration measuring.Under the situation of primary particle size less than 2nm of colloid silica, in the time of will mixing with basic aluminium salt as the silicon dioxide gel of raw material, the easy gelation of silicon dioxide gel, therefore not preferred.On the other hand, under the situation of this primary particle size, when the silica-alumina composite sol that obtains is made tunicle on solid surface, can not obtain transparent tunicle greater than 13nm, therefore not preferred.
As the aqueous silica sol of raw material, can be that the prepared using known method is made in the present invention with water glass, organoalkoxysilane etc.
The colloidal alumina hydrate particles is boehmite, pseudobochmite or unbodied hydrated alumina in the present invention.It is shaped as the fibril shape to this colloidal alumina hydrate particles in transmission electron microscope is observed, and major diameter is that 50～500nm and minor axis are 2～10nm.In addition, small in the present invention colloidal alumina hydrate particles is boehmite, pseudobochmite or unbodied hydrated alumina.This small colloidal alumina hydrate particles in transmission electron microscope is observed its be shaped as granular, the not enough 2nm of particle diameter.
The so-called in the present invention colloid silica particle that has been covered by small colloidal alumina hydrate particles combines with the colloidal alumina hydrate particles, is Chemical bond or chemisorption.The now known silicon dioxide gel and the colloidal sol that contains the alumina sol of colloidal alumina hydrate particles that contains the colloid silica particle that has been covered by basic aluminium salt that mixed simply, because this colloid silica particle and this colloidal alumina hydrate particles repel mutually owing to electrostatic repulsion, or physical adsorption only takes place, so be different with silica-alumina composite sol of the present invention.
Silica-alumina composite sol of the present invention, preferred silicon-dioxide (SiO
2) solids component and aluminum oxide (Al
2O
3) the mass ratio SiO of conversion solids component
2: Al
2O
3Scope for 70:30～20:80.Silicon-dioxide (SiO
2) solids component is from the colloidal silicon dioxide component that silica-alumina composite sol contained, aluminum oxide (Al
2O
3) the conversion solids component is from colloidal alumina hydrate particles and small colloidal alumina hydrate particles that silica-alumina composite sol contained.Alumina composition is less than under the situation of 70:30 in this mass ratio, and the growing amount of colloidal alumina hydrate particles is insufficient, thereby can not obtain silica-alumina composite sol of the present invention.On the other hand, under the situation of alumina composition more than 20:80, silica-alumina composite sol becomes unstable in the hydrothermal treatment consists operation, and gelation easily is therefore not preferred.The total of the silica solid composition of this silica-alumina composite sol and aluminum oxide conversion solids component is preferably the scope of 1～30 quality %.If these solids components amount to less than 1 quality %, when then making tunicle and use composition, its solid component concentration is low excessively, so dry need long-time, need great energy, so not preferred.If greater than 30 quality %, the viscosity of the silica-alumina composite sol that then obtains is too high in addition, so operational difficulty is therefore not preferred.
The pH of silica-alumina composite sol of the present invention is preferably 2～7 scope.No matter pH is less than 2 or greater than 7, and the viscosity of the colloidal sol that obtains all rises and becomes unstable, and is therefore not preferred.
As the dispersion medium of silica-alumina composite sol of the present invention, can make water and/or organic solvent.As organic solvent, can enumerate methyl alcohol, ethanol, propyl alcohol, ethylene glycol etc.
The manufacture method of silica-alumina composite sol of the present invention is, (A): with acidic aqueous silicon dioxide gel and basic aluminium salt aqueous solution, (B): carry out hydrothermal treatment consists.The acidic aqueous silicon dioxide gel that uses in the operation (A), can use described aqueous silica sol become acidity with known method such as cationic exchange and material.At this moment the silica solid composition in the acidic aqueous silicon dioxide gel is preferably 1～50 quality %, more preferably 5～30 quality %.Under the situation of silica solid composition less than 1 quality % in acidic aqueous silicon dioxide gel, the production efficiency of silica-alumina composite sol is low, if surpass 50 quality % in addition, aggegation or gelation then take place with the basic aluminium salt aqueous solution time sometimes, therefore not preferred.
As basic aluminium salt, can use and utilize the basic aluminium salt that known manufacture method easily obtains or can be used as the basic aluminium salt that commercially available industrial medicine obtains.For example as commercially available industrial medicine, basic aluminium chloride ( キ バ イ Application (registered trademark): many wooden chemistries (strain) are made) is arranged, as known manufacture method, can enumerate that special public clear 45-38121 communique, spy are opened clear 50-154197 communique (alkaline aluminum nitrate), the spy opens flat 9-2999 communique (alkaline Aluctyl), No. 3644051 communiques of patent (alkaline aluminum acetate) etc.At this moment, basic aluminium salt is converted into Al
2O
3Solids component be preferably the scope of 1～50 quality %, the more preferably scope of 2～30 quality %.The Al that is converted at basic aluminium salt
2O
3The situation of solids component less than 1 quality % under, the basic aluminium salt colloid silica particle that can not fully be covered, therefore not preferred.If surpass 50 quality % in addition, then can not with the silicon dioxide gel uniform mixing, the silicon dioxide gel that contains the colloid silica particle that has been covered by basic aluminium salt that the obtains unstable that becomes, therefore not preferred.
In the manufacture method of silica-alumina composite sol of the present invention, during with acidic aqueous silicon dioxide gel and basic aluminium salt aqueous solution, about the blended order, any one formerly all can, utilization adds the method for acidic aqueous silicon dioxide gel in the basic aluminium salt aqueous solution, add any of method of the basic aluminium salt aqueous solution in acidic aqueous silicon dioxide gel, all can obtain the required silicon dioxide gel that contains the colloid silica particle that has been covered by basic aluminium salt.
To the blending ratio of the acidic aqueous silicon dioxide gel and the basic aluminium salt aqueous solution, the preferred silicon-dioxide (SiO in acidic aqueous silicon dioxide gel
2) aluminum oxide (Al of solids component and basic aluminium salt
2O
3) the mass ratio SiO of the solids component that converts
2: Al
2O
3Mix in the scope for 70:30～20:80.In this mass ratio under the situation of the quality of aluminum oxide less than 60:40, even the silicon dioxide gel of the colloid silica particle that containing of obtaining has been covered by basic aluminium salt carries out hydrothermal treatment consists, also owing to existing basic aluminium salt in the colloidal sol is less, therefore the growing amount of colloidal alumina hydrate particles is insufficient, so can not obtain silica-alumina composite sol of the present invention.In addition in this mass ratio under the situation of the quality of aluminum oxide more than 20:80, the easy gelation because the salt concn in the colloidal sol is too high, so not preferred.
In addition, with acidic aqueous silicon dioxide gel and basic aluminium salt aqueous solution and obtain containing in the operation of silicon dioxide gel of the colloid silica particle that has been covered by basic aluminium salt, can add acid as required.Because by adding acid, make the speed of growth of major diameter of the colloidal alumina hydrate particles that hydrothermal treatment consists generated reduce, so control major diameter easily.When adding acid, both can in acidic aqueous silicon dioxide gel, add acid, also can in basic aluminium salt, add acid, can also in both, all add.Perhaps can in the silicon dioxide gel that contains the colloid silica particle that has been covered by basic aluminium salt, add acid.Preferably use decollator etc. under agitation to carry out when adding acid.The addition of acid is preferably with respect to the aluminum oxide (Al of basic aluminium salt
2O
3) solids component that converts is the scope of 20～200 quality %.Addition as tartaric acid is less than 20 quality %, and then the effect of Tian Jiaing is little, if more than 200 quality %, then the negatively charged ion in the colloidal sol is spent height and gelation easily, and is therefore not preferred.
The acid of adding can be used and be selected from more than at least a in hydrochloric acid, nitric acid, lactic acid, formic acid and the acetate.In addition, select to add sour the time, be preferably the acid identical with the acid group of the basic aluminium salt that uses.When for example using alkaline aluminum acetate, as the preferred acetate that uses of the acid of adding as basic aluminium salt.
During with acidic aqueous silicon dioxide gel and basic aluminium salt aqueous solution, the temperature of the silicon dioxide gel and the basic aluminium salt aqueous solution is 5～90 ℃ a scope, is preferably 20～50 ℃ scope.Under the situation of 5 ℃ of less thaies, basic aluminium salt is insufficient with combining of colloid silica particle, so can not obtain having required stability, the silica-alumina composite sol of performance.If surpass 90 ℃, then the time with acidic aqueous silicon dioxide gel and basic aluminium salt aqueous solution, the independent hydrolysis of basic aluminium salt sometimes, the basic aluminium salt colloid silica particle that can not evenly be covered.
Silicon dioxide gel by colloid silica particle that containing of obtaining in the operation (A) has been covered by basic aluminium salt uses autoclave to carry out hydrothermal treatment consists in (B) operation, can obtain silica-alumina composite sol of the present invention.The temperature of carrying out hydrothermal treatment consists is preferably 103～250 ℃, more preferably 103～130 ℃.If 103 ℃ of less thaies, the basic aluminium salt that then contains in the silicon dioxide gel of the colloid silica particle that has been covered by basic aluminium salt can not fully not be hydrolyzed, therefore the colloidal alumina hydrate particles can not be generated, silica-alumina composite sol can not be obtained.If surpass 250 ℃, the then excessive hydrolysis of basic aluminium salt, silica-alumina composite sol generation aggegation or gelation, therefore not preferred.
Hydrothermal treatment consists was carried out 1～30 hour usually.If less than 1 hour, then insufficient the and colloidal alumina hydrate particles of basic aluminium salt hydrolysis generate insufficient, so be difficult to obtain required silica-alumina composite sol.The hydrothermal treatment consists that surpasses 30 hours in addition is uneconomic.
In the silicon dioxide gel of the colloid silica particle that containing of obtaining in operation (A) has been covered by basic aluminium salt, basic aluminium salt is except lining colloid silica particle, and a part is not dissolved in the dispersion medium with not being covered colloid silica and exists.Carry out hydrothermal treatment consists by the described silicon dioxide gel that will obtain in the operation (A), make be covered the colloid silica particle the basic aluminium salt hydrolysis and become small colloidal alumina hydrate particles, be dissolved on the other hand in the described dispersion medium and the basic aluminium salt hydrolysis that exists and become the colloidal alumina hydrate particles.The basic aluminium salt hydrolysis that the basic aluminium salt hydrolysis of colloid silica particle exists with being dissolved in the dispersion medium because be covered takes place simultaneously, and be hydrolyzed under the state that the part of these basic aluminium salts is contacting with each other, so generate chemical bond in the part of colloid silica particle surface small colloidal alumina hydrate particles that generates and the colloidal alumina hydrate particles that in dispersion medium, generates in this silicon dioxide gel.Like this, obtained silica-alumina composite sol of the present invention.
Can add basic aluminium salt in the silica-alumina composite sol that obtains.By adding basic aluminium salt, can under the state of the ageing stability that does not reduce this colloidal sol, reduce the viscosity of colloidal sol.
The silica-alumina composite sol that obtains can be condensed into high density as required.By this colloidal sol is made high density, can relax the composition to the coating fluid made etc., the restriction of concentration.As the concentration method of this colloidal sol, can enumerate ultrafiltration process, utilize the heating method of enrichment of vaporizer etc.And then can use ultra-filtration equipment, vaporizer etc. that solvent exchange is become organic solvent as required, thereby make organosol.
The physics value of the silica-alumina composite sol that obtains is that pH2～7, specific conductivity 500～50000 μ S/cm, solid component concentration are with silicon-dioxide (SiO
2) solids component and aluminum oxide (Al
2O
3) total solids composition meter that the solids component that converts adds up to, be 1～30 quality %, silicon-dioxide (SiO
2) solids component and aluminum oxide (Al
2O
3) the mass ratio SiO of conversion solids component
2: Al
2O
3Scope for 70:30～20:80.
Because silica-alumina composite sol of the present invention is positively charged, so with positively charged ion be that tensio-active agent, cationic colloid, positively charged ion are consistency, miscibility and the excellent dispersion of emulsion, cationic powder slurry etc., can and use with these positively charged ion based materials.
Silica-alumina composite sol of the present invention has the feature of silicon dioxide gel and alumina sol.Silica-alumina composite sol of the present invention dry and tunicle, if dry on solid surface, then show high transparent and excellent film-forming properties, water tolerance.The ageing stability of silica-alumina composite sol of the present invention is also excellent in addition.Because have these features, thus can in various uses, usefully use, and can add various one-tenth according to application target and assign to use, perhaps also use.
As add or and the composition of usefulness, can enumerate alumina sol, silicon dioxide gel, other metal oxide sol, alkali metal silicate aqueous solution, the partial hydrolysis liquid of alkyl silicate, polyvinyl alcohol, Natvosol, water-soluble polymers such as gelatin, melamine resin, urea resin, acrylic resin, Synolac, polyolefin resin, styrene resin, vinyl acetate resin, Resins, epoxy, phenol resins, organic resins such as urethane resin, the resin emulsion of acrylic acid series etc., wilkinite, thickening materials such as sodium alginate, ethylene glycol, methyl alcohol, N, dinethylformamide organic solvents such as (DMF), the partial hydrolysis liquid of coupling agent, tensio-active agent, various acid, various alkali, the refractory body powder, metal-powder, pigment, coating etc.
Below, the concrete demonstration makes use-case.
(1) silica-alumina composite sol of the present invention can be used as electro-magnetic steel plate use effectively with surface treatment agent.Silica-alumina composite sol of the present invention has the characteristic of alumina sol, and the tunicle that obtains is because Young's modulus is big, coefficient of thermal expansion is little, so have excellent tension force.Also have the feature of silicon dioxide gel in addition,, then can obtain the low iron loss electro-magnetic steel plate of excellent corrosion resistance if in the surface treatment agent of electro-magnetic steel plate, use.
Silica-alumina composite sol of the present invention, as the electro-magnetic steel plate surface treatment agent, can with melamine resin, urea resin, acrylic resin, Synolac, polyolefin resin, styrene resin, vinyl acetate resin, Resins, epoxy, phenol resins, resinous principles such as urethane resin, silicon dioxide gel, alumina sol, zirconia sol, tin oxide sol, antimony oxide sol, Tungsten oxide 99.999 colloidal sol, inorganic oxides such as ferric oxide colloidal sol, magnesium bichromate, aluminum dichromate, calcium bichromate, primary magnesium phosphate, aluminium dihydrogen phosphate, monocalcium phosphate, inorganic componentss such as primary zinc phosphate, ethylene glycol, organic reducing agents such as glycerine, phosphoric acid, acid such as boric acid are as the sodium of second-order transition temperature adjustment agent, potassium, basic metal such as lithium etc. also are used for using.
For example, surface treatment method as non-oriented electromagnetic steel sheet having, the melamine resin that is selected from respect to 100 mass parts, urea resin, acrylic resin, Synolac, polyolefin resin, styrene resin, vinyl acetate resin, Resins, epoxy, phenol resins, at least a above resin in the urethane resin, the solids component that mixed oxide converts is the silica-alumina composite sol of the present invention of 3～300 mass parts, and/or mix and convert with oxide compound, resin with respect to 100 mass parts, be the selenium that is selected from of 0.1～100 mass parts, tellurium, arsenic, antimony, bismuth, tin, manganese, more than one metal ingredients in the tungsten, and then as required, with respect to solids component 100 mass parts that convert with the oxide compound of oxide compound conversion silica-alumina composite sol, the sodium that is selected from of agent is adjusted in interpolation as second-order transition temperature, potassium, more than one basic metal 0.1～5 mass parts in the lithium, thereby the making surface treatment liquid uses rolling method on electro-magnetic steel plate, flow coat, spraying, the scraper coating waits and is coated with.After the coating, by using hot air type, infrared type or induce method such as heating-type under 50～300 ℃ temperature, to toast, thereby can obtain having the non-oriented electromagnetic steel sheet having of excellent insulation tunicle such as anti-nitriability, adhesivity, erosion resistance, solvent resistance and adhesion inhibiting properties.
Perhaps to being selected from more than one resins in melamine resin, urea resin, acrylic resin, Synolac, polyolefin resin, styrene resin, vinyl acetate resin, Resins, epoxy, phenol resins, the urethane resin, with respect to 100 mass parts resins, the solids component that adds the mixed oxide conversion is the silica-alumina composite sol of the present invention of 3～300 mass parts.Then with respect to 100 mass parts resins, add and mix 50～2000 mass parts being selected from the phosphoric acid salt such as chromic salt such as magnesium bichromate, aluminum dichromate, calcium bichromate and primary magnesium phosphate, aluminium dihydrogen phosphate, monocalcium phosphate, primary zinc phosphate more than one.And then under the situation of having added chromic salt, for the Cr that promotes that chromic salt contains
6+Be reduced to Cr
3+Reduction reaction, add to mix organic reducing agents such as ethylene glycol, glycerine and make surface treatment liquid.Use rolling method, flow coat, spraying, scraper coating etc. that this surface treatment liquid is coated on the electro-magnetic steel plate.After the coating, by using hot air type, infrared type, induce method such as heating-type under 800～1000 ℃ temperature, to toast, thereby can obtain having the non-oriented electromagnetic steel sheet having of excellent insulation tunicle such as anti-nitriability, adhesivity, erosion resistance, solvent resistance, non-stick property.
Surface treatment method as grain-oriented magnetic steel sheet, the solids component that converts with respect to the oxide compound of the silica-alumina composite sol of the present invention of 100 mass parts, interpolation is scaled the phosphoric acid salt such as aluminum phosphate, calcium phosphate, trimagnesium phosphate of 50～300 mass parts with oxide compound, and adds as required and use CrO
3Be scaled the chromic salt of 10～50 mass parts, thereby obtain treatment solution, use rolling method, flow coat, spraying, scraper coating etc. to be coated on the electro-magnetic steel plate this treatment solution.After the coating, by under 800～1000 ℃ temperature, toasting, thereby can obtain having the grain-oriented magnetic steel sheet of the insulation tunicle of high tensile and magnetic properties, excellent corrosion resistance.
(2) silica-alumina composite sol of the present invention can be used as in automobile, household electrical appliances, building materials purposes etc. the zinc that uses, aluminium etc. plated steel sheet anti-corrosion treating agent additive and use effectively.Silica-alumina composite sol of the present invention is as anticorrosive agent, can with inorganic oxide sols such as silicon dioxide gel, alumina sol, zirconia sol, tin oxide sol, antimony oxide sol, Tungsten oxide 99.999 colloidal sol, ferric oxide colloidal sol, inorganic componentss such as polyvalent metal phosphoric acid salt, borate, chromic salt, various resinous principles as required, hydrophilic organic solvent, inhibiter become to grade and with and use.
For example, with respect to more than one the resin or the resin emulsion in melamine resin, urea resin, acrylic resin, Synolac, polyolefin resin, styrene resin, vinyl acetate resin, Resins, epoxy, phenol resins and the urethane resin of being selected from of 100 mass parts, adding the solids component that its oxide compound converts is the silica-alumina composite sol of the present invention of 1～100 mass parts.
Then, as inorganic components,, add the Cr that is selected from of 1～100 mass parts with respect to the described resin of 100 mass parts
6+Based compound (chromic acid chromium etc.), Cr
3+(chromium sulphate, chromium nitrate, chromium acetate, chromium fluoride etc.), aluminium based compound (aluminum nitrate, Tai-Ace S 150 etc.), titanium sub-group compound (Titanium Nitrate, titanium sulfate etc.), zirconium compound (zirconium nitrate, zirconium carbonate ammonium, the fluorine zirconic acid, zirconium-n-propylate etc.), the calcium based compound (for example, Calucium Silicate powder, lime carbonate etc.), manganese sub-group compound (for example, manganous nitrate etc.), the magnesium based compound (for example, magnesium nitrate, magnesium acetate etc.), nickel series compounds (for example, nickelous acetate, nickelous nitrate etc.), the cobalt based compound (for example, cobaltous acetate, Xiao Suangu etc.), iron series compound (for example, iron nitrate etc.), titanium, molybdenum, vanadium, the oxysalt of tungsten etc. (for example, potassium titanate, sodium titanate, molybdic acid, zinc molybdate, lithium metavanadate, sodium metavanadate, wolframic acid, lithium tungstate, sodium wolframate, and phosphoric acid salt (for example, zinc phosphate ammonium tungstate etc.),, aluminum phosphate, trimagnesium phosphate, calcium phosphate, Plessy's green etc.) more than one in.
In addition, as required as silane coupling agent, with respect to the above-mentioned resin of 100 mass parts, add for example γ-(2-amino-ethyl) TSL 8330 that is selected from of 1～300 mass parts, γ-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, γ-(2-amino-ethyl) aminopropyltriethoxywerene werene, γ-(2-amino-ethyl) aminopropyl methyldiethoxysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane, the gamma-methyl allyl acyloxypropyl methyl dimethoxysilane, the gamma-methyl allyl acyloxypropyl triethoxyl silane, the gamma-methyl allyl acyloxypropyl methyldiethoxysilane, N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl trimethoxy silicane, N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl group methyl dimethoxysilane, N-β-(N-vinyl benzyl amino-ethyl)-γ-An Jibingjisanyiyangjiguiwan, N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl group methyldiethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl group methyl dimethoxysilane, γ-glycidoxy propyl-triethoxysilicane, γ-glycidoxy propyl group methyldiethoxysilane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl group methyl dimethoxysilane, γ-sulfydryl propyl-triethoxysilicane, γ-sulfydryl propyl group methyldiethoxysilane, methyltrimethoxy silane, dimethyldimethoxysil,ne, Union carbide A-162, dimethyldiethoxysilane, vinyltriacetoxy silane, γ-r-chloropropyl trimethoxyl silane, gamma-chloropropylmethyldimethoxysilane, γ-chloropropyl triethoxysilane, γ-chloropropyl methyldiethoxysilane, hexamethyldisilazane, γ-anilino propyl trimethoxy silicane, γ-anilino propyl group methyl dimethoxysilane, γ-anilino propyl-triethoxysilicane, γ-anilino propyl group methyldiethoxysilane, vinyltrimethoxy silane, the vinyl methyl dimethoxysilane, vinyltriethoxysilane, the vinyl methyldiethoxysilane, octadecyl dimethyl [3-(trimethoxysilyl) propyl group] ammonium chloride, octadecyl dimethyl [3-(methyl dimethoxy oxygen base silyl) propyl group] ammonium chloride, octadecyl dimethyl [3-(triethoxysilyl) propyl group] ammonium chloride, octadecyl dimethyl [3-(methyl diethoxy silyl) propyl group] ammonium chloride, METHYL TRICHLORO SILANE, dimethyldichlorosilane(DMCS), trimethylchlorosilane etc., the vinyl methoxy silane, vinyltrimethoxy silane, the vinyl Ethoxysilane, vinyltriethoxysilane, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, the 3-methyl allyl acyloxypropyl trimethoxysilane, 3-sulfydryl propyl trimethoxy silicane, N-(1,3-dimethyl butylidene)-3-(triethoxysilyl)-1-propylamine, N, N '-two [3-(trimethoxysilyl) propyl group] quadrol, N-(beta-aminoethyl)-gamma-amino propyl group methyl dimethoxysilane, N-(beta-aminoethyl)-gamma-amino propyl trimethoxy silicane, the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, γ-glycidoxy propyl group methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, the gamma-methyl allyl acyloxypropyl triethoxyl silane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane and N-[2-(vinyl benzyl amino) ethyl]-in the 3-TSL 8330 more than one.
And then as required as inhibiter (inhibitor) composition, with respect to the described resin of 100 mass parts, adding 0.01～100 mass parts is selected from as the thiocarbamide that contains the compound of thiocarbonyl, dimethyl thiourea, 1, the 3-dimethyl thiourea, the dipropyl thiocarbamide, dibutyl thiourea, 1,3-phenylbenzene-2-thiocarbamide, 2,2-xylyl thiocarbamide, thioacetamide, N, N-Sodium dimethyldithiocarbamate 40min salt, tetramethylthiuram monosulfide, tetrabutylthiuram disulfide, N-ethyl-N-phenyl zinc dithiocarbamate, ziram, 1,5-piperidine pentamethylene dithiocarbamate salt, zinc diethyldithiocarbamate, Thiocarb, zinc isopropyl xanthate, ethylene thiourea, curing dimethyl yellow ortho ester, rubeanic acid, Polydithiocarbamate or its salt, carbohydrazide as hydrazine derivative, the propionyl hydrazine, salicylyl hydrazine, adipic dihydrazide, sebacic dihydrazide, dodecanedicarboxylic acid two hydrazides, isophthalic dihydrazide, thiocarbohydrazide, 4,4 '-oxybis-benzenesulfonyl hydrazide, Benzophenonehydrazones, hydrazide compounds such as toxilic acid hydrazides, pyrazoles, 3, the 5-dimethyl pyrazole, 3-methyl-5-pyrazolone, pyrazole compounds such as 3-amino-5-methylpyrazole, 1,2, the 4-triazole, 3-amino-1,2, the 4-triazole, 4-amino-1,2, the 4-triazole, 3-sulfydryl-1,2, the 4-triazole, 5-amino-3-sulfydryl-1,2, the 4-triazole, 2,3-dihydro-3-oxo-1,2, the 4-triazole, the 1H-benzotriazole, I-hydroxybenzotriazole (monohydrate), 6-methyl-8-hydroxyl Triazolopyridazines, 6-phenyl-8-hydroxyl Triazolopyridazines, 5-hydroxyl-7-methyl isophthalic acid, 3, triazole compounds such as 8-triazoindolizine, 5-phenyl-1,2,3, the 4-tetrazolium, 5-sulfydryl-1-phenyl-1,2,3, tetrazole compounds such as 4-tetrazolium, 5-amino-2-mercapto phenyl formic-1,3, the 4-thiadiazoles, 2,5-dimercapto-1,3, thiadiazole compounds such as 4-thiadiazoles, and 3, the 6-dichloro-pyridazine, 6-methyl-3-pyridazinone, 4,5-two chloro-3-pyridazinones, 4,5-two bromo-3-pyridazinones, 6-methyl-4, more than one in 5-dihydro-pyridazine compounds such as 3-pyridazinone, thereby modulation surface treatment liquid.Adjust agent as pH as required, can in surface treatment agent, add organic acids such as mineral acids such as phosphoric acid, sulfuric acid, nitric acid, acetate, succsinic acid, toxilic acid, alkali cpds such as potassium hydroxide, sodium hydroxide, ammonium hydroxide etc.Using roller coating machine, extrusion coater, mould to be coated with machine etc. the surface treatment liquid that obtains is coated on the plated steel sheet of zinc, aluminium etc.After the coating, can under 30～300 ℃ temperature, carry out drying by using moisture eliminator, hotblast stove, high-frequency induction process furnace, infrared heating heating furnace etc., thereby obtain the surface treatment capsule of non-corrosibility excellence.Can form organic resin coating on the upper strata of the surface treatment capsule that forms as mentioned above in addition.
(3) silica-alumina composite sol of the present invention can use in the tackiness agent that fire-resistant coating agent is used etc. effectively at soaker, the tackiness agent of refractory body, goes for base materials such as pottery, glass, metal, plastics, timber, paper.With silica-alumina composite sol of the present invention, with fire-resistant thermotolerance powder such as aluminum oxide, silicon-dioxide, silica-alumina, zirconium white, pure aluminium silicate, zirconium silicate, clays, and thereby mixing such as water as required, inorganic fibre, thickening material, anti-sedimentation agent obtains slurries, by these slurries being flowed into the mould of regulation shape, the demoulding after the dry solidification, thus the refractory body of target obtained.In addition, the slurries of similarly making can also be coated on the required base material as fire-resistant Liniment and use.
(4) silica-alumina composite sol of the present invention can be used as little filler that ink jet recording medium uses and uses effectively.With silica-alumina composite sol of the present invention, mix with water-base resins such as polyvinyl alcohol, resin emulsions, be coated on paper, plastic film, the sheet, by forming ink absorbing layer, thereby can obtain the good ink jet recording mediums such as distinctiveness, color, gloss, surface hardness of absorptivity, the printing of printing ink.
(5) silica-alumina composite sol of the present invention can be used as the raw material that sapphire whisker uses and uses effectively.With silica-alumina composite sol of the present invention, mix and make spinning solution with water-soluble high-molecular compound and as required the basic aluminium salt aqueous solution, silicon dioxide gel, carry out spinning by using this spinning solution, thereby make sapphire whisker.
(6) silica-alumina composite sol of the present invention can be used as the tackiness agent, strengthening agent of various catalyzer and uses effectively.With silica-alumina composite sol of the present invention, with aluminum oxide, silicon-dioxide, alumina silica is that carrier components such as oxide compound, zeolite and water mix and makes slurries, by these slurries are carried out granulation, thereby can obtain Powdered, granulous support of the catalyst.In addition by these slurries being coated with on the such base material that is suitable for catalyst applications of honeycomb structure body or flooding and dry, or be immersed in the cellulosic base material and dry, thereby can obtain the support of the catalyst of various forms.In addition, silica-alumina composite sol of the present invention, can be by contain the catalyst fines of the compound with catalyst activity of titanium, molybdenum, vanadium, tungsten etc. in use, aluminum oxide, silicon-dioxide, alumina silica are carrier components such as oxide compound, zeolite, flood in the catalyzer that uses such base material that is suitable for catalyst applications of honeycomb structure body or various tackiness agent and make, thereby use effectively as the strengthening agent of catalyzer.
(7) silica-alumina composite sol of the present invention can be used as the tackiness agent that the ceramic fiber moulding uses and uses effectively.With silica-alumina composite sol of the present invention, mix with ceramic fibers such as aluminum oxide, silicon-dioxide, alumina silica, zirconium whites, thereby and add entry as required and obtain slurries, in these slurries, further add agglutinants such as starch as required, make the ceramic fiber aggegation, by methods such as utilization vacuumizes dehydration, be molded into the regulation shape, thereby obtain the moulding product of ceramic fiber then.These moulding product can use in thermotolerance thermal insulation material etc.
(8) silica-alumina composite sol of the present invention can be used as the antifogging agent of film and uses effectively.With silica-alumina composite sol of the present invention, with water, hydrophilic media such as alcohols, and silicon dioxide gel as required, mineral colloids such as alumina sol, polyethylene oxide, water soluble resins such as methylcellulose gum, Sodium octoate, Sodium decanoic acid, Sodium n-caproate, anionic surfactants such as sodium dodecylbenzene etc. mix and modulation treatment liquid, then by being coated on acrylic resin, polyolefin-based resins, polyvinyl chloride, vinyl chloride methyl methacrylate, poly-inclined to one side 1, chlorine such as 1-Ethylene Dichloride are resin, polyethylene terephthalate, the surface of thermoplastic resins such as polyester based resins such as Polyethylene Naphthalate or sour vinyl resin, and it is dry, thereby can obtain antifog property, the film of excellent in te pins of durability is useful as film for agricultural use.
Below, by embodiment in detail the present invention is described in detail particularly.
Embodiment
Embodiment 1
Operation (A): in the polystyrene container made of 3L, drop into the 1369g alkalescence aluminum acetate aqueous solution (Al
2O
3Conversion solids component 5.8 quality %, proportion 1.068, pH5.9, specific conductivity 5730 μ S/cm, Ostwald (Ostwald) viscosity 3.0mPas).This aqueous solution is used decentralized stirrer (the Na シ of the dispersion blade that has diameter 60mm
ヨNa Le ベ PVC-モ- SCVS75W (trade(brand)name): Matsushita Electric Industries's industry (strain) is made) stir with 4000rpm, added 68 quality % acetic acid aqueous solution 120g continuously with 5 minutes simultaneously, continue to stir 2 hours.Then, through adding the commercially available acidic aqueous silicon dioxide gel (ス ノ-テ of 511g in 1 hour continuously
StarNetwork ス OXS (trade(brand)name): Ostwald's viscosity 1.1mPas, silicon-dioxide (SiO under daily output chemical industry (strain) manufacturing, proportion 1.059, pH2.9,25 ℃
2) concentration 10.2 quality %, the primary particle size 5nm that utilizes the Sears volumetry to record), continuously stirring 2 hours, thus the transparent mixed sols of 2000g obtained.The mixed sols that obtains contains 2.7 quality %SiO
2, 4.1 quality %Al
2O
3, SiO
2: Al
2O
3Mass ratio is 40:60.In addition, the content of acetate is with respect to the Al in the mixed sols
2O
3Be 100 quality %.For just, proportion is 1.064 to the ζDian Shi of this mixed sols in the scope of pH3～9, and pH is 4.7, specific conductivity 4330 μ S/cm, and the particle diameter by dynamic light scattering determination is that 22nm, Ostwald's viscosity (25 ℃) are 1.9mPas.
(B) operation: the mixed sols that 909g is obtained is transferred in the polystyrene container made of 3L, adds the 1591g pure water, dilutes to make SiO
2Be 1.0 quality %, Al
2O
3Be 1.5 quality %.The pH of this dilution colloidal sol is 4.9, and specific conductivity is 2400 μ S/cm.1950g should be diluted the autoclave vessel that colloidal sol is transferred to the lass lining lining, stirred, simultaneously 105 ℃ of hydrothermal treatment consists of carrying out 5 hours with 200rpm.The pH of the colloidal sol that obtains is 4.0, specific conductivity is 1810 μ S/cm, particle diameter by dynamic light scattering determination is 35nm, observe with transmission electron microscope, the result is by the particle shape of the colloidal alumina hydrate particles be combined into of the colloid silica particle of small colloidal alumina hydrate particles lining and fibril shape.The colloid silica particle is spherical and primary particle size is 5～10nm, and the particle diameter of small colloidal alumina hydrate particles is not enough 2nm.The minor axis of colloidal alumina hydrate particles is 2～5nm, and major diameter is 50～300nm.Then use ultra-filtration equipment to concentrate this colloidal sol of 1900g, thereby obtain SiO
2Be 4.7 quality %, Al
2O
3Be the silica-alumina composite sol 410g of 5.7 quality %.The proportion of the colloidal sol that obtains is 1.083, and pH is 4.5, and specific conductivity is 2900 μ S/cm, and the particle diameter that utilizes dynamic light scattering method to record is 46nm, and the Type B viscosity under 25 ℃ is 12.5mPas (with the value after No. 1 rotor rotation 30 seconds), SiO
2: Al
2O
3Mass ratio is 45:55.Even the silica-alumina composite sol that obtains is placed more than 1 month at 20 ℃, do not find fallout yet, and tackify, gelation do not take place, be stable.
Embodiment 2
Operation (A): in the polystyrene container made of 3L, add the 432g alkalescence aluminum acetate aqueous solution (Al
2O
3Conversion solids component 5.8 quality %, proportion 1.068, pH5.9, specific conductivity 5730 μ S/cm, Ostwald's viscosity (25 ℃) 3.0mPas).This aqueous solution is used decentralized stirrer (the Na シ of the dispersion blade that has diameter 60mm
ヨNa Le ベ PVC-モ- SCVS75W (trade(brand)name): Matsushita Electric Industries's industry (strain) is made) stir with 1000rpm, add the 698g pure water simultaneously and dilute, make Al
2O
3Be 2.2 quality %.Stirring velocity is become 4000rpm,, continue to stir 2 hours with in this aqueous solution, adding 68 quality % acetic acid aqueous solution 37g in 5 minutes continuously.Then, keep identical stirring velocity, added following acidic aqueous silicon dioxide gel continuously with 1 hour simultaneously, described acidic aqueous silicon dioxide gel is acidic aqueous silicon dioxide gel (ス ノ-テ that 245g is commercially available
StarNetwork ス OXS (trade(brand)name): daily output chemical industry (strain) manufacturing, proportion 1.059, pH2.9, Ostwald's viscosity (25 ℃) 1.1mPas, silica concentration 10.2 quality %, the primary particle size 5nm that utilizes the Sears volumetry to record) is diluted to SiO with the 588g pure water
2Be that 3.0 quality % get, then, continue to stir 2 hours, thereby obtain the transparent mixed sols of 2000g.The mixed sols that obtains contains 1.3 quality %SiO
2, 1.3 quality %Al
2O
3, SiO
2: Al
2O
3Mass ratio is 50:50.In addition, the content of acetate is with respect to the Al in the mixed sols
2O
3Be 100 quality %.The rerum natura of this mixed sols is, for just, proportion is 1.028 to ζDian Shi in the scope of pH3～9, and pH is 4.3, and specific conductivity is 2890 μ S/cm, and the particle diameter that utilizes dynamic light scattering method to record is 20nm, and Ostwald's viscosity (25 ℃) is 1.5mPas.
(B) operation: the mixed sols that 1980g is obtained is transferred in the autoclave vessel of lass lining lining, stirs with 200rpm, simultaneously 105 ℃ of hydrothermal treatment consists of carrying out 5 hours.The pH of the colloidal sol that obtains is 3.9, specific conductivity is 2110 μ S/cm, the dynamic light scattering method particle diameter is 81nm, observe with transmission electron microscope, the result is by the particle shape of the colloidal alumina hydrate particles be combined into of the colloid silica particle of small colloidal alumina hydrate particles lining and fibril shape.The colloid silica particle is spherical and primary particle size is 5～10nm, and the particle diameter of small colloidal alumina hydrate particles is not enough 2nm.The minor axis of colloidal alumina hydrate particles is 2～5nm, and major diameter is 50～300nm.Then use ultra-filtration equipment to concentrate this colloidal sol of 1950g, thereby obtain SiO
2Be 6.5 quality %, Al
2O
3Be the silica-alumina composite sol 390g of 4.7 quality %.The proportion of the colloidal sol that obtains is 1.084, and pH is 4.3, and specific conductivity is 3290 μ S/cm, and the particle diameter that utilizes dynamic light scattering method to record is 102nm, and Type B viscosity (25 ℃) is 9.1mPas (with 30 seconds values afterwards of No. 1 rotor rotation), SiO
2: Al
2O
3Mass ratio is 58:42.Even the silica-alumina composite sol that obtains is placed more than 1 month at 20 ℃, do not find fallout yet, and tackify, gelation do not take place, be stable.Embodiment 3
Operation (A): in the polystyrene container made of 3L, add 146g alkalescence aluminum nitrate aqueous solution (Al
2O
3Conversion solids component 20.6 quality %, proportion 1.068, pH5.9, specific conductivity 5730 μ S/cm, Ostwald's viscosity (25 ℃) 3.0mPas).With decentralized stirrer (the Na シ of this aqueous solution with the dispersion blade that has diameter 60mm
ヨNa Le ベ PVC-モ- SCVS75W (trade(brand)name): Matsushita Electric Industries's industry (strain) is made) stir with 1000rpm, under agitation add the 1187g pure water simultaneously and dilutes, make Al
2O
3The conversion solids component is 2.3 quality %.Stirring velocity is become 4000rpm, then, continue to stir 2 hours.Then, keep stirring velocity, added following acidic aqueous silicon dioxide gel continuously with one hour simultaneously, described acidic aqueous silicon dioxide gel is acidic aqueous silicon dioxide gel (ス ノ-テ that 196g is commercially available
StarNetwork ス OXS (trade(brand)name): daily output chemical industry (strain) manufacturing, proportion 1.059, pH2.9, Ostwald's viscosity (25 ℃) 1.1mPas, silica concentration 10.2 quality %, the primary particle size 5nm that utilizes the Sears volumetry to record) is diluted to SiO with the 471g pure water
2Be that 3.0 quality % get, then, continue to stir 2 hours, thereby obtain the transparent mixed sols of 2000g.The mixed sols that obtains contains 1.0 quality %SiO
2, 1.5 quality %Al
2O
3, SiO
2: Al
2O
3Mass ratio is 40:60.The rerum natura of this mixed sols is: for just, proportion is 1.029 to ζDian Shi in the scope of pH3～9, and pH is 3.6, and specific conductivity is 12900 μ S/cm, and the particle diameter that utilizes dynamic light scattering method to record is 1.5mPas for 16nm, Ostwald's viscosity (25 ℃).
(B) operation: the mixed sols that 1988g is obtained is transferred in the autoclave vessel of lass lining lining, stirs with 200rpm, simultaneously 105 ℃ of hydrothermal treatment consists of carrying out 5 hours.The pH of the colloidal sol that obtains is 3.8, specific conductivity is 13400 μ S/cm, the dynamic light scattering method particle diameter is 52nm, observe with transmission electron microscope, the result is by the particle shape of the colloidal alumina hydrate particles be combined into of the colloid silica particle of small colloidal alumina hydrate particles lining and fibril shape.The colloid silica particle is spherical and primary particle size is 5～10nm, and the particle diameter of small colloidal alumina hydrate particles is not enough 2nm.The minor axis of colloidal alumina hydrate particles is 2～5nm, and major diameter is 50～200nm.Then use ultra-filtration equipment to concentrate this colloidal sol of 1965g, contain 5.2 quality %SiO thereby obtain 380g
2, 3.2 quality %Al
2O
3Silica-alumina composite sol.The proportion of the colloidal sol that obtains is 1.072, and pH is 3.8, and specific conductivity is 18000 μ S/cm, and the particle diameter that utilizes dynamic light scattering method to record is 52nm, and Type B viscosity (25 ℃) is 5.5mPas (with 30 seconds values afterwards of No. 1 rotor rotation), SiO
2: Al
2O
3Mass ratio is 62:38.Even the silica-alumina composite sol that obtains is placed more than 1 month at 20 ℃, do not find fallout yet, and tackify, gelation do not take place, be stable.Comparative example 1
In the polystyrene container made of 3L, add the 138g alkalescence aluminum acetate aqueous solution (Al
2O
3Conversion solids component 5.8 quality %, proportion 1.068, pH5.9, specific conductivity 5730 μ S/cm, Ostwald's viscosity (25 ℃) 3.0mPas).This aqueous solution is used decentralized stirrer (the Na シ of the dispersion blade that has diameter 60mm
ヨNa Le ベ PVC-モ- SCVS75W (trade(brand)name): Matsushita Electric Industries's industry (strain) is made) stir with 1000rpm, add the 462g pure water simultaneously and dilute, make Al
2O
3Be 1.3 quality %.Stirring velocity is become 4000rpm,, continue to stir 2 hours with in this aqueous solution, adding 68 quality % acetic acid aqueous solution 2.4g in 5 minutes continuously.Then, keep identical stirring velocity, added following acidic aqueous silicon dioxide gel continuously with one hour simultaneously, described acidic aqueous silicon dioxide gel is acidic aqueous silicon dioxide gel (ス ノ-テ that 412g is commercially available
StarNetwork ス OXS (trade(brand)name): daily output chemical industry (strain) manufacturing, proportion 1.059, pH2.9, Ostwald's viscosity (25 ℃) 1.1mPas, silica concentration 10.2 quality %, the primary particle size 5nm that utilizes the Sears volumetry to record) is diluted to SiO with the 986g pure water
2Be that 3.0 quality % get, continue to stir 2 hours, thereby obtain the transparent mixed sols of 2000g.The mixed sols that obtains contains 2.1 quality %SiO
2, 0.4 quality %Al
2O
3, the mass ratio of silica solid composition and aluminum oxide solids component is 85:15.The content of acetate is with respect to the Al in the mixed sols in addition
2O
3Be 2 quality %.For just, proportion is 1.021 to the ζDian Shi of this mixed sols in the scope of pH3～9, and pH is 4.3, and specific conductivity is 620 μ S/cm, and the dynamic light scattering method particle diameter is that 23nm, Ostwald's viscosity (25 ℃) are 1.4mPas.This mixed sols is transferred in the autoclave vessel of lass lining lining, stirs, simultaneously 105 ℃ of hydrothermal treatment consists of carrying out 5 hours with 200rpm.The pH of the colloidal sol that obtains is 4.1, specific conductivity is that 590 μ S/cm, dynamic light scattering method particle diameter are 24nm, observe by transmission electron microscope, the result does not observe the colloidal alumina hydrate particles of growth slenderly, only observes by the colloid silica particle of small colloidal alumina hydrate particles lining.This colloid silica particle is spherical and primary particle size is 5～10nm, and the particle diameter of small colloidal alumina hydrate particles is not enough 2nm.Then use ultra-filtration equipment to concentrate this colloidal sol of 1780g, contain 8.8 quality %SiO thereby obtain 400g
2, 1.7 quality %Al
2O
3The silicon dioxide gel of positively charged.The proportion of the colloidal sol that obtains is 1.069, and pH is 4.5, and specific conductivity is 810 μ S/cm, and the particle diameter that utilizes dynamic light scattering method to record is 33nm, and Type B viscosity (25 ℃) is 37mPas (with 30 seconds values afterwards of No. 1 rotor rotation), SiO
2: Al
2O
3Mass ratio is 84:16.
Comparative example 2
In the polystyrene container made of 3L, add the 484g alkalescence aluminum acetate aqueous solution (Al
2O
3Conversion solids component 5.8 quality %, proportion 1.068, pH5.9, specific conductivity 5730 μ S/cm, Ostwald's viscosity 3.0mPas).This aqueous solution is used decentralized stirrer (the Na シ of the dispersion blade that has diameter 60mm
ヨNa Le ベ PVC-モ- SCVS75W (trade(brand)name): Matsushita Electric Industries's industry (strain) is made) stir with 1000rpm, add the 1516g pure water simultaneously and dilute, make Al
2O
3Be 1.3 quality %.This aqueous solution is transferred in the autoclave vessel of lass lining lining, stirs, simultaneously 105 ℃ of hydrothermal treatment consists of carrying out 5 hours with 200rpm.The aqueous solution after the hydrothermal treatment consists does not produce fallout.Transmission electron microscope is observed, and it is that 50～200nm, minor axis are the colloidal particle of the fibril shape of 2～5nm that results verification has major diameter.This colloidal particle is carried out the X-ray diffraction analysis, and the result has the pseudobochmite structure, and this aqueous solution is alumina sol.The pH of this alumina sol is 4.6, and specific conductivity is 1850 μ S/cm, and the particle diameter that utilizes dynamic light scattering method to record is 74nm.Use ultra-filtration equipment to concentrate this alumina sol of 1990g, contain 7.9 quality %Al thereby obtain 200g
2O
3Colloidal alumina colloidal sol.The pH of the colloidal sol that obtains is 5.1, and specific conductivity is 3900 μ S/cm, and the particle diameter that utilizes dynamic light scattering method to record is 75nm.
Comparative example 3
With 50g contain obtain in the comparative example 1 by the alumina sol that obtains in the colloidal sol of the colloid silica particle of small colloidal alumina hydrate particles lining and the 40g comparative example 2, make in the container at the polystyrene of 100mL and to mix, make silica solid composition and aluminum oxide (Al
2O
3) mass ratio of the solids component that converts is 45:55.This silica-alumina mixed sols contains 4.3 quality %SiO
2, 5.2 quality %Al
2O
3PH is 4.8, specific conductivity is 2500 μ S/cm, the particle diameter that utilizes dynamic light scattering method to record is 68nm, observe with transmission electron microscope, the result be the colloidal alumina hydrate particles of fibril shape with by the colloid silica particle of small colloidal alumina hydrate particles lining between do not find to combine, be dispersive state respectively.
Comparative example 4
In the polystyrene container made of 3L, add the 776g alkalescence aluminum acetate aqueous solution (Al
2O
3Conversion solids component 5.8 quality %, proportion 1.068, pH5.9, specific conductivity 5730 μ S/cm, Ostwald's viscosity (25 ℃) 3.0mPas).This aqueous solution is used decentralized stirrer (the Na シ of the dispersion blade that has diameter 60mm
ヨNa Le ベ PVC-モ- SCVS75W (trade(brand)name): Matsushita Electric Industries's industry (strain) is made) stir with 1000rpm, add the 1044g pure water simultaneously and dilute, make Al
2O
3Be 2.4 quality %.Stirring velocity is become 4000rpm, in this aqueous solution, add 68 quality % acetic acid aqueous solution 13.2g, continue to stir 2 hours.Then, add acidic aqueous silicon dioxide gel continuously with 1 hour, this acidic aqueous silicon dioxide gel is acidic aqueous silicon dioxide gel (ス ノ-テ that 49g is commercially available
StarNetwork ス OXS (trade(brand)name): the primary particle size 5nm that the manufacturing of daily output chemical industry (strain), proportion 1.059, pH2.9, Ostwald's viscosity (25 ℃) 1.1mPas, silica concentration 10.2 quality %, Sears volumetry record) be diluted to SiO with the 118g pure water
2Be that 3.0 quality % get, then, continue to stir 2 hours, thereby obtain the transparent mixed sols of 2000g.The mixed sols that obtains contains 0.25 quality %SiO
2, 2.25 quality %Al
2O
3, the mass ratio of silica solid composition and aluminum oxide solids component is 10:90.In addition, the content of acetate is with respect to the Al in the mixed sols
2O
3Be 20 quality %.For just, proportion is 1.030 to the ζDian Shi of this mixed sols in the scope of pH3～9, and pH is 5.0, and specific conductivity is 3050 μ S/cm, and the dynamic light scattering method particle diameter is that 15nm, Ostwald's viscosity (25 ℃) are 1.6mPas.This mixed sols of 1960g is transferred in the autoclave vessel of lass lining lining, stirs, simultaneously 105 ℃ of hydrothermal treatment consists of carrying out 5 hours with 200rpm.The pH of the colloidal sol that obtains is 4.6, and specific conductivity is 2720 μ S/cm, and the dynamic light scattering method particle diameter is 115nm, and Ostwald's viscosity (25 ℃) is 1.9mPas.Observe with transmission electron microscope, the result is by the particle shape of the colloidal alumina hydrate particles be combined into of the colloid silica particle of small colloidal alumina hydrate particles lining and fibril shape,, 10～100 of the colloidal alumina hydrate particles of fibril shape generate the set bundle but being arranged in parallel, the minor axis of colloid hydrate particles is 20～30nm in fact, and major diameter is 100～200nm.The colloid silica particle is spherical and primary particle size is 5～10nm, and the particle diameter of small colloidal alumina hydrate particles is not enough 2nm.Then use ultra-filtration equipment to concentrate this colloidal sol of 1940g, contain 3.1 quality %SiO thereby obtain 380g
2, 5.5 quality %Al
2O
3Silica-alumina colloidal sol.The proportion of the colloidal sol that obtains is 1.078, and pH is 5.0, and specific conductivity is 4120 μ S/cm, and the particle diameter that utilizes dynamic light scattering method to record is 105nm, and Type B viscosity (25 ℃) is 5.0mPas (with 30 seconds values afterwards of No. 1 rotor rotation), SiO
2: Al
2O
3Mass ratio is 28:72.
Estimate embodiment
The evaluation method of film-forming properties
With silica-alumina colloidal sol, the acidic aqueous silicon dioxide gel (ス ノ-テ that obtains in the silica-alumina mixed sols that obtains in the silica-alumina composite sol that obtains among the embodiment 1,2, the comparative example 3, the comparative example 4
StarNetwork ス OXS: daily output chemical industry (strain) is made) and comparative example 2 in the alumina sol that obtains use spinner under the condition of 500rpm, to be coated on the surface of transparency glass plate respectively, then 150 ℃ of heat treated of carrying out 5 minutes, thereby on sheet glass, form tunicle, observe according to range estimation and scanning electron microscope (SEM), estimate the state of tunicle with the 2 following stages.Show the result in table 1.
[table 1] film-forming properties evaluation result
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Film-forming properties | ○ | ○ | ○ |
| Sample | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Film-forming properties | × | × | × |
| Sample | Comparative example 4 | スノ—テ ツクス OXS |
| Film-forming properties | × | × |
Zero: form flawless, level and smooth and fine and close tunicle.Good adhesion with sheet glass.
*: tunicle cracks, or does not form tunicle.
Water-proof evaluation method
In film-forming properties is estimated, the sheet glass that will have level and smooth and fine and close tunicle flooded 5 hours in 80 ℃ hot water bath, wash with pure water then, make it dry at 150 ℃, degree that the tunicle of observing dipping front and back in hot water bath according to range estimation and SEM is peeled off from sheet glass and tunicle are to the solvability of warm water.Become following 3 stages to estimate by state classification with tunicle.Show the result in table 2.
[table 2] water tolerance evaluation result
Zero: tunicle is not peeled off.
*: tunicle is peeled off.
Silica-alumina composite sol of the present invention (embodiment 1,2,3) dry and tunicle have high transparent and excellent film-forming properties.On the other hand, the silica-alumina mixed sols that obtains in the comparative example 3, independent silicon dioxide gel, independent alumina sol can not obtain sufficient film-forming properties.In addition, before and after silica-alumina composite sol of the present invention flooded in 80 ℃ hot water bath, the thickness of tunicle did not change, and has excellent in water resistance.
The industry utilizability
Silica-alumina composite sol of the present invention dry and tunicle, if be dried at the surface of solids, then showing high transparent and excellent film forming, resistance to water, is useful as electromagnetic steel plate with the additive of the anti-corrosion treating agent of the plated steel sheet of surface conditioning agent, automobile, household electrical appliances, the employed zinc of building materials, aluminium etc.
Claims (6)
1. silica-alumina composite sol, it contains the composite gel particle of following colloid silica particle and following colloidal alumina hydrate particles be combined into, the colloid silica particle that described colloid silica particle has been covered by small colloidal alumina hydrate particles, described colloidal alumina hydrate particles be major diameter be this colloid silica particle primary particle size more than 10 times and minor axis be the colloidal alumina hydrate particles of 2～10nm.
2. silica-alumina composite sol according to claim 1, the silicon-dioxide (SiO in the described silica-alumina composite sol
2) solids component and aluminum oxide (Al
2O
3) the mass ratio SiO of conversion solids component
2: Al
2O
3Be 70:30～20:80.
3. silica-alumina composite sol according to claim 1 and 2, the primary particle size of the described colloid silica particle that has been covered by small colloidal alumina hydrate particles is 2～13nm, and the major diameter of colloidal alumina hydrate particles is 50～500nm.
4. the manufacture method of each described silica-alumina composite sol of a claim 1～3 is characterized in that, comprises following operation (A) and operation (B):
(A): with silicon-dioxide (SiO
2) solids component is that the primary particle size of 0.5～50 quality %, colloid silica particle is acidic aqueous silicon dioxide gel and the aluminum oxide (Al of 2～13nm
2O
3) the conversion solids component is the basic aluminium salt aqueous solution of 0.5～50 quality %, at silica solid composition and aluminum oxide (Al
2O
3) the mass ratio SiO of conversion solids component
2: Al
2O
3Mix in the scope for 70:30～20:80, thereby obtain containing the operation of the silicon dioxide gel of the colloid silica particle that has been covered by basic aluminium salt;
(B): the silicon dioxide gel that obtains in the operation (A) is carried out hydrothermal treatment consists at 103～250 ℃, thereby obtain the operation of silica-alumina composite sol, described silica-alumina composite sol contains the composite gel particle of following colloid silica particle and following colloidal alumina hydrate particles be combined into, the colloid silica particle that described colloid silica particle has been covered by small colloidal alumina hydrate particles, described colloidal alumina hydrate particles be major diameter be this colloid silica particle primary particle size more than 10 times and minor axis be the colloidal alumina hydrate particles of 2～10nm.
5. the manufacture method of silica-alumina composite sol according to claim 4 is 103～130 ℃ of hydrothermal treatment consists of carrying out described (B) operation.
6. according to the manufacture method of claim 4 or 5 described silica-alumina composite sols, described basic aluminium salt is be selected from compound in basic aluminium chloride, alkaline aluminum nitrate, alkaline Aluctyl and the alkaline aluminum acetate at least a.
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|---|---|---|---|
| JP302611/2006 | 2006-11-08 | ||
| JP2006302611 | 2006-11-08 | ||
| PCT/JP2007/071558 WO2008056668A1 (en) | 2006-11-08 | 2007-11-06 | Silica-alumina composite sol and process for production thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101535182A true CN101535182A (en) | 2009-09-16 |
| CN101535182B CN101535182B (en) | 2012-02-08 |
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Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5141908B2 (en) |
| KR (1) | KR20090082913A (en) |
| CN (1) | CN101535182B (en) |
| TW (1) | TW200837012A (en) |
| WO (1) | WO2008056668A1 (en) |
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-
2007
- 2007-11-06 KR KR1020097011400A patent/KR20090082913A/en active IP Right Grant
- 2007-11-06 CN CN2007800411702A patent/CN101535182B/en not_active Expired - Fee Related
- 2007-11-06 JP JP2008543087A patent/JP5141908B2/en active Active
- 2007-11-06 WO PCT/JP2007/071558 patent/WO2008056668A1/en active Application Filing
- 2007-11-08 TW TW096142257A patent/TW200837012A/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5141908B2 (en) | 2013-02-13 |
| KR20090082913A (en) | 2009-07-31 |
| WO2008056668A1 (en) | 2008-05-15 |
| TW200837012A (en) | 2008-09-16 |
| CN101535182B (en) | 2012-02-08 |
| JPWO2008056668A1 (en) | 2010-02-25 |
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