CN1506306A - Process for producing silicon sol and silicon sol - Google Patents

Process for producing silicon sol and silicon sol Download PDF

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Publication number
CN1506306A
CN1506306A CNA2003101213045A CN200310121304A CN1506306A CN 1506306 A CN1506306 A CN 1506306A CN A2003101213045 A CNA2003101213045 A CN A2003101213045A CN 200310121304 A CN200310121304 A CN 200310121304A CN 1506306 A CN1506306 A CN 1506306A
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particle
median size
silicic acid
active silicic
silicon sol
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CN1312035C (en
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西田广泰
宪
若宫义宪
郎
小松通郎
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GC CATALYSTS AND CHEMICALS LT
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Catalysts and Chemicals Industries Co Ltd
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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
    • C01B33/141—Preparation of hydrosols or aqueous dispersions
    • C01B33/142—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates
    • C01B33/143—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates of aqueous solutions of silicates
    • C01B33/1435—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates of aqueous solutions of silicates using ion exchangers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Cosmetics (AREA)
  • Colloid Chemistry (AREA)

Abstract

The method for manufacturing the silica sol comprises adding continuously or intermittently the activated silicic acid particle dispersion liquid (b) to the seed particle dispersion liquid (a) while heating them, and carrying out the particle growth by sticking the activated silicic acid particle to the seed particle. (a) is a water-based seed particle dispersion liquid with an average particle diameter (D<SB>LS</SB>) measured with a dynamic light scattering method using a laser beam in the range of 5-1,000 nm, and with a pH in the range of 7-12. (b) is the activated silicic acid particle dispersion liquid with an average particle diameter (D<SB>LF</SB>) measured with the dynamic light scattering method using the laser beam in a range of 2-50 nm (provided, however, that the average particle diameter (D<SB>LF</SB>) is smaller than the average particle diameter (D<SB>LS</SB>) ) and the average particle diameter (D<SB>NaF</SB>) measured with the NaOH titration method is in the range of 0.9-6 nm. Furthermore, the ratio (D<SB>LF</SB>)/(D<SB>NaF</SB>) of the average particle diameter (D<SB>LF</SB>) to the average particle diameter (D<SB>NaF</SB>) is in the range of 1.8-30 and the pH is in the range of 5-11.

Description

The manufacture method of silicon sol and silicon sol
Technical field
The present invention relates to use the manufacture method of silicon sol of kind of particle dispersion and the silicon sol that obtains by this manufacture method.
Background technology
Motion about the manufacture method of silicon sol in the past has a lot, wherein alkalimetal silicate is sloughed the acidic silicate solution that obtains behind the alkali and be added into method in kind of the particle dispersion, particle diameter with resulting colloid silica particle is even, and can be adjusted to advantages such as desirable particle diameter.For example the present inventor opens the manufacture method that discloses a kind of silicon sol in the clear 63-45114 communique the spy, particle is planted in i.e. modulation, and add method such as spent ion exchange resin therein alkali metal silicate aqueous solutions such as water glass sloughed the acidic silicate solution that alkali obtains, acidic silicic acid kind of particle surface in conjunction with, stacked, separate out and make kind of particle increase.
But in kind of particle dispersion, add in the method for acidic silicic acid liquid, (1) because the polymerization degree of acidic silicic acid lower (1～4 degree), particle increases needs the long period, in particular for obtaining containing the silicon sol even and silicon dioxide granule that particle diameter is big, be necessary to repeat the increase step of particle.And (2) reduce owing to particle surface is long-pending along with the particle increase, are necessary for example to reduce the interpolation speed of acidic silicic acid liquid, so throughput and formation efficiency reduce.On the other hand, if improve the interpolation speed of acidic silicic acid liquid for the shortening time, then particle produces aggegation, produces new fine particles, has problems such as the size distribution of silicon sol of gained is inhomogeneous.In addition, (3) are owing to acidic silicic acid liquid is stable low, so the condition of necessary strict control engineering management.
Summary of the invention
The invention provides a kind of manufacture method of silicon sol, is to add the active silicic acid dispersion of particles liquid contain the defined size in kind of particle dispersion, makes the manufacture method of the silicon sol that kind of particle can increase rapidly.
In addition, the purpose of this invention is to provide the silicon sol that obtains by above-mentioned manufacture method.
The manufacture method of silicon sol of the present invention is characterised in that, in the kind particle dispersion of following (a), the limit heating edge continuously or the active silicic acid particle dispersion of the interpolation following (b) that is interrupted makes the active silicic acid particle attached on kind of the particle thus, and particle is increased.
(a) planting particle dispersion, is by the median size (D of laser with dynamic light scattering determination LS) the aqueous liquid dispersion of kind particle in 5～1000nm scope, pH is in 7～12 scopes;
(b) silicic acid particle dispersion is by the median size (D of laser with dynamic light scattering determination LF) (still, median size (D in 2～50nm scope LF) less than median size (D LS)), and with the median size (D of NaOH titration measuring NaF) in 0.9～6nm scope, moreover, above-mentioned median size (D LF) and above-mentioned median size (D NaF) ratio (D LF)/(D NaF) in 1.8～30 scopes, be the aqueous liquid dispersion of active silicic acid particle, its pH is in 5～11 scopes.
In this manufacture method, preferred above-mentioned heating is carried out in 60～160 ℃ temperature range.
In addition, described active silicic acid particle preferably uses following 2 kinds: (a) the silicate base metal is generated silica hydrogel under acid neutralization, the active silicic acid particle that its dispergation is obtained with alkali; (b) the silicate base metal is generated silica hydrogel with the acid neutralization, the limit is carried out active silicic acid particle that granular obtain with mechanical force to it with its dispergation limit with alkali.
Median size (the D that works as above-mentioned kind of particle in addition LS) when 12nm or 12nm are following, the median size (D of above-mentioned active silicic acid particle LF) be preferably above-mentioned median size (D LS) below 7/10 or 7/10.Median size (D when above-mentioned kind of particle LS) when surpassing 12nm, the median size (D of above-mentioned active silicic acid particle LF) be preferably above-mentioned median size (D LS) below 5/10 or 5/10.
Silicon sol of the present invention is characterised in that, by the median size (D of laser with dynamic light scattering determination LZ) in 12～200nm scope, and with the median size (D of NaOH titration measuring NaZ) in 5～30nm scope, and above-mentioned median size (D LZ) and above-mentioned median size (D NaZ) ratio (D LZ)/(D NaZ) in 2～30 scope.
Utilize the manufacture method of silicon sol of the present invention to make to have that active silicic acid particle particle diameter, reactive high increases particle, so the increase of this particle can promptly be carried out attached to kind of a particle surface in the defined scope.Can shorten the manufacturing time of silicon sol thus, very economical.In addition, can obtain containing the silicon sol of homogeneous large grain size silicon dioxide granule.
Embodiment
Describe the present invention below in detail.
[kind particle dispersion]
As of the present invention kind of particle dispersion, can use by the median size (D of laser with dynamic light scattering determination LS) the aqueous liquid dispersion of kind particle in 5nm～1000nm scope, pH is in 7～12 scopes.
The kind particle of the kind particle dispersion that uses as the present invention can use SiO 2, Al 2O 3, TiO 2, ZrO 2Deng the particulate of inorganic oxide or their composite oxides, wherein preferably use SiO 2This particle uses with the state of dispersive aqueous sol in water usually.
In addition, can use other known in the past kind of particle dispersions, for example can use above-mentioned spy to open disclosed kind (seed) solution in the clear 63-45114 communique.Particularly, for example with silicate base metal water solution with and/or alkali aqueous solution mix with acidic silicic acid liquid, with the SiO of silicic acid liquid 2/ M 2(M: basic metal) mol ratio is adjusted to after 2.8～10 O, and slaking under the temperature more than 60 ℃ obtains kind of a solution (kind particle dispersion).
Plant the particle diameter of particle, particle diameter of the silicon-dioxide of the silicon sol that can obtain according to final hope etc. carries out appropriate selection, but owing to pushing the speed of particle in the manufacture method of silicon sol of the present invention is very fast, so may not need the kind particle of spended time general use this moment in advance to be modulated into the kind particle of increase, so long as in the scope of the function that can play kind of particle, can use the kind particle of small particle size.
The median size of this class kind particle, when using dynamic light scattering determination by laser, probable ranges is at 5nm～1000nm, preferably in 7nm～100nm scope.But when median size is lower than 5nm, plant the particle instability, when adding the active silicic acid particle dispersion, can produce gelation or aggegation takes place.When median size surpasses 1000nm, need spended time when particle is planted in modulation usually in addition, so deviate from mutually with the aim that kind of particle is increased to improve formation efficiency rapidly of the present invention.
There is no particular limitation to the concentration of kind of particle dispersion, is converted into oxide compound and can uses 0.1～20 weight % usually, preferably uses 0.5～10 weight %.When under this value is converted into the situation of oxide compound, being lower than 0.1 weight %,, particle being reduced, or disappear, can not bring into play the function of kind of particle so be easy to dissolving because concentration is low.When under the concentration of kind of particle dispersion is being converted into the situation of oxide compound, being higher than 20 weight %, plant particles aggregate, so can't obtain monodispersed colloidal sol with uniform grading.Owing to plant the concentration height of particle, the feed speed of active silicic acid particle dispersion is slow in addition, is necessary to prevent the generation of aggegation etc.In addition, because it is many to plant the quantity of particle, particle pushing the speed one by one is suppressed, and can hinder the rapid increase of particle.
The pH value of planting particle dispersion is usually preferably in 7～12 scopes, more preferably in 8～11 scope.When pH was lower than 7, the current potential of particle surface reduced, particle generation aggegation.If pH surpasses 12, then plant the particle dissolving, or the active silicic acid particle that adds dissolving, so the particle increase is slack-off, the distribution of particle diameter becomes inhomogeneous.
In kind of particle dispersion, preferably add the basic metal aqueous solution such as NaOH, KOH or ammonia soln etc. as required.Plant SiO in the particle dispersion 2/ M 2(M: mol ratio basic metal) is 2.8～200 to O, in 2.8～120 scopes.Work as SiO 2/ M 2The mol ratio of O is lower than at 2.8 o'clock, plants the particle dissolving, works as SiO on the contrary 2/ M 2The mol ratio of O surpasses at 200 o'clock, and the pH of dispersion liquid reduces particle generation aggegation when supplying with the active silicic acid particle dispersion in kind of particle dispersion.
[active silicic acid particle dispersion]
As active silicic acid particle dispersion of the present invention, be the aqueous liquid dispersion of the active silicic acid particle that meets the following conditions, it is by the median size (D of laser with dynamic light scattering determination LF) (still, median size (D in 2～50nm scope LF) less than median size (D LS)), and with the median size (D of NaOH titration measuring NaF) in the scope of 0.9～6nm, moreover, above-mentioned median size (D LF) and above-mentioned median size (D NaF) ratio (D LF)/(D NaF) in 1.8～30 scopes, pH is in 5～11 scope.
The active silicic acid particle that uses from the present invention helps kind of particle increase aspect rapidly to consider, requires in its particle size range that is in regulation.In addition, since the active silicic acid particle attached on kind of the particle particle being increased gradually, so require the median size of the median size of active silicic acid particle less than kind of particle.Therefore, as the active silicic acid particle that uses among the present invention, can use porous active silicic acid particle.About the manufacture method of this active silicic acid particle, there is no particular limitation, the active silicic acid particle that for example useful silicon water-sol is modulated into as raw material etc.In addition, because the active silicic acid particle that the present invention uses is porous,, also must obtain measured value by the NaOH volumetry so, just do not obtain measured value with dynamic light scattering method by laser as the prescriptive procedure of its median size.
Below be elaborated with regard to this problem.
Median size (D when the active silicic acid particle LF) when the active silicic acid particle dispersion that is lower than 2nm is added in kind of the particle dispersion, plants the particle of particle and push the speed slowly, and this active silicic acid particle dispersion and acidic silicic acid liquid instability equally, be difficult to reach high density.If the active silicic acid particle dispersion of lower concentration is added in kind of the particle dispersion, then the kind particle concentration in the dispersion liquid also reduces, and the result reduces production efficiency.
In addition, as the median size (D of active silicic acid particle LF) when surpassing 50nm, the particle that almost is helpless to kind of particle increases.So median size (D of this active silicic acid particle LF) preferably in 3～40nm scope.
The particle diameter that records with dynamic light scattering method by laser for example can be with particle size distribution analyzer (Particle Sizing Systems corporate system: NICOMP-380) measure, obtain visual measured value.
In addition, push the speed in order to obtain faster particle, as the median size (D of above-mentioned kind of particle LS) be 12nm or 12nm when following, the median size (D of above-mentioned active silicic acid particle LF) be preferably above-mentioned median size (D LS) below 7/10 or 7/10; Median size (D when above-mentioned kind of particle LS) when surpassing 12nm, the median size (D of above-mentioned active silicic acid particle LF) be preferably above-mentioned median size (D LS) below 5/10 or 5/10.
In addition, above-mentioned active silicic acid particle is with the median size (D of NaOH titration measuring NaF) in the scope of 0.9～6nm, and above-mentioned median size (D LF) and median size (D NaF) ratio (D LF)/(D NaF) in 1.8～30 scopes.
When above-mentioned median size (NaF) when being lower than 0.9nm, pushing the speed of kind of particle slow equally when using acidic silicic acid liquid in the past, in addition because active silicic acid particle dispersion stable insufficient so the active silicic acid particle dispersion can not reach high density, can't improve formation efficiency.As above-mentioned median size (D NaF) when surpassing 6nm, though also depend on the particle diameter of kind of particle, do not separate out selectively on the surface of kind of particle, generate new particle, the size distribution of the silicon dioxide granule that finally the obtains uneven tendency that becomes.
By the ratio (D of laser with median size with the median size of this particle of using the NaOH titration measuring of the active silicic acid particle of dynamic light scattering determination LF)/(D NaF) be lower than at 1.8 o'clock, because of above-mentioned median size (D LF) size and different, active silicic acid particle reactive low, the particle effect that improves and insufficient of pushing the speed.In addition, as the ratio (D of above-mentioned median size LF)/(D NaF) surpassing at 30 o'clock, the particle intensity of resulting silicon dioxide granule dies down, and for example as grinding when being used for the abrasive substance of semiconductor substrate etc. with particle, can not obtain sufficient grinding rate.
With the particle diameter that the NaOH volumetry obtains, can be at the specific surface area (SA that measures with Sears method activity calculated silicic acid Na) afterwards, calculate by following formula (1).
D Na＝6000/(2.2×2.2SA Na)????(1)
In the formula, constant 2.2 is true specific gravities of silicon-dioxide.When measuring with the NaOH volumetry, when particle was not porous matter, measurement result was with roughly the same with the value of above-mentioned laser determination, but when particle was porous matter, it is bigger that particle diameter seems, so will reduce calculating the time.
Infer that this is because porous matter active silicic acid particle is high with the reactivity of planting particle, attached to the result who causes easily on kind of the particle that particle increases.
As above-mentioned active silicic acid particle dispersion, mainly consider from the reason of synthesizing, can use the material of pH in 5～11 scopes.Being difficult to obtain sufficient particle when exceeding this scope pushes the speed.
[manufacturing of active silicic acid particle dispersion]
Above-mentioned active silicic acid particle can pass through prepared in various methods, but the active silicic acid particle that is preferably made by following 2 kinds of methods: (a) with alkali with the silica hydrogel dispergation; (b) limit is silica hydrogel alkaline hydrolysis glue, the limit with mechanical force with its granular.In addition, also can mix the active silicic acid particle that use is obtained by above-mentioned (a) and method (b).
In addition, as silica hydrogel, preferably with the silica hydrogel that obtains with the silicate base metal in the acid.At this moment,, can use alkalimetal silicates such as water glass, potassium silicate, obtain by in its aqueous solution, adding acid-responss such as hydrochloric acid, nitric acid, sulfuric acid as the silicate base metal.
In and the time the concentration of alkali metal silicate aqueous solution, with SiO 2Meter being preferably 1～10 weight %, more preferably 2～8 weight %, and temperature is normal temperature (common 15～35 ℃).PH after the neutralization is in 3～7 scopes.This concentration is with SiO 2When meter was discontented with 1 weight %, the polymerization of silicic acid (gelation) was insufficient, the particle diameter (D of resulting active silicic acid particle LF) diminish, particle is pushed the speed insufficient.In addition, when this concentration with SiO 2When meter surpasses 10 weight %, can not evenly neutralize, the polymerization of silicic acid is inhomogeneous, the particle diameter (D of resulting active silicic acid particle LF) be distributed with the uneven tendency that becomes.
The silica hydrogel that neutralizes and obtain, preferably washing back use as required thus.
As the 1st method for making of active silicic acid particle dispersion, for example have in the dispersion liquid of silica hydrogel, to add the method for alkali with the silica hydrogel dispergation.At this moment, the concentration of the dispersion liquid of silica hydrogel is with SiO 2Count 0.5～5 weight %, more preferably in 1～4 weight % scope.When this concentration was lower than 0.5 weight %, the ratio of dissolved silicon-dioxide increased, the median size (D of resulting active silicic acid particle LF) diminish, be difficult to obtain adding the effect that fast particle is pushed the speed.Work as this concentration in addition with SiO 2When meter surpasses 5 weight %, the median size (D of resulting silicic acid particle LF) surpass 50nm or become inhomogeneous, though also depend on the size of kind of particle, the size distribution of resulting silicon sol becomes inhomogeneous.
As alkali, can use alkali metal hydroxide or ammonium hydroxide such as KOH, NaOH, also can use ammonia soln.The usage quantity of alkali is preferably the SiO in the dispersion liquid that can make silica hydrogel 2Mole number (Ms) and alkali (with M 2O represents) mole number (M A) ratio (Ms)/(M A) in 5～100 scope, use, this ratio is used in 10～50 scope.As above-mentioned mol ratio (Ms)/(M A) be lower than at 5 o'clock, with the median size (D of NaOH titration measuring NaF) be lower than 0.9nm easily, and the ratio of dissolved silicon-dioxide increases the production efficiency of silicon sol and yield reduction.In addition, if above-mentioned mol ratio (Ms)/(M A) surpass 100, then dispergation becomes insufficient, makes above-mentioned median size (D NaF) surpassing 6nm, the activity of active silicic acid particle dispersion reduces, and is used in the active silicic acid particle minimizing that kind of particle increases thus, and the size distribution of resulting silicon sol becomes inhomogeneous.PH is preferably in 5～11 scopes during dispergation.When pH was lower than 5, because the high viscosityization of dispersion liquid, becoming was difficult to obtain stable active silicic acid particle.When pH surpassed 11, silicon-dioxide became and is easy to dissolving, became unstable.
The temperature of above-mentioned silica hydrogel during with alkaline hydrolysis glue is 50～150 ℃, more preferably in 60～95 ℃ of scopes.When being lower than 50 ℃, can not full and uniform ground dispergation.When temperature surpasses 150 ℃, median size (D NaF) surpass 10nm, the size distribution of the resulting silicon sol uneven tendency that becomes.
The 2nd method for making of active silicic acid particle dispersion, be the limit with alkali with the silica hydrogel dispergation, the limit with mechanical force with its granular.Granular is to add alkali in the dispersion liquid of silica hydrogel, and dispergation limit, limit is handled about 10 minutes to a few hours with pulverizers such as sand mill, ball mills.
[manufacturing of silicon sol]
The manufacture method of silicon sol of the present invention is that the limit heating edge is continuously or the above-mentioned active silicic acid particle dispersion of adding that is interrupted in kind of particle dispersion.The temperature that plant particle dispersion this moment is preferably at 60～160 ℃, more preferably in 70～120 ℃ of scopes.When this temperature was lower than 60 ℃, because the active silicic acid particle is slow at the speed of separating out of kind of particle surface, so the interpolation speed of the active silicic acid particle dispersion that is necessary to slow down, the result had hindered the rapid increase of planting particle.When temperature surpassed 160 ℃, the silicon-dioxide meltage of planting particle increased, or produces agglutination particle, the tendency of the yield reduction of silicon sol occurred.In addition, when being added into the active silicic acid particle dispersion in kind of the particle dispersion, preferably stir slowly usually.In addition, this operation also can be used autoclave as required.
The active silicic acid particle dispersion that adds, can with obtain according to the method described above with SiO 2The active silicic acid particle dispersion that meter concentration is approximately 0.5～5 weight % directly adds, and also can dilute as required or concentrate the back and use.In this case, the concentration of the active silicic acid particle dispersion during interpolation is with SiO 2Count 0.5～10 weight %, preferably in the scope of 1～8 weight %.When this concentration is lower than 0.5 weight %, along with the interpolation of active silicic acid particle dispersion, the concentration of planting particle dispersion reduces, and heat carry out down particle when increasing the solubleness of silicon-dioxide increase, it is unstable that dispersion liquid becomes, and particle generation aggegation or yield reduce.In addition, when this concentration surpasses 10 weight %, though different because of the interpolation speed of active silicic acid particle dispersion, generate new particulate, can't obtain the equally distributed silicon sol of particle diameter.
The ratio of the active silicic acid particle dispersion that in kind of particle dispersion, adds, difference difference because of the polymerization degree of the concentration of the kind particle in kind of the particle dispersion, the particle diameter of planting particle, active silicic acid particle and the temperature of kind particle dispersion etc., preferably push the speed at 0.5～5nm/ hour, more preferably regulated in the scope at 1～4nm/ hour at the particle diameter that can make kind of particle.Under the adding proportion of active silicic acid particle dispersion makes the situation that is lower than 0.5nm/ hour of pushing the speed of kind of particle diameter, with the not very big difference of manufacture method of the silicon sol that used acidic silicic acid liquid in the past, can not give full play to and improve the effect that particle is pushed the speed.Under the adding proportion of active silicic acid particle dispersion makes that kind of a particle diameter is pushed the speed greater than 5nm/ hour situation,, generate new particulate between the active silicic acid particle in addition, can not obtain the equally distributed silicon sol of particle diameter owing to add excessive velocities.
After the interpolation of active silicic acid particle dispersion finishes, can carry out slaking as required.If carry out slaking, can obtain the uniform silicon sol of particle diameter.
Like this, the silicon sol that is obtained by the manufacture method of silicon sol of the present invention is by the median size (D of laser with dynamic light scattering determination LZ) be 12～200nm, preferably in 15～180nm scope; Median size (D with the NaOH titration measuring NaZ) be 5～30nm, preferably in 5～20nm scope.
Ratio (the D of median size in addition LZ)/(D NaZ) be 2～30, preferably in 2～20 scopes.As above-mentioned ratio (D LZ)/(D NaZ) be lower than at 2 o'clock, be necessary to carry out long slaking, or need at high temperature carry out slaking, cancel out each other with the effect that particle of the present invention increases rapidly.In addition, as (D LZ)/(D NaZ) surpassing at 30 o'clock, the particle intensity of silicon dioxide granule is insufficient, for example as grinding when being used for the abrasive substance of semiconductor substrate etc. with particle, can not obtain desirable grinding rate.
Silicon sol of the present invention can concentrate or dilute the back as required and use.As spissated method, make the method for moisture evaporation as heating, use the method for ultra-filtration membrane.This moment silicon sol with SiO 2The concentration of meter is adjusted in 10～50 weight % scopes usually.
In addition, silicon sol of the present invention can carry out solvent exchange with organic solvent as required and form organosol.The organic solvent that uses in the solvent exchange for example has alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, Pyranton, furfural, tetrahydrofurfural, ethylene glycol, hexylene glycol; Ester such as methyl acetate, ethyl acetate class; Ethers such as ether, methyl glycol, glycol monoethyl ether, ethylene glycol monobutyl ether; Ketones such as acetone, methyl ethyl ketone, methyl ethyl diketone, acetylacetic ester; Amides such as N-Methyl pyrrolidone, dimethyl formamide etc.These materials can use separately, also can use mixing more than 2 kinds or 2 kinds.
[embodiment 1]
The present invention is described by the following examples, but the present invention is not limited thereto.Among the following embodiment and comparative example, ((Particle SizingSystems corporate system: NICOMP-380), the result is as shown in table 1 with particle size distribution analyzer with the median size of dynamic light scattering determination kind particle, active silicic acid particle and silicon sol by laser.In addition, average particle size determination by the specific surface area that calculates in NaOH volumetry (Sears method), the result provides in table 1 equally.
In addition, give the kind particle dispersion that uses in following embodiment and the comparative example and the pH value of active silicic acid particle dispersion, the median size (D of above-mentioned active silicic acid particle in the table 1 LF) and median size (D NaF) ratio (D LF)/(D NaF) value, and the median size (D of above-mentioned active silicic acid particle LF) with the median size (D of above-mentioned kind of particle LS) ratio (D LF)/(D LS) value.
The modulation of acidic silicic acid liquid
Will be with SiO 2The concentration of meter is the sodium silicate aqueous solution (SiO of 24 weight % 2/ Na 2The mol ratio of O is 3.1) with the deionized water dilution, be modulated into SiO 2Meter concentration is the dilution sodium silicate aqueous solution of 5.2 weight %.(Mitsubishi Chemical's (strain) system: post Diaion SK-1B) is modulated into acidic silicic acid liquid by having filled Hydrogen ion exchange resin with this solution.The SiO of acidic silicic acid liquid 2Concentration is 5.0 weight %, and pH is 2.7.Be 1nm by laser with the median size of dynamic light scattering determination in addition.
Plant the modulation of particle dispersion (1)
In the stainless steel vessel of the 30L that return channel, stirrer, temperature-detecting device are housed, will be with SiO 2Meter concentration is the sodium silicate aqueous solution (SiO of 24 weight % 2/ Na 2The mol ratio of O is 3.1) 163g deionized water 2760g dilution.Synthetic above-mentioned acidic silicic acid liquid 4420g mixes in this solution in addition, heats 30 minutes down at 60 ℃ afterwards, is modulated into SiO 2Meter concentration is the kind particle dispersion (1) of 4.6 weight %.By the median size (D of laser with dynamic light scattering determination kind particle LS) be 5nm, SiO 2/ Na 2The mol ratio of O is 20.
The modulation of active silicic acid particle dispersion (1)
Will be with SiO 2Meter concentration is the sodium silicate aqueous solution (SiO of 24 weight % 2/ Na 2The mol ratio of O is 3.1) with the deionized water dilution, be modulated into SiO 2Meter concentration is the dilution sodium silicate aqueous solution of 5.2 weight %.In this sodium silicate aqueous solution, add the sulfuric acid neutralization, be modulated into silica hydrogel.Behind this silica hydrogel water thorough washing, obtain with SiO 2Meter concentration is the silica hydrogel dispersion liquid 43kg of 5 weight %, and to wherein adding the NaOH aqueous solution 955g that concentration is 20 weight %, 80 ℃ of following dispergation 3 hours are modulated into active silicic acid particle dispersion (1).This moment SiO 2Concentration be 3 weight %, SiO 2Mole number (Ms) and alkali (with M 2O represents) mole number (M A) ratio (Ms)/(M A) be 15.In addition, by the median size (D of laser with dynamic light scattering determination LF) be 3nm, with the median size (D of NaOH titration measuring NaF) be 1nm.
The modulation of silicon sol (1)
In kind particle dispersion (1) 410g of 80 ℃ of modulated, added active silicic acid particle dispersion (1) 42716g, be modulated into silicon sol (1) with 11 hours.The SiO of silicon sol 2Concentration, by laser with the median size (D of dynamic light scattering determination LZ), the median size (D of NaOH titration measuring Na) and particle push the speed as shown in table 1.Use by the median size (D of laser when in addition, the calculating particle is pushed the speed with dynamic light scattering determination LZ) measured value.
[embodiment 2]
Plant the modulation of particle dispersion (2)
In the stainless steel vessel of the 30L that return channel, stirrer, temperature-detecting device are housed, will be with SiO 2Meter concentration is the sodium silicate aqueous solution (SiO of 24 weight % 2/ Na 2The mol ratio of O is 3.1) 163g deionized water 2760g dilution.After in this solution, mixing synthetic similarly to Example 1 acidic silicic acid liquid 18200g, heated 30 minutes down, be modulated into SiO at 80 ℃ 2Meter concentration is the kind particle dispersion (2) of 4.6 weight %.By the median size (D of laser with dynamic light scattering determination LS) be 12nm, SiO 2/ Na 2The mol ratio of O is 70.
The modulation of active silicic acid particle dispersion (2)
Except that the NaOH aqueous solution that with concentration is 20 weight % changed 480g into, other modulator approaches by active silicic acid particle dispersion (1) were carried out equally, obtain active silicic acid particle dispersion (2).This moment SiO 2Concentration be 3 weight %, SiO 2Mole number (Ms) and alkali (with M 2O represents) mole number (M A) ratio (Ms)/(M A) be 30.In addition, by the median size (D of laser with dynamic light scattering determination LF) be 6nm, with the median size (D of NaOH titration measuring NaF) be 2nm.
The modulation of silicon sol (2)
In kind particle dispersion (2) 410g of 80 ℃ of modulated, added active silicic acid particle dispersion (2) 24556g, be modulated into silicon sol (2) with 15 hours.It is same to press embodiment 1, the SiO of the silicon sol that obtains 2Concentration, median size and particle are pushed the speed as shown in table 1.
[embodiment 3]
The modulation of active silicic acid particle dispersion (3)
Will be with SiO 2Meter concentration is the sodium silicate aqueous solution (SiO of 24 weight % 2/ Na 2The mol ratio of O is 3.1) with the deionized water dilution, be modulated into SiO 2Meter concentration is the dilution sodium silicate aqueous solution of 5.2 weight %.In this sodium silicate aqueous solution, add the sulfuric acid neutralization, be modulated into silica hydrogel.Behind this silica hydrogel water thorough washing, obtain with SiO 2Meter concentration is the silica hydrogel dispersion liquid of 5 weight %, and adding concentration in silica hydrogel dispersion liquid 25kg is the NaOH aqueous solution 555g of 20 weight %, and 80 ℃ of following dispergation 3 hours are modulated into active silicic acid particle dispersion (3).This moment SiO 2Concentration be 3 weight %, SiO 2Mole number (Ms) and alkali (with M 2O represents) mole number (M A) ratio (Ms)/(M A) be 25.In addition, by the median size (D of laser with dynamic light scattering determination LF) be 4nm, with the median size (D of NaOH titration measuring NaF) be 2nm.
The modulation of silicon sol (3)
In kind particle dispersion (2) 410g of 80 ℃ of modulated, added active silicic acid particle dispersion (3) 24556g, be modulated into silicon sol (3) with 15 hours.Carry out the SiO of the silicon sol that obtains equally by embodiment 1 2Concentration, median size and particle are pushed the speed as shown in table 1.
[embodiment 4]
The modulation of active silicic acid particle dispersion (4)
Will be with SiO 2Meter concentration is the sodium silicate aqueous solution (SiO of 24 weight % 2/ Na 2The mol ratio of O is 3.1) with the deionized water dilution, be modulated into SiO 2Meter concentration is the dilution sodium silicate aqueous solution of 5.2 weight %.In this sodium silicate aqueous solution, add the sulfuric acid neutralization, be modulated into silica hydrogel.Behind this silica hydrogel water thorough washing, obtain with SiO 2Meter concentration is the silica hydrogel dispersion liquid of 5 weight %, and adding concentration in silica hydrogel dispersion liquid 35kg is the NaOH aqueous solution 167g of 20 weight %, and 80 ℃ of following dispergation 3 hours are modulated into active silicic acid particle dispersion (4).This moment SiO 2Concentration be 3 weight %, SiO 2Mole number (Ms) and alkali (with M 2O represents) mole number (M A) ratio (Ms)/(M A) be 70.In addition, by the median size (D of laser with dynamic light scattering determination LF) be 8nm, with the median size (D of NaOH titration measuring NaF) be 2nm.
The modulation of silicon sol (4)
In kind particle dispersion (2) 410g of 80 ℃ of modulated, added active silicic acid particle dispersion (4) 24556g, be modulated into silicon sol (3) with 15 hours.Carry out the SiO of the silicon sol that obtains equally by embodiment 1 2Concentration, median size and particle are pushed the speed as shown in table 1.
[embodiment 5]
Plant the modulation of particle dispersion (3)
In the stainless steel vessel of the 30L that return channel, stirrer, temperature-detecting device are housed, will be with SiO 2Meter concentration is the sodium silicate aqueous solution (SiO of 24 weight % 2/ Na 2The mol ratio of O is 3.1) 163g deionized water 2760g dilution.After in this solution, mixing synthetic similarly to Example 1 acidic silicate solution 25220g, heated 30 minutes down, be modulated into SiO at 90 ℃ 2Meter concentration is the kind particle dispersion (3) of 4.6 weight %.By the median size (D of laser with dynamic light scattering determination kind particle LS) be 25nm, SiO 2/ Na 2The mol ratio of O is 100.
The modulation of active silicic acid particle dispersion (5)
Except that the NaOH aqueous solution that with concentration is 20 weight % changes 480g into, beyond 90 ℃ of following dispergation, other modulator approaches by active silicic acid particle dispersion (1) are carried out, and obtain active silicic acid particle dispersion (5).This moment SiO 2Concentration be 3 weight %, SiO 2Mole number (Ms) and alkali (with M 2O represents) mole number (M A) ratio (Ms)/(M A) be 30.In addition, by the median size (D of laser with dynamic light scattering determination LF) be 12nm, with the median size (D of NaOH titration measuring NaF) be 2nm.
The modulation of silicon sol (5)
In kind particle dispersion (3) 410g of 87 ℃ of modulated, added active silicic acid particle dispersion (5) 12382g, be modulated into silicon sol (5) with 17 hours.Carry out the SiO of the silicon sol that obtains equally by embodiment 1 2Concentration, median size and particle are pushed the speed as shown in table 1.
[embodiment 6]
Plant the modulation of particle dispersion (4)
In the stainless steel vessel of the 30L that return channel, stirrer, temperature-detecting device are housed, CatalloidS1-80P (Catalysts ﹠ Chem Ind Co's system) is mixed with deionized water 363g, obtain with SiO 2Meter concentration is the kind particle dispersion (4) of 4.6 weight %.By the median size (D of laser with dynamic light scattering determination kind particle LS) be 100nm, SiO 2/ Na 2The mol ratio of O is 100.
The modulation of active silicic acid particle dispersion (6)
Except that the NaOH aqueous solution that with concentration is 20 weight % changed 320g into, other modulator approaches by active silicic acid particle dispersion (1) were carried out equally, obtain active silicic acid particle dispersion (6).This moment SiO 2Concentration be 3 weight %, SiO 2Mole number (Ms) and alkali (with M 2O represents) mole number (M A) ratio (Ms)/(M A) be 45.In addition, by the median size (D of laser with dynamic light scattering determination LF) be 20nm, with the median size (D of NaOH titration measuring NaF) be 2nm.
The modulation of silicon sol (6)
In kind particle dispersion (4) 410g of 95 ℃ of modulated, added active silicic acid particle dispersion (6) 2728g, be modulated into silicon sol (6) with 20 hours.Carry out the SiO of the silicon sol that obtains equally by embodiment 1 2Concentration, median size and particle are pushed the speed as shown in table 1.
[embodiment 7]
The modulation of active silicic acid particle dispersion (7)
Will be with SiO 2Meter concentration is the sodium silicate aqueous solution (SiO of 24 weight % 2/ Na 2The mol ratio of O is 3.1) with the deionized water dilution, be modulated into SiO 2Meter concentration is the dilution sodium silicate aqueous solution of 5.2 weight %.In this sodium silicate aqueous solution, add the sulfuric acid neutralization, be modulated into silica hydrogel.Behind this silica hydrogel water thorough washing, obtain with SiO 2Meter concentration is the silica hydrogel dispersion liquid of 3 weight %, and (peace river motor (strain) system: Sandmill) processing is 0.5 hour, is modulated into active silicic acid particle dispersion (7) with pulverizer with it.This moment SiO 2Concentration be 3 weight %, by laser with the median size (D of dynamic light scattering determination LF) be 3nm, with the median size (D of NaOH titration measuring NaF) be 1nm.
The modulation of silicon sol (7)
In kind particle dispersion (1) 410g of 80 ℃ of modulated, added active silicic acid particle dispersion (7) 42716g, be modulated into silicon sol (7) with 11 hours.Carry out the SiO of the silicon sol that obtains equally by embodiment 1 2Concentration, median size and particle are pushed the speed as shown in table 1.
[embodiment 8]
Plant the modulation of particle dispersion (5)
Except that using Sphelicaslurry-100P (Catalysts ﹠ Chem Ind Co's system) replaced C atalloid S1-80P, other carry out equally by kind of the modulator approach of particle dispersion (4), are modulated into kind of a particle dispersion (5).This moment SiO 2Concentration be 4.6 weight %, by the median size (D of laser with dynamic light scattering determination kind particle LS) be 120nm, SiO 2/ Na 2The mol ratio of O is 100.
The modulation of active silicic acid particle dispersion (8)
Except that the NaOH aqueous solution that with concentration is 20 weight % changed 285g into, other modulator approaches by active silicic acid particle dispersion (1) were carried out, and obtain active silicic acid particle dispersion (8).This moment SiO 2Concentration be 3 weight %, SiO 2Mole number (Ms) and alkali (with M 2O represents) mole number (M A) ratio (Ms)/(M A) be 15.In addition, by the median size (D of laser with dynamic light scattering determination LF) be 40nm, with the median size (D of NaOH titration measuring NaF) be 2nm.
The modulation of silicon sol (8)
In kind particle dispersion (5) 410g of 150 ℃ of modulated, added active silicic acid particle dispersion (8) 1600g, be modulated into silicon sol (8) with 20 hours.Carry out the SiO of the silicon sol that obtains equally by embodiment 1 2Concentration, median size and particle are pushed the speed as shown in table 1.
[comparative example 1]
The modulation of active silicic acid particle dispersion (9)
Except that the NaOH aqueous solution that with concentration is 20 weight % changed 950g into, other modulator approaches by active silicic acid particle dispersion (1) were carried out, and are modulated into active silicic acid particle dispersion (9).This moment SiO 2Concentration be 3 weight %, SiO 2Mole number (Ms) and alkali (with M 2O represents) mole number (M A) ratio (Ms)/(M A) be 15.In addition, by the median size (D of laser with dynamic light scattering determination LF) be 3nm, with the median size (D of NaOH titration measuring NaF) be 2nm.
The modulation of silicon sol (9)
In kind particle dispersion (2) 400g of 80 ℃ of modulated, added active silicic acid particle dispersion (9) 1744g, be modulated into silicon sol (9) with 15 hours.Carry out the SiO of the silicon sol that obtains equally by embodiment 1 2Concentration, median size and particle are pushed the speed as shown in table 1.
[comparative example 2]
The modulation of active silicic acid particle dispersion (10)
Except that the NaOH aqueous solution that with concentration is 20 weight % changed 240g into, other modulator approaches by active silicic acid particle dispersion (1) were carried out, and obtain active silicic acid particle dispersion (10).This moment SiO 2Concentration be 3 weight %, SiO 2Mole number (Ms) and alkali (with M 2O represents) mole number (M A) ratio (Ms)/(M A) be 60.In addition, by the median size (D of laser with dynamic light scattering determination LF) be 80nm, with the median size (D of NaOH titration measuring NaF) be 2nm.
The modulation of silicon sol (10)
In kind particle dispersion (3) 400g of 87 ℃ of modulated, added active silicic acid particle dispersion (10) 1744g, be modulated into silicon sol (10) with 15 hours.Carry out the SiO of the silicon sol that obtains equally by embodiment 1 2Concentration, median size and particle are pushed the speed as shown in table 1.
Table 1
Plant particle dispersion The active silicic acid particle dispersion Silicon sol
No. Median size (D LS) ?SiO 2Concentration ??SiO 2/M 2O ??Ph ??No. The median size relation ??SiO 2/M 2O ??Ph The interpolation time Particle is pushed the speed ??No. Temperature Median size ????SiO 2Concentration
??D LF ??D NaF ????D LF/D NaF ??D LF/D LS ??D LZ ??D NaZ ?D LZ/D NaZ Weight %
nm Weight % Mol ratio ??nm ??nm Mol ratio ??hr ??nm/hr ????℃ ??nm ??nm ????30
Embodiment 1 (1) 5 ?4.6 ??20 ??9.8 ??(1) ??3 ??1 ????3 ??0.60 ??15 ??11.0 ??11 ??1.7 ??(1) ????80 ??24 ??8 ?3 ????30
Embodiment 2 (2) 12 ?4.6 ??70 ??10.0 ??(2) ??6 ??2 ????3 ??0.50 ??30 ??10.0 ??15 ??2.4 ??(2) ????80 ??48 ??12 ?4 ????30
Embodiment 3 (2) 12 ?4.6 ??70 ??10.0 ??(3) ??4 ??2 ????2 ??0.33 ??25 ??10.8 ??15 ??2.4 ??(3) ????80 ??48 ??6 ?8 ????30
Embodiment 4 (2) 12 ?4.6 ??70 ??10.0 ??(4) ??8 ??2 ????4 ??0.67 ??70 ??8.0 ??15 ??2.4 ??(4) ????80 ??48 ??16 ?3 ????30
Embodiment 5 (3) 25 ?4.6 ??100 ??9.8 ??(5) ??12 ??2 ????6 ??0.48 ??30 ??10.2 ??17 ??3.2 ??(5) ????87 ??80 ??10 ?8 ????30
Embodiment 6 (4) 100 ?4.6 ??100 ??9.6 ??(6) ??20 ??2 ????10 ??0.20 ??45 ??9.8 ??20 ??4 ??(6) ????95 ??160 ??10 ?16 ????30
Embodiment 7 (1) 5 ?4.6 ??20 ??9.8 ??(7) ??3 ??1 ????3 ??0.60 ??(50) *1 ??10.5 ??11 ??1.7 ??(7) ????80 ??24 ??8 ?3 ????30
Embodiment 8 (5) 120 ?4.6 ??100 ??10.3 ??(8) ??40 ??2 ????20 ??0.33 ??15 ??10.7 ??20 ??4.5 ??(8) ????150 ??140 ??29 ?4.8 ????30
Comparative example 1 (2) 12 ?4.6 ??70 ??10.0 ??(9) ??3 ??2 ????1.5 ??0.25 ??15 ??11.0 ??15 ??0.3 ??(9) ????80 ??17 ??14 ?1.2 ????30
Comparative example 2 (3) 25 ?4.6 ??100 ??9.8 ??(10) ??80 ??2 ????40 ??3.20 ??60 ??9.1 ??15 ??0.1 ??(10) ????87 ??27 ??16 ?1.7 ????30
*1) gel is pulverized
Silicon sol of the present invention is especially suitable for use as the abrasive substance of hard paint, filler for plastic, camera lens or the silicon wafer etc. of transparent substrates such as transparent plastics, glass.

Claims (5)

1. the manufacture method of silicon sol is characterized in that in the kind particle dispersion of following (a), and the limit heating edge continuously or the active silicic acid particle dispersion of the interpolation following (b) that is interrupted makes the active silicic acid particle attached to particle is increased thus,
(a) planting particle dispersion, is by the median size (D of laser with dynamic light scattering determination LS) the aqueous liquid dispersion of kind particle in 5～1000nm scope, pH is in 7～12 scopes;
(b) active silicic acid particle dispersion is by the median size (D of laser with dynamic light scattering determination LF) (but median size (D in 2～50nm scope LF) less than median size (D LS)) and with the median size (D of NaOH titration measuring NaF) in the scope of 0.9～6nm, moreover, above-mentioned median size (D LF) and above-mentioned median size (D NaF) ratio (D LF)/(D NaF) the aqueous liquid dispersion of active silicic acid particle in 1.8～30 scopes, pH is in 5～11 scopes.
2. the manufacture method of the silicon sol of claim 1 record is characterized in that described heating carries out in 60～160 ℃ temperature range.
3. the manufacture method of silicon sol of claim 1 or 2 records is characterized in that described active silicic acid particle is following (a) or (b),
(a) with the silicate base metal with acid neutralization, generate silica hydrogel, the active silicic acid particle that this silica hydrogel is obtained with alkaline hydrolysis glue;
(b) with the silicate base metal with acid neutralization, while the active silicic acid particle of using alkaline hydrolysis glue its granular to be obtained the silica hydrogel that generates with mechanical force.
4. the manufacture method of the silicon sol of each record in the claim 1,2 or 3 is characterized in that the median size (D when described kind of particle LS) be 12nm or 12nm when following, the median size (D of described active silicic acid particle LF) be described median size (D LS) below 7/10 or 7/10; Median size (D when described kind of particle LS) when surpassing 12nm, the median size (D of described active silicic acid particle LF) be described median size (D LS) below 5/10 or 5/10.
5. silicon sol is characterized in that by the median size (D of laser with dynamic light scattering determination LZ) in the scope of 12～200nm, and with the median size (D of NaOH titration measuring NaZ) in 5～30nm scope, described in addition median size (D LZ) and described median size (D NaZ) ratio (D LZ)/(D NaZ) in 2～30 scopes.
CNB2003101213045A 2002-12-12 2003-12-11 Process for producing silicon sol and silicon sol Expired - Fee Related CN1312035C (en)

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Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2900348A (en) * 1954-02-02 1959-08-18 Grace W R & Co Preparation of silica sols
JPS627622A (en) * 1985-07-04 1987-01-14 Nissan Chem Ind Ltd Production of silica sol having extremely fine grain diameter
JPS6345114A (en) * 1986-08-13 1988-02-26 Catalysts & Chem Ind Co Ltd Production of silica sol
JPS6345113A (en) * 1986-08-13 1988-02-26 Catalysts & Chem Ind Co Ltd Silica sol having low turbidity and low viscosity
JPS6364911A (en) * 1986-09-01 1988-03-23 Catalysts & Chem Ind Co Ltd Production of silica sol containing silica particle having large particle size
US6632489B1 (en) * 1998-09-10 2003-10-14 Nissan Chemical Industries, Ltd. Moniliform silica sol, process for producing the same, and ink-jet recording medium
JP3758391B2 (en) * 1998-12-15 2006-03-22 日本化学工業株式会社 High-purity silica aqueous sol and method for producing the same
JP4222582B2 (en) * 1999-03-04 2009-02-12 日本化学工業株式会社 Method for producing high purity silica sol
CZ299846B6 (en) * 1999-05-04 2008-12-10 Akzo Nobel N. V. Sols containing silica-based particles, process of their preparation and use
TW530029B (en) * 1999-11-17 2003-05-01 Akzo Nobel Nv A method for manufacturing of silica sols

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