CN102666383A - Process for production of silica-alumina sol, silica-alumina sol, coating agent for formation of transparent coating film which comprises the sol, and substrate having transparent coating film attached thereto - Google Patents

Process for production of silica-alumina sol, silica-alumina sol, coating agent for formation of transparent coating film which comprises the sol, and substrate having transparent coating film attached thereto Download PDF

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CN102666383A
CN102666383A CN2010800517978A CN201080051797A CN102666383A CN 102666383 A CN102666383 A CN 102666383A CN 2010800517978 A CN2010800517978 A CN 2010800517978A CN 201080051797 A CN201080051797 A CN 201080051797A CN 102666383 A CN102666383 A CN 102666383A
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silica alumina
transparent coating
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alumina particulate
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CN102666383B (en
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二神涉
箱嶋夕子
松田政幸
村口良
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GC CATALYSTS AND CHEMICALS LT
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    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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Abstract

Disclosed are: a silica-alumina sol which is stable even when the sol is used at a high concentration and has good dispersibility in a matrix component; and a process for producing the sol. Silica-alumina particles are prepared by removing any cation (an alkali metal ion) that is derived from a production raw material from a silica-alumina sol, reducing the amount of any contaminant ion contained in the silica-alumina sol, and adjusting the amount of a negative charge present on the surface of the silica-alumina sol to a value falling within a predetermined range. The silica-alumina particles are used. An organosilicon compound is adsorbed on the surfaces of the particles in advance, and the compound is hydrolyzed, thereby treating the surfaces of the particles.

Description

The method of manufacture of silicon-aluminum sol, silicon-aluminum sol, the transparent coating that contains this colloidal sol form with coating and have the base material of transparent coating
Technical field
The present invention relates to method of manufacture, the silicon-aluminum sol of silicon-aluminum sol stable under high density (silica-alumina sol), the transparent coating that contains this colloidal sol forms with coating and has the base material of transparent coating.
More detailed; Relating to method of manufacture, the silicon-aluminum sol of following silicon-aluminum sol, the transparent coating that contains this colloidal sol forms with coating and has the base material of transparent coating; Even said silicon-aluminum sol is the also stable and good dispersibility in matrix components under high density, therefore, transparent coating is formed with the coating high densityization; Even and coating is also excellent under high density; Can thick filmization, with excellences such as the adaptation of base material, scratch resistance, film hardness, film toughness, the transparency, mist degrees, can be preferred for making the base material that has transparent coating simultaneously.
Background technology
Known scratch resistance for the substrate surface that improves glass, plastics sheet, plastic lens etc., display unit etc. forms the transparent coating with hard coat function at substrate surface.Particularly, form organic resin film or mineral membrane on the surface of glass or plastics, display unit base material etc. with transparency.At this moment, in organic resin film or mineral membrane, cooperate inorganic particles such as resin particle or silicon-dioxide, and then the adaptation of raising and base material, scratch resistance etc.
In addition, in order to suppress interference fringe, cooperate the composite oxide particle of high refractive index particle such as titanium oxide, zirconium white or high refractive index etc., dwindle refringence with base material.
In addition, in order to give antistatic property, cooperate electroconductibility inorganic oxide particles such as antimony peroxide, tin-doped indium oxide, antimony doped tin oxide.
When using above-mentioned inorganic oxide particle,, carry out surface treatment with silane coupling agent in order to improve the dispersiveness in matrix components.
And then; In order to improve the stability of silicon sol; Known method of modification is carried out on the surface of silicon dioxide granule with aluminium, after for example disclosing acidic silicasol that de-ionized was handled in the patent documentation 1 and the tart aluminum saline solution mixing, the silicon sol of pH4～5 of heating gained.
In addition, patent documentation 2 discloses following method of manufacture, promptly; The Zeo-karb that is used as ammonia type or amine type is handled the above silica aqueous solution of pH6; After adding the metal-salt of aluminic acid, heat-treating more than 70 ℃, be manufactured on silicon sol stable in acidity or the neutral region.
For patent documentation 1 and patent documentation 2 described silicon sol; The surface of silicon dioxide granule is owing to covered by white lake or aluminum oxide; So stability improves; But because the particle surface of above-mentioned silicon dioxide granule has positive charge, so there is following problems: cause aggegation when cooperating with the organic cpds that contains the organic group with negative charge easily, the transparency during as coating composition descends.
In addition, for the existing coating that cooperates particle, high densityization is limited, has the problem that is not suitable for forming thick film.
Even can high densityization, stability be also insufficient, sometimes reductions such as the adaptation of the transparent coating of gained and base material, film toughness, scratch resistance.In addition because viscosity uprises during high density, so coating reduce, therefore sometimes with reductions such as the adaptation of base material, film toughness, scratch resistance.
Patent documentation 1: No. 4451388 communique of USP
Patent documentation 2: japanese kokai publication sho 58-110415 communique
Summary of the invention
The inventor etc. further investigate in view of the above problems, and the result finds that the particle that obtains as follows compares with existing particle, dispersion stable and can high densityization; Viscosity is also low, and the coating fluid that has used this particle also can high densityization and excellent in stability, thereby has accomplished the present invention; Said particle obtains as follows: remove the positively charged ion (alkalimetal ion) from the manufacturing raw material that exists in the silicon-aluminum sol; Minimizing simultaneously is mingled with ion, and the surface negative charge amount is adjusted in the specialized range, uses the silica alumina particle that obtains thus; Make silicoorganic compound be adsorbed on particle surface in advance, surface treatment is carried out in hydrolysis afterwards.
The object of the present invention is to provide a kind of method of manufacture, silicon-aluminum sol of silicon-aluminum sol, the transparent coating that contains this colloidal sol to form and have the base material of transparent coating with coating; Even said silicon-aluminum sol is also stable under high density; And the good dispersibility in matrix components; Transparent coating is formed with the coating high densityization; The coating of said coating is excellent and can thick filmization, with excellences such as the adaptation of base material, scratch resistance, film hardness, film toughness, the transparency, mist degrees, can be preferred for making the base material that has transparent coating simultaneously.
The method of manufacture of silicon-aluminum sol of the present invention is characterised in that, comprises the steps (a)～(f).
(a) spent ion exchange resin carries out the dispersive aqueous dispersions to the silica alumina particulate with solid component concentration and handles in the scope of 1～30 weight %, makes ion (remove H+, OH -Outside) concentration reaches in the silica alumina particulate and to be the step below the 50ppm, the median size of said silica alumina particulate is in the scope of 5～100nm, and the alumina content in the particle is with Al 2O 3Meter is in 0.01～5 weight % scope;
(b) solvent exchange with silica alumina particulate aqueous dispersions is the step of alcohol
(c) in silica alumina particulate alcohol dispersion liquid, add the silicoorganic compound that following formula (1) is represented, as R n-SiO (4-n)/2Step in the scope of 1～50 weight % of silica alumina particulate;
R n-SiX 4-n (1)
(in the formula, R is that carbonatoms is 1～10 nothing replacement or substituted hydrocarbon radical, each other can be identical, and also can be different.X is alkoxyl group, hydroxyl, halogen, the hydrogen of carbonatoms 1～4, and n is 1～3 integer)
(d) while stirring silica alumina particulate alcohol dispersion liquid, making above-mentioned silicoorganic compound be adsorbed on the step on the silica alumina particulate;
(e) add water and hydrolysis and use catalyzer, the step that silicoorganic compound are hydrolyzed;
(f) in 0.5～24 hour step of 40～120 ℃ of following slakings.
Above-mentioned steps (a) preferably includes following step (a1) and reaches (a2).
(a1) handle with Zeo-karb, make the step of pH in 1.0～6.0 scope;
(a2): handle with anionite-exchange resin, make the pH of dispersion liquid be higher than pH, the step in 2.0～7.0 scope of the dispersion liquid in the above-mentioned steps (a1).
In above-mentioned steps (f) afterwards, preferably carry out following step (g) and/or (h).
(g) be replaced into the step of organic solvent;
(h) spissated step.
The negative charge amount of the per unit surface-area of the silica alumina particulate of the silica alumina particulate aqueous dispersions that obtains in the preferred above-mentioned steps (a) under the condition of pH2.0～7.0 at 0.1～1.5 μ eq/m 2Scope in.
Mole number (the M of the water in the preferred above-mentioned steps (e) H2O) with the mole number (M of silicoorganic compound OC) mol ratio (M H2O)/(M OC) in 1～300 scope.
Hydrolysis in the preferred above-mentioned steps (e) uses catalyzer to be ammonia, the mole number (M of ammonia NH3) with the mol ratio (M of the mole number (Moc) of silicoorganic compound NH3)/(M OC) in 0.1～12 scope.
Preferably for the negative charge amount of the per unit surface-area of the silica alumina particulate of the silica alumina particulate aqueous dispersions that obtains in the above-mentioned steps (f); When using solid component concentration to be the dispersion liquid mensuration of 0.5 weight %, pH7.5 ± 1.5, at 0.5～2.0Micro-coulombs/cm 2Scope in.
Organic solvent in the preferred above-mentioned steps (g) be selected from ethers, ester class, ketone, the alcohols more than a kind or 2 kinds.
Preferred solid component concentration is in the scope of 20～70 weight %, and viscosity is 1～10, in the scope of 000cp.
Silicon-aluminum sol of the present invention is that the alumina content of median size in the scope of 5～100nm, in the particle is with Al 2O 3Meter has carried out the dispersion liquid of surface-treated silica alumina particulate in the scope of 0.01～5 weight % and with the silicoorganic compound of following formula (1) expression; It is characterized in that the per unit surface-area negative charge amount (Q of this surface treatment silica alumina particulate 1) with the per unit surface-area negative charge amount (Q that carries out the silica alumina particulate before the surface treatment with silicoorganic compound 2) ratio (Q 1)/(Q 2) in 0.2～0.8 scope.
R n-SiX 4-n (1)
(in the formula, R is that the nothing of carbonatoms 1～10 replaces or substituted hydrocarbon radical, each other can be identical or different.X is alkoxyl group, hydroxyl, halogen, the hydrogen of carbonatoms 1～4, and n is 1～3 integer)
Silicon-aluminum sol as claimed in claim 9 is characterized in that, above-mentioned negative charge amount (Q 1) when using solid component concentration to be the dispersion liquid mensuration of 0.5 weight %, pH7.5 ± 1.5, at 0.5～2.0Micro-coulombs/cm 2Scope in.
Transparent coating of the present invention forms and is characterised in that with coating; By above-mentioned each described silicon-aluminum sol, matrix forms composition and dispersion medium is formed; Total solid component concentration is in the scope of 30～70 weight %; The concentration that matrix forms composition in solid state component in the scope of 6～63 weight %, the concentration of silica alumina particulate in solid state component in the scope of 3～56 weight %.
Preferred above-mentioned matrix is formed into and is divided into silicon class matrix formation composition or organic resin matrix formation composition, contains polyfunctional acrylic ester resin or multifunctional silicone resin.
The preferred silicon class stain control agent of counting 0.003～0.7 weight % with solid state component that also contains.
The preferred even paint of counting 0.003～0.56 weight % with solid state component that also contains.
Preferred above-mentioned dispersion medium be selected from ethers, ester class, ketone, the alcohols more than a kind or 2 kinds.
The base material that has transparent coating of the present invention is formed by base material and the transparent coating that is formed on the base material, it is characterized in that, this transparent coating is to use above-mentioned each described transparent coating to form and forms with coating.
The content of the silica alumina particulate in the preferred above-mentioned transparent coating in solid state component in the scope of 10～80 weight %, the content of matrix components in solid state component in the scope of 20～90 weight %.
The thickness of preferred above-mentioned transparent coating is in the scope of 0.5～20 μ m.
According to the present invention, though can provide a kind of under high density the silicon-aluminum sol and the method for manufacture thereof of excellent dispersion also stable, in matrix components.
In addition, form and use coating even can access the transparent coating that contains that above-mentioned silicon-aluminum sol viscosity under high density is also lower, stable, coating is excellent and can thick filmization.
Can also obtain a kind of base material that has transparent coating; Even excellences such as the adaptation of said transparent coating and base material, scratch resistance, film hardness, film toughness, the transparency, mist degree are through also keeping for a long time excellent chemical proofing, water tolerance, water-repellancy, grease proofness, anti-fingerprint tack.
Embodiment
[method of manufacture of silicon-aluminum sol]
The method of manufacture of silicon-aluminum sol of the present invention is characterised in that, comprises the steps (a)～(f).
Step (a)
(a) spent ion exchange resin carries out the dispersive aqueous dispersions to the silica alumina particulate with solid component concentration and carries out processed steps in the scope of 1～30 weight %, makes ion (remove H+, OH -Outside) concentration is below the 50ppm in the silica alumina particulate, the median size of said silica alumina particulate is in the scope of 5～100nm, and the alumina content in the particle is with Al 2O 3Meter is in the scope of 0.01～5 weight %.
Silica alumina particle dispersion liquid for the present invention's use; If the median size of silica alumina particulate and the content of aluminum oxide are in above-mentioned scope; Then not special restriction; Can use existing known silica alumina particulate aqueous dispersions (below, be called the sial water-sol sometimes).
The pH of the silica alumina particulate aqueous dispersions that the present invention can preferably use is regional in 8～12 alkalescence usually.
The median size of silica alumina particulate is preferably in the scope of 5～100nm, more preferably in the scope of 10～80nm.
Median size is during less than 5nm, and gained silicon-aluminum sol stable insufficient is difficult to obtain the silicon-aluminum sol of high density, therefore, also is difficult to obtain high density and stable transparent coating and forms and use coating fluid.
When the median size of silica alumina particulate surpasses 100nm; Because particle diameter is big; So the surface negative charge amount of the silica alumina particulate that obtains in the following step (b) is low, therefore, the adsorptive capacity of the silicoorganic compound in the step (d) becomes insufficient; Be difficult to obtain the dispersiveness in organic solvent, the silica alumina particle dispersion liquid of excellent in stability, equally also be difficult to obtain high density and stable transparent coating and form and use coating fluid.
In addition, with Al 2O 3Meter, the alumina content in the silica alumina particulate is preferably in the scope of 0.01～5 weight %, more preferably in the scope of 0.05～3 weight %.Alumina content in the silica alumina particulate is with Al 2O 3Meter is during less than 0.01 weight %; The surface negative charge amount of the silica alumina particulate that obtains in the step (a) is low; The adsorptive capacity of the silicoorganic compound in the following step (d) becomes insufficient, is difficult to obtain the dispersiveness in organic solvent, the silica alumina particle dispersion liquid of excellent in stability.
With Al 2O 3Meter; Even the alumina content in the silica alumina particulate surpasses 5 weight %; The surface negative charge amount of the silica alumina particulate that obtains in the step (a) can further not raise yet; When only using Zeo-karb in the removing of the minimizing of the alkali in the silica alumina particulate (Na) and aluminum oxide, the ion exchange resin treatment decrease in efficiency.
In addition, the sial water-sol uses ultrafiltrationmembrane process or ion-exchange-resin process to clean after manufacturing, but from the alkali of raw material remain in the particle and dispersion medium in.
For the residual quantity of alkali, to be present in the amount in the silica alumina particulate, probably 1000～10, in the scope of 000ppm.In addition, except that above-mentioned alkali, also have other positively charged ions, negatively charged ion from raw material, device etc. to exist, the ionic concn that these ions amount to is 1,200～12,000ppm.
For the concentration of silica alumina particulate aqueous dispersions, if can use following ion exchange resin to carry out the dealkalize treated cation, remove and be mingled with ion, then not special restriction is with SiO 2Al 2O 3Meter is preferred general in the scope of 1～30 weight %, more preferably in the scope of 2～25 weight %.
As ion exchange resin, can use Zeo-karb or Zeo-karb and anionite-exchange resin or two ion exchange resin.
The method of ion exchange resin treatment usually adopts following method: in silica alumina particulate aqueous dispersions, mix the method for above-mentioned resin or make the method for the post of silica alumina particulate aqueous dispersions through being filled with above-mentioned ion exchange resin.
Ionic concn in the silica alumina particle dispersion liquid of crossing for ion exchange resin treatment to be present in the ionometer in the silica alumina particulate, is preferably below the 500ppm, more preferably below the 250ppm.
As the ion of ionic concn, can enumerate the Na that uses in the manufacturing of silicon-aluminum sol here, for positively charged ion +, K +Deng the alkaline earth metal ion that exists with the impurity form sometimes in alkalimetal ion, the above-mentioned alkalimetal ion, other sometimes from the manufacturing installation of silicon-aluminum sol dissolving separate out and the metals ion of sneaking into etc.
For negatively charged ion, mainly can enumerate sulfate ion that contains sometimes in cl ions from the hydrochloric acid that in the manufacturing of silicon-aluminum sol, uses sometimes, the raw material etc.
Need to prove, do not contain H in the ion of above-mentioned ionic concn +And OH -
When the above-mentioned ionic concn in the silica alumina particle dispersion liquid that ion exchange resin treatment is crossed surpasses 500ppm; Reason may not be clear and definite; But perhaps because the adsorptive capacity of the silicoorganic compound in the following step (d) reduces, and the adsorptive power to the silica alumina microparticle surfaces dies down simultaneously, so the high densityization of the silicon-aluminum sol of final gained is insufficient; Even can high densityization, also there be the stability inadequate tendency that becomes.
Among the present invention, above-mentioned ionic concn uses ICP emission spectrometry method (emission spectro-photometric analysis) to measure.
Above-mentioned steps (a) preferably includes following step (a1) and reaches (a2).
Step (a1)
At first, handle with Zeo-karb, the pH that makes the silica alumina particle dispersion liquid is in 1.0～6.0 scope, preferably in 1.5～4.0 scope.
The pH of the silica alumina particle dispersion liquid after Zeo-karb is handled was less than 1.0 o'clock; Aluminum oxide in the silica alumina particulate becomes very few; The negative charge amount step-down of the per unit surface-area of the particle that obtains in the following step (a); The adsorptive capacity of the silicoorganic compound in the step (d) becomes insufficient, therefore, can not get high density and stable silicon-aluminum sol sometimes.
The pH of the silica alumina particle dispersion liquid after Zeo-karb is handled was above 6.0 o'clock; The concentration of positively charged ion in the silica alumina particulate (Na ion) or foreign cations can not be reduced in the above-mentioned scope sometimes; In this case; Also perhaps because the adsorptive capacity of the silicoorganic compound in the following step (d) reduces, the adsorptive power to the silica alumina microparticle surfaces dies down simultaneously, so the high densityization of the silicon-aluminum sol that finally obtains is insufficient; Even can high densityization, also there be the stability inadequate tendency that becomes.
Step (a2)
Next, handle, make the pH of dispersion liquid be higher than the pH of the dispersion liquid in the above-mentioned steps (a1), in 2.0～7.0 scope, preferably in 2.5～6.0 scope with anionite-exchange resin.
The pH of the silica alumina particle dispersion liquid after the anion-exchange resin treatment is less than 2.0 o'clock, anionicly removes insufficiently, and therefore, following sometimes surperficial negative charge amount becomes insufficient.
For the silica alumina particle dispersion liquid after the anion-exchange resin treatment, if can carry out predetermined process in the above-mentioned steps (a1), then pH can not surpass 7.0, and anion concentration can further not reduce yet.
The negative charge amount of the per unit surface-area of the silica alumina particulate of the silica alumina particulate aqueous dispersions that obtains in the above-mentioned steps (a) is under the condition of pH2.0～7.0, preferably at 0.1～1.5 μ eq/m 2Scope in, more preferably at 0.2～1.5 μ eq/m 2Scope in.
The negative charge amount of the per unit surface-area of silica alumina particulate seldom, less than 0.1 μ eq/m 2Situation under, perhaps because the adsorptive capacity of silicoorganic compound in the following step (d) is few, adsorptive power also a little less than, so be difficult to obtain the dispersiveness in organic solvent, the silica alumina particle dispersion liquid of excellent in stability.
The negative charge amount of per unit surface-area that is difficult to obtain the silica alumina particulate is more, surpass 1.5 μ eq/m 2The silica alumina particle dispersion liquid; Even can access, the adsorptive capacity of silicoorganic compound yet can further not increase and then be difficult to obtain the silica alumina particle dispersion liquid of dispersiveness, excellent in stability and high density in organic solvent.
Among the present invention, the specific surface area (m of particle 2/ g) use the BET method to measure, negative charge amount (μ eq/g) is used particle charge meter (Spectris (strain) system: PCD-03), to use solid component concentration be that the silica alumina particulate aqueous dispersions of 10 weight % is measured.
The negative charge amount of per unit surface-area (μ eq/m 2) obtain divided by surface-area with above-mentioned negative charge amount (μ eq/g).
Step (b)
With the solvent exchange of silica alumina particulate aqueous dispersions is alcohol.
Here, the purpose of solvent exchange is in step (c), to be dissolved with organic silicon compound and not make its hydrolysis, in step (d), silicoorganic compound is adsorbed on the silica alumina particulate.
The method of solvent exchange can change according to the kind of alcohol, preferred ultrafiltrationmembrane process.
The concentration of the silica alumina particulate alcohol dispersion liquid behind the solvent exchange is preferably in the scope of 1～30 weight %, more preferably in the scope of 2～20 weight %.
Need to prove that the residual quantity of the moisture in the pure dispersion liquid of silica alumina particulate also according to the kind of silicoorganic compound, water-disintegrable etc. and different, is preferably below the 5 weight %, more preferably below the 1 weight % in dispersion liquid.
When the residual quantity of the moisture in the silica alumina particulate alcohol dispersion liquid surpasses 5 weight %, hydrolysis in the liquid taking place in step (c) sometimes, causes that in step (d) absorption suppresses, in step (e), generates gelling material, perhaps generation particles aggregate in step (f).
The mensuration of the amount of moisture of this moment uses Ka Er Fischer moisture meter to measure.
Step (c)
Then, in the pure dispersion liquid of silica alumina particulate, add the silicoorganic compound of following formula (1) expression, though according to the difference of the particle diameter of silica alumina particulate and difference makes it with R n-SiO (4-n)/2Meter is in the scope of 1～50 weight % of silica alumina particulate, more preferably in the scope of 5～40 weight %.
R n-SiX 4-n (1)
(wherein, in the formula, R is that the nothing of carbonatoms 1～10 replaces or substituted hydrocarbon radical, each other can be identical, and also can be different.X: the alkoxyl group of carbonatoms 1～4, hydroxyl, halogen, hydrogen, the integer of n:1～3)
Silicoorganic compound as above-mentioned formula (1) expression; Can enumerate methyltrimethoxy silane, dimethyldimethoxysil,ne, phenyltrimethoxysila,e, dimethoxydiphenylsilane, Union carbide A-162, dimethyldiethoxysilane, phenyl triethoxysilane, phenylbenzene diethoxy silane, isobutyl-Trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (β methoxy ethoxy) silane, 3; 3; 3-trifluoro propyl Trimethoxy silane, methyl-3; 3; 3-trifluoro propyl dimethoxy silane, β-(3，4-Huan Yanghuanjiji)Yi Jisanjiayangjiguiwan, γ-glycidoxy methyltrimethoxy silane, γ-glycidoxy Union carbide A-162, γ-glycidoxy ethyl trimethoxy silane, γ-glycidoxy ethyl triethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, γ-glycidoxy propyl-triethoxysilicane, γ-(beta epoxide propoxy-oxyethyl group) propyl trimethoxy silicane, γ-(methyl) acryloxy methyltrimethoxy silane, γ-(methyl) acryloxy Union carbide A-162, γ-(methyl) acryloxy ethyl trimethoxy silane, γ-(methyl) acryloxy ethyl triethoxysilane, γ-(methyl) acryloxy propyl trimethoxy silicane, γ-(methyl) acryloxy propyl trimethoxy silicane, γ-(methyl) acryloxy propyl-triethoxysilicane, γ-(methyl) acryloxy propyl-triethoxysilicane, butyl trimethoxy silane, isobutyl-triethoxyl silane, hexyl triethoxy sila octyl group (silaoctyl) triethoxyl silane, decyl triethoxyl silane, butyl triethoxyl silane, isobutyl-triethoxyl silane, hexyl triethoxyl silane, octyltri-ethoxysilane, decyl triethoxyl silane, 3-urea groups sec.-propyl propyl-triethoxysilicane, perfluoro capryl ethyl trimethoxy silane, perfluoro capryl ethyl triethoxysilane, perfluoro capryl ethyl three isopropoxy silane, trifluoro propyl Trimethoxy silane, N-β (amino-ethyl) gamma-amino propyl group methyl dimethoxysilane, N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N-phenyl-gamma-amino propyl trimethoxy silicane, γ-Qiu Jibingjisanjiayangjiguiwan, trimethyl silicane alkanol, METHYL TRICHLORO SILANE etc.
Wherein, For the X as above-mentioned formula (1) is the silicoorganic compound of the alkoxyl group of carbonatoms 1～4; Even the residual quantity of the moisture in above-mentioned silica alumina particulate alcohol dispersion liquid for more for a long time, also is not easy hydrolysis in above-mentioned scope, the tendency of absorption is arranged; Can improve dispersed surface treatment effectively, so preferred.
The addition of silicoorganic compound is with R n-SiO (4-n)/2Meter is during less than 1 weight % of silica alumina particulate, and high-concentration and stable, the dispersiveness in matrix components of the silica alumina of gained surface treatment sometimes particulate become insufficient.
The addition of silicoorganic compound is with R n-SiO (4-n)/2When meter surpasses 50 weight % of silica alumina particulate; Though according to the difference of median size and difference, the absorption difficulty, excessive sometimes silicoorganic compound generate gelling material or in step (f), become the reason of particles aggregate in step (e); Even absorption; Perhaps also only be range upon range of, the amount increase of hydrolysis silicoorganic compound of silica alumina microparticle surfaces, dispersed not further the raising can not high densityization.
Step (d)
Next, Yi Bian stir silica alumina particulate alcohol dispersion liquid, Yi Bian silicoorganic compound are adsorbed on the silica alumina particulate.
The not special restriction of the temperature of the dispersion liquid of this moment is below the boiling point for normal temperature (general 20 ℃)～alcoholic solvent.
Step (e)
Next, add water and hydrolysis and use catalyzer, silicoorganic compound are hydrolyzed.
At this moment, the mole number (M of the water of interpolation H2O) with the mole number (M of silicoorganic compound OC) mol ratio (M H2O)/(M OC) preferably in 1～300 scope, more preferably in 5～200 scope.
Mol ratio (M H2O)/(M OC) less than 1 o'clock, it is insufficient that hydrolysis becomes, and need remove not hydrolysis silicoorganic compound, even remove, also is difficult to obtain the excellent silicon-aluminum sol of high-concentration and stable.
Mol ratio (M H2O)/(M OC) surpass at 300 o'clock, need remove afterwards, but it removes difficulty, form when use coating fluid at the transparent coating that is used to use following organic solvent, stability becomes insufficient sometimes, can not get stablizing and the coating fluid of high density.
In addition, preferred ammonia is used catalyzer as hydrolysis.When using ammonia, also remove easily,, then can significantly not damage the stability of coating fluid, also can not damage the performance of the transparent coating that uses this coating fluid formation if residual quantity is a small amount of even remain in the coating fluid.
Mole number (the M of the ammonia that adds NH3) with the mole number (M of silicoorganic compound OC) mol ratio (M NH3)/(M OC) preferably in 0.1～12 scope, more preferably in 0.2～10 scope.
Mol ratio (M NH3)/(M OC) less than 0.1 o'clock, it is insufficient that hydrolysis becomes, and need remove unhydrolysed silicoorganic compound, even remove, also is difficult to obtain the excellent silicon-aluminum sol of high-concentration and stable.
Mol ratio (M NH3)/(M OC) surpass at 12 o'clock, though hydrolyzate can be not residual, ammonia is residual more, the stability of coating fluid, the performance of transparent coating (scratch resistance, the transparency, outward appearance etc.) become insufficient, therefore, cause removing residual ammonia.
The addition means of water and ammonia also can add respectively separately, but preferably adds with the form of ammoniacal liquor.
Step (f)
Next, at 40 ℃～120 ℃, special general 0.5～24 hour in the following slaking of the boiling point of solvent.
Through slaking under these conditions, the hydrolysis of the silicoorganic compound that the silica alumina microparticle surfaces is adsorbed finishes, and promotes the bonding reaction of particle surface and hydrolyzate, can access high density and silicon-aluminum sol stable, excellent dispersion.
Negative charge amount for the per unit surface-area of the silica alumina particulate of the silica alumina particulate aqueous dispersions that obtains in the above-mentioned steps (f); When using solid component concentration to be the dispersion liquid mensuration of 0.5 weight %, pH7.5 ± 1.5, preferably at 0.5～2.0Micro-coulombs/cm 2Scope in.
The negative charge amount (Q 1) of per unit surface-area that is difficult to obtain surface treatment silica alumina particulate is less, less than 0.5Micro-coulombs/cm 2Silica alumina particulate aqueous dispersions, negative charge amount (Q1) is more, surpass 2.0Micro-coulombs/cm 2Even silica alumina particulate aqueous dispersions do not use the method for the invention described above, utilize existing known method, handle through silane coupling agent and also can obtain, it is insufficient that the dispersiveness in organic solvent, stability become sometimes.Assay method for the negative charge amount of per unit surface-area is described below.
Among the present invention, in above-mentioned steps (f) afterwards, preferably carry out following step (g) and/or (h).
Step (g)
Be replaced into organic solvent.
As organic solvent, the organic solvent that uses in the preferred following coating.
Particularly, be preferably be selected from ethers, ester class, ketone, the alcohols more than a kind or 2 kinds.
If be above-mentioned organic solvent, then can access high density and stable silicon-aluminum sol, and then, use above-mentioned silicon-aluminum sol, can access high density and stable coating.
As the method that is replaced into organic solvent, as long as can replace, not special restriction, but common preferably ultrafiltrationmembrane process, distillation method.Need to prove, at this moment, also can concentrate.
Through being replaced into organic solvent, can remove impurity, unreacted reactants etc. such as hydrolysts such as residual moisture or ammonia, can access simultaneously spendable in the coating of the present invention can high densityization and stable silicon-aluminum sol.
Step (h)
Next, concentrate as required.
As concentrating means, (g) likewise can adopt ultrafiltrationmembrane process, distillation method with step.
Need to prove that among the present invention, also a step in implementation step (g) and the step (h) only also can be implemented two steps, and can the replacing order.
The solid component concentration of the silicon-aluminum sol that obtains as stated is preferably in the scope of 20～70 weight %, more preferably in the scope of 30～70 weight %.
Even the solid component concentration of silicon-aluminum sol not according to the present invention, also can obtain stable sols during less than 20 weight %, in addition, even in transparent coating forms with coating fluid, cooperate, also can not get the coating fluid of high density.
Be difficult to obtain the silicon-aluminum sol of the solid component concentration of silicon-aluminum sol above 70 weight %, even obtain, stability is also insufficient, is not suitable for the formation of transparent coating.
In addition, the viscosity of silicon-aluminum sol is different because of the difference of concentration, preferably 1～10, in the scope of 000cp, more preferably 2～5, in the scope of 000cp.The viscosity of silicon-aluminum sol is during less than 1cp; Be difficult to obtain the silicon-aluminum sol of above-mentioned concentration range, surpass 10, during 000cp; Permanent stability descend and coating descends, and are difficult to form excellent transparent coatings such as uniform film thickness and scratch resistance, the transparency, outward appearance sometimes.
Need to prove that the mensuration of medium viscosity of the present invention can be used viscometer (eastern machine industry (strain) system: BL type viscosity agent) measure.
[silicon-aluminum sol]
Silicon-aluminum sol of the present invention is the dispersion liquid of silica alumina particulate, and the alumina content of the median size of said silica alumina particulate in the scope of 5～100nm, in the particle is with Al 2O 3Meter is in the scope of 0.01～5 weight %, and the silicoorganic compound of representing with following formula (1) have carried out surface treatment, it is characterized in that the per unit surface-area negative charge amount (Q of this surface treatment silica alumina particulate 1) and carry out the per unit surface-area negative charge amount (Q of the silica alumina particulate before the surface treatment with silicoorganic compound 2) ratio (Q 1)/(Q 2) in 0.2～0.8 scope.
R n-SjX 4-n (1)
(wherein, in the formula, R is that the nothing of carbonatoms 1～10 replaces or substituted hydrocarbon radical, each other can be identical, and also can be different.X: the alkoxyl group of carbonatoms 1～4, hydroxyl, halogen, hydrogen, the integer of n:1～3)
Surface treatment silica alumina particulate
Among the present invention, the alumina content of surface treatment silica alumina particulate is with Al 2O 3Meter is preferably in the scope of 0.01～5 weight %, more preferably in the scope of 0.05～3 weight %.
Alumina content in the surface treatment silica alumina particulate is with Al 2O 3Meter is during less than 0.01 weight %; Silicon dioxide microparticle in the existing silicon sol or existingly carried out surface-treated silicon dioxide microparticle and following per unit surface-area negative charge amount (Q1) for degree and more with silane coupling agent is difficult to obtain the dispersiveness in organic solvent, the silica alumina particle dispersion liquid of excellent in stability.
Alumina content in the surface treatment silica alumina particulate is with Al 2O 3Even meter surpasses 5 weight %, per unit surface-area negative charge amount (Q1) can further not tail off yet, and the dispersiveness in organic solvent, stability can further significantly not raise yet.
The median size of surface treatment silica alumina particulate is preferably in the scope of 5～100nm, more preferably in the scope of 10～80nm.
Median size is during less than 5nm, and surface treatment silica alumina particle dispersion liquid stable insufficient is difficult to obtain the silicon-aluminum sol of high density, therefore, also is difficult to obtain high density and stable transparent coating and forms and use coating fluid.
When the median size of surface treatment silica alumina particulate surpasses 100nm; Because particle diameter is big; So the surface negative charge amount of the silica alumina particulate that in above-mentioned steps (b), obtains is few, therefore, the adsorptive capacity of the silicoorganic compound in step (d) becomes insufficient; Be difficult to obtain the dispersiveness in organic solvent, the surface treatment silica alumina particle dispersion liquid of excellent in stability, equally also be difficult to obtain high density and stable transparent coating and form and use coating fluid.
The per unit surface-area negative charge amount (Q1) of surface treatment silica alumina particulate and the per unit surface-area negative charge amount (Q that carries out surface treatment silica alumina particulate before with silicoorganic compound 2) ratio (Q 1)/(Q 2) preferably in 0.2～0.8 scope, more preferably in 0.2～0.6 scope.
Be difficult to obtain above-mentioned than (Q 1)/(Q 2) silica alumina particulate less than 0.2, above-mentioned than (Q 1)/(Q 2) surpass at 0.8 o'clock, even do not use the method for the invention described above, and use has known method now, also can obtain through the silane coupling agent processing, the dispersiveness in organic solvent, stability become insufficient sometimes.
Negative charge amount (Q for the per unit surface-area of surface treatment silica alumina particulate 1), when using solid component concentration to be the dispersion liquid mensuration of 0.5 weight %, pH7.5 ± 1.5, preferably at 0.5～2.0Micro-coulombs/cm 2, more preferably at 0.5～1.6Micro-coulombs/cm 2Scope in.
Be difficult to obtain the negative charge amount (Q of the per unit surface-area of surface treatment silica alumina particulate 1) less, less than 0.5Micro-coulombs/cm 2Surface treatment silica alumina particulate, for the negative charge amount (Q of per unit surface-area 1) more, surpass 2.0Micro-coulombs/cm 2Surface treatment silica alumina particulate, even do not use the method for the invention described above, and use existing known method, handle through silane coupling agent and also can access, the dispersiveness in organic solvent, stability become insufficient sometimes.
The per unit surface-area negative charge amount (Q of surface treatment silica alumina particulate of the present invention 1), carry out the per unit surface-area negative charge amount (Q of the silica alumina particulate before the surface treatment with silicoorganic compound 2) measuring method be described below: carry out to surface treatment silica alumina particle dispersion liquid or with silicoorganic compound adding entry in the silica alumina particle dispersion liquid before the surface treatment; With solid component concentration be adjusted to 0.5 weight %, pH regulator is pH7.5 ± 1.5; Use particle charge meter (Spectris (strain) system: PCD-03); The diallyl dimethyl ammoniumchloride of using 0.001N is as titrating solution; Measure surface negative charge amount (μ eq/g), with the surface negative charge amount divided by specific surface area and be scaled Micro-coulombs/cm 2And obtain.Need to prove, convert and use following relation.
1Micro-coulombs/cm 2＝0.0628charges/nm 2(RALPH?K.ILER，THE?CHEMISTRY?OF?SILICA：John&Sons.Inc：1979)
[transparent coating forms and uses coating]
Transparent coating of the present invention forms and is characterised in that with coating; Form composition and dispersion medium forms by above-mentioned silicon-aluminum sol, matrix; Total solid component concentration is in the scope of 30～70 weight %; In the scope of 6～63 weight %, the concentration of silica alumina particulate is in the scope of 3～56 weight % in solid state component for the concentration of matrix formation composition.
Silicon-aluminum sol
As silicon-aluminum sol, the silicon-aluminum sol that can use above-mentioned silicon-aluminum sol, adopt the method for manufacture of above-mentioned silicon-aluminum sol to obtain.
Matrix forms composition
The matrix of using as the present invention forms composition, can use organic resin class matrix to form composition or silicon class (collosol and gel class) matrix formation composition.
Form composition as organic resin class matrix, can use existing known organic resin.
Particularly, as coating resin, can adopt in known thermosetting resin, the thermoplastic resin etc. any.For example, can enumerate all the time thermosetting resins such as thermoplastic resin, urethane resin, melamine resin, silicone resin, butyral resin, reactive silicone resin, resol, epoxy resin, unsaturated polyester resin, thermosetting acrylic resin such as the vibrin that uses, polycarbonate resin, polyamide resin, polyphenylene oxide resin, thermoplastic acrylic resin, vinyl chloride resin, fluoro-resin, vinyl acetate resin, organo-silicone rubber etc.
And then, can be the multipolymer more than 2 kinds or the modification body of above-mentioned resin.
Above-mentioned resin can be emulsion resin, water soluble resin, hydrophilic resin.Can also be thermosetting resin, ultraviolet curing resin, electronic beam solidified resin, the situation of thermosetting resin can contain curing catalysts.
Among the present invention, wherein preferably use polyfunctional acrylic ester resin, multifunctional silicone resin.Functional group as this moment can enumerate (methyl) acrylic or epoxy group(ing).
As the polyfunctional acrylic ester resin, can enumerate acrylate resin, (2) 2 functional acrylate's resins and/or 2 officials ability silicone resin that (1) has the above functional group of 3 officials ability.
As acrylate resin, particularly, can enumerate 3 functional acrylate's resins such as pentaerythritol triacrylate, Viscoat 295, trimethylolpropane trimethacrylate with the above functional group of 3 officials ability; 4 functional acrylate's resins such as tetramethylol methane tetraacrylate; 6 functional acrylate's resins such as dipentaerythritol acrylate; 3 officials such as tetramethylolmethane hexamethylene diisocyanate carbamate prepolymer ability urethane acrylate resin; Tetramethylolmethane polyglycidyl ether propenoate etc. contains 4 functional acrylate's resins of epoxy group(ing); Cresols-line style phenolic epoxy propenoate, bisphenol A diglycidyl ether vinylformic acid affixture etc. contain the polyfunctional acrylic ester resin of epoxy group(ing) etc., also can preferably use their mixture.
Have the acrylate resin of the above functional group of 3 officials ability, can use monomer, also can use dimer above oligomer, polymkeric substance.
Next; As (2) 2 functional acrylate's resins, can enumerate glycols propenoate such as polyethyleneglycol diacrylate, neopentylglycol diacrylate, tripropylene glycol diacrylate, polypropyleneglycol diacrylate, polyethylene glycol dimethacrylate, TD 1523, tripropylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polypropylene glycol dimethacrylate.
Can also enumerate 1; 4-butylene glycol dimethacrylate, 1; 6-hexanediol dimethacrylate, 1; 9-nonanediol dimethacrylate, decamethylene-glycol dimethacrylate, USP Kosher dimethacrylate, 2-hydroxyl-3-acryloxy propyl methyl acid esters, 1,6 hexanediol diacrylate, 1; 9-nonanediol diacrylate, dihydroxymethyl-tristane diacrylate, 2-hydroxyl-non-glycols propenoate such as 3-acryloxy propyl methyl acid esters also can preferably use their mixture.
Next, as 2 officials ability silicone resin, can use the resin of following chemical formula (1) expression.In the chemical formula (1), R 1, R 3～R 5Expression replaces, the alkyl of no substituted carbonatoms 1～6, X 1, X 2Expression propenyl, methylpropenyl, glycidyl can be identical, also can be different.N is 1～10 integer.
Figure BPA00001559827600191
Particularly, can enumerate diacrylate modified polyorganosiloxane, dimethacrylate modified polyorganosiloxane, diglycidyl modified polyorganosiloxane, two polyester modification ZGK 5, two polyethers modified polyorganosiloxanes etc. and their mixture.
At this moment, 2 functional acrylate's resins, 2 officials can preferably use monomer by silicone resin.
When using monomer; Perhaps since promoted with and usefulness above-mentioned have the bonding that acrylate resin and following 1 official of the functional group that 3 officials can be above can silicone resin (silicone based stain control agent); So excellences such as water-repellancy, grease proofness, anti-fingerprint tack, chemical proofing; Can suppress the disengaging that 1 official can silicone resin (below, be called sometimes and ooze out), can the long term maintenance water-repellancy, grease proofness, anti-fingerprint tack, chemical proofing.
And then transparent coating forms with in the coating, preferably use following chemical formula (2) expression, (3) 1 officials can silicone resin as silicone based stain control agent.In the chemical formula (2), R 1～R 5Expression replaces, the alkyl of no substituted carbonatoms 1～3, and X representes propenyl, methylpropenyl, glycidyl.N is 1～20 integer.
Figure BPA00001559827600192
Particularly, can enumerate acroleic acid modified polysiloxane, methylacrylic acid modified polyorganosiloxane, glycidyl modified polyorganosiloxane, polyester-modified polysiloxanes, polyether-modified ZGK 5 etc. and their mixture.For example, can enumerate single end (methyl) vinylformic acid silicone oil, single terminal glycidyl group silicone oil etc.In addition, also preferred acrylic acid or the like silicone resin monomer or its polymkeric substance (silicone oil), epoxies silicone resin monomer or its polymkeric substance (silicone oil), polyester silicone resin monomer or polymkeric substance (silicone oil).
And then,, transparent coating preferably contains even paint in forming with coating.
As even paint, can enumerate T 46155 three decyl ethers, polyoxyethylene lauryl ether, polyoxyalkylene lauryl ether, Vilaterm isodecyl ether, Vilaterm polyoxypropylene block polymer, polyoxyethylene oleate, T 46155 SUNSOFT Q-182S, Witconol 5909, other special silicone based or special acrylic acid or the like etc. as even paint or skimmer and known material.When containing above-mentioned even paint, can access the excellent transparent coating of outward appearance.
Dispersion medium
The dispersion medium that uses among the present invention be preferably be selected from ethers, ester class, ketone, the alcohols more than a kind or 2 kinds.
Specifically can enumerate alcohols such as methyl alcohol, ethanol, propyl alcohol, 2-propyl alcohol (IPA), butanols, Pyranton, furfuryl alcohol, tetrahydrofurfuryl alcohol; Polyalcohols such as terepthaloyl moietie, pinakon; Ester classes such as methyl acetate, ETHYLE ACETATE, isopropyl acetate, propyl acetate, isobutyl acetate, butylacetate, Isoamyl Acetate FCC, pentyl acetate, acetate 3-methoxyl group butyl ester, acetate 2-ethyl butyl ester, hexalin acetate, ethylene glycol acetate; Ethers such as ether, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, terepthaloyl moietie isopropyl ether, diglycol monotertiary methyl ether, carbiphene, propylene glycol monomethyl ether, Ucar 35 list ethyl ether; Ketones such as acetone, methyl ethyl ketone, MIBK, butyl methyl ketone, pimelinketone, methylcyclohexanone, butyrone, Methyl amyl ketone, DIBK.Above-mentioned substance can use separately, or mixes more than 2 kinds and use.
Polymerization starter
Among the present invention, when containing matrix formation composition, silica alumina particulate, can contain polymerization starter.As polymerization starter, can especially restrictedly not use known material, for example can enumerate two (2; 4,6-Three methyl Benzene formyl) phenyl phosphine oxide, two (2,6-dimethoxy benzoyl) 2; 4; 4-trimethylammonium-amyl group phosphine oxide, 2-hydroxyl-methyl-2-methyl-phenyl-propane-1-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone, 1-hydroxyl-cyclohexyl-phenyl-ketone, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino propane-1-ketone etc.
Coating is formed
Transparent coating forms total solid component concentration with coating preferably in the scope of 30～70 weight %, more preferably in the scope of 40～65 weight %.
When transparent coating forms total solid component concentration with coating less than 30 weight %,, also can easily obtain stable coating fluid even not according to the present invention; Even can access; Sometimes also being difficult to utilize 1 coating to obtain thickness is the above transparent coating of 0.5 μ m, and when repeating coating, repetition drying, the hardness of gained transparent coating and scratch resistance become insufficient; Or mist degree or degraded appearance, or reductions such as productivity, fabrication reliability.
When transparent coating forms total solid component concentration with coating above 70 weight %; According to the time when using; Sometimes the viscosity of coating uprises, coating reduces, or the mist degree of gained transparent coating uprises, or surfaceness becomes big, scratch resistance and becomes insufficient.
Transparent coating form concentration with the silica alumina particulate in the coating in solid state component in the scope of 3～56 weight %, more preferably in the scope of 6～39 weight %.
Transparent coating forms concentration with the silica alumina particulate in the coating in solid state component during less than 3 weight %, can not get cooperating with the raising of the adaptation of base material, film toughness, scratch resistance etc. the effect of silica-based fine particles sometimes.
When transparent coating forms concentration with the silica alumina particulate in the coating and surpasses 56 weight % in solid state component, owing to matrix components is few, so become insufficient with adaptation, film toughness, the scratch resistance of base material sometimes.
Then, transparent coating forms with the concentration of the formation of the matrix in coating composition preferred in the scope of 6～63 weight %, more preferably in the scope of 16～55 weight % in solid state component.
Mean that matrix forms composition and contains above-mentioned polyfunctional acrylic ester resin, multifunctional silicone resin and following silicone based stain control agent, even paint here.
Transparent coating form form composition with the matrix in the coating concentration in solid state component during, owing to matrix components is few, so become insufficient with adaptation, film toughness, the scratch resistance of base material sometimes less than 6 weight %.
Transparent coating form form composition with the matrix in the coating concentration in solid state component during above 63 weight %, become insufficient with the adaptation of base material, film toughness, scratch resistance etc. sometimes.
Transparent coating form with above-mentioned (1) in the coating have 3 officials can more than the acrylate resin of functional group in the concentration of solid state component preferably in the scope of 6～63 weight %, more preferably in the scope of 16～55 weight %.
Transparent coating form with in the coating have 3 officials can more than the acrylate resin of functional group in the concentration of solid state component during less than 6 weight %, the adaptation of transparent coating and base material, intensity, scratch resistance etc. become insufficient sometimes.
When transparent coating forms with the acrylate resin with functional group that 3 officials can be above in the coating in the concentration of solid state component above 63 weight %; Sometimes become insufficient with the adaptation of base material, film toughness, scratch resistance etc.; Or because the matrix components of (2) and/or (3) is few; So transparent coating cracks, can not get sufficient water-repellancy, grease proofness, anti-fingerprint tack etc.
Transparent coating form with above-mentioned (2) the 2 functional acrylate's resins in the coating and/or 2 officials ability silicone resin in the concentration of solid state component preferably in the scope of 0.6～6.3 weight %, more preferably in the scope of 1.6～5.5 weight %.
When transparent coating forms with 2 functional acrylate's resins in the coating and/or 2 officials ability organosilicon in the concentration of solid state component less than 0.6 weight %; Sometimes on transparent coating, crack; Or with following 1 official can silicone resin combine become insufficient; Water-repellancy, grease proofness, anti-fingerprint tack, chemical proofing etc. become insufficient; In addition, cause the disengaging (be called sometimes and ooze out) that 1 official can silicone resin sometimes, water-repellancy, grease proofness, anti-fingerprint tack, chemical proofing etc. through the time reduce.
Even transparent coating form with 2 functional acrylate's resins in the coating and/or 2 officials can organosilicon in the concentration of solid state component above 6.3 weight %; With 1 official can silicone resin combine can not increase yet; Therefore; Water-repellancy, grease proofness, anti-fingerprint tack, chemical proofing etc. can further not improve, and can not suppress the disengaging (oozing out) of 1 official ability silicone resin.And then, become insufficient with the adaptation of base material, film toughness etc. sometimes.
Transparent coating forms with the concentration of the silicone based stain control agent in the coating preferred in the scope of 0.003～0.7 weight %, more preferably in the scope of 0.008～0.52 weight % in solid state component.
Transparent coating forms concentration with the silicone based stain control agent in the coating in solid state component during less than 0.003 weight %; Though according to the thickness of gained transparent coating and difference, water-repellancy, grease proofness, anti-fingerprint tack, chemical proofing etc. become insufficient sometimes.
Even the concentration that transparent coating forms with the silicone based stain control agent in the coating surpasses 0.7 weight % in solid state component; Water-repellancy, grease proofness, anti-fingerprint tack, chemical proofing etc. also can further not improve, and become insufficient with the adaptation of base material, film toughness etc. sometimes.
And then transparent coating forms with in the coating, preferably contains the even paint of 0.003～0.56 weight % in solid state component, more preferably contains the even paint of 0.008～0.33 weight %.
Transparent coating forms concentration with the even paint in the coating in solid state component during less than 0.003 weight %, and generation defective etc. except that the appearance degradation of gained transparent coating, can not get sufficient scratch resistance sometimes.
Even the concentration that transparent coating forms with the even paint in the coating surpasses 0.56 weight % in solid state component, outward appearance can further not improve yet, and film toughness becomes insufficient sometimes.
The formation method of using above-mentioned transparent coating to form the transparent coating of coating is described below; Promptly; Can use pickling process, spray method, spin-coating method, rolling method, rod to be coated with known method such as method, woodburytype, nick version print process is coated on the base material; Make its curing through usual methods such as drying, uviolizing, heat treated, form transparent coating thus.
Gained has the thickness of transparent coating of base material of transparent coating preferably in the scope of 0.5～20 μ m.
[base material that has transparent coating]
The base material that has transparent coating of the present invention is formed by base material and the transparent coating that is formed on the base material, it is characterized in that this transparent coating uses above-mentioned transparent coating to form and forms with coating fluid.
Base material
Base material as the present invention uses can especially restrictedly not use known material, can enumerate plastics sheets such as glass, polycarbonate, vinyl resin, PET, TAC, plastic film etc., plastic front board etc.Wherein, can preferably use the resene base material.
Transparent epithelium
Transparent coating is formed by silica alumina particulate and matrix components.
The silica alumina particulate
The content of the silica alumina particulate in the transparent coating is in solid state component, preferably in the scope of 10～80 weight %, more preferably in the scope of 15～60 weight %.
The content of the silica alumina particulate in the transparent coating is in solid state component during less than 10 weight %, becomes insufficient with the adaptation of base material, film toughness, scratch resistance etc. sometimes.
Even the content of the silica alumina particulate in the transparent coating surpasses 80 weight % in solid state component, because matrix components is few, therefore, adaptation, film toughness, the scratch resistance with base material becomes insufficient sometimes.
Matrix components
As matrix components, can use above-mentioned silicone based matrix components, organic resin matrix components.Need to prove that organic resin matrix forms composition curing in transparent coating.
The organic resin matrix components preferably contains above-mentioned polyfunctional acrylic ester.
As polyfunctional acrylic ester, can preferably use above-mentioned polyfunctional acrylic ester.
As the polyfunctional acrylic ester resin, can enumerate acrylate resin, (2) 2 functional acrylate's resins and/or 2 officials ability silicone resin that above-mentioned (1) has the above functional group of 3 officials ability.
The content of the matrix components in the transparent coating is preferred in the scope of 20～90 weight %, more preferably in the scope of 40～85 weight % in solid state component.
Not in above-mentioned scope the time, adaptation, film toughness, the scratch resistance with base material becomes insufficient to the content of the matrix components in the transparent coating sometimes in solid state component.
It is preferred in the scope of 20～90 weight %, more preferably in the scope of 40～80 weight % in solid state component that (1) in the transparent coating has the content of organic resin of the functional group that 3 officials can be above.
During less than 20 weight %, the adaptation of transparent coating and base material, intensity, scratch resistance etc. become insufficient to the content of organic resin that (1) in the transparent coating has a functional group that 3 officials can be above sometimes in solid state component.
When the content that (1) in the transparent coating has an organic resin of the functional group that 3 officials can be above surpasses 90 weight % in solid state component; The matrix components of following (2) and/or (3) is few; Therefore, can not get sufficient water-repellancy, grease proofness, anti-fingerprint tack etc. sometimes.
Then, the content of 2 officials of (2) in transparent coating ability organic resin and/or 2 officials ability silicone resin is preferred in the scope of 2～9 weight %, more preferably in the scope of 4～8.5 weight % in solid state component.
In the transparent coating (2) 2 officials can organic resin and/or 2 officials can silicone resin content in solid state component during less than 2 weight %; Sometimes with following (3) 1 officials can silicone resin combine become insufficient; Water-repellancy, grease proofness, anti-fingerprint tack, chemical proofing etc. become insufficient; In addition; Contain 1 official can silicone resin the time, cause the disengaging (be called sometimes and ooze out) that 1 official can silicone resin, sometimes water-repellancy, grease proofness, anti-fingerprint tack, chemical proofing etc. through the time reduce.
(2) in the transparent coating are even the content of 2 officials ability organic resin and/or 2 officials ability silicone resin surpasses 9 weight % in solid state component; With (3) 1 officials can silicone resin combine can not increase yet; Therefore; Water-repellancy, grease proofness, anti-fingerprint tack, chemical proofing etc. can further not improve, and also can not suppress the disengaging (oozing out) of 1 official ability silicone resin.And then, become insufficient with the adaptation of base material, film toughness etc. sometimes.
Above-mentioned (3) the 1 officials ability of preferred use silicone resin is as silicone based stain control agent in the transparent coating.
The content of 1 official of (3) in transparent coating ability silicone resin (silicone based stain control agent) is preferred in the scope of 0.01～1 weight %, more preferably in the scope of 0.02～0.8 weight % in solid state component.
1 official in the transparent coating can silicone resin content in solid state component during less than 0.01 weight %, though according to the thickness of transparent coating and difference, water-repellancy, grease proofness, anti-fingerprint tack, chemical proofing etc. become insufficient sometimes.
When the content of the 1 official ability silicone resin in the transparent coating surpasses 1 weight % in solid state component; Water-repellancy, grease proofness, anti-fingerprint tack, chemical proofing etc. also can further not improve, and become insufficient with the adaptation of base material, film toughness etc. sometimes.
And then, can use above-mentioned even paint in the transparent coating.
The content of the even paint in the transparent coating is preferred in the scope of 0.01～0.8 weight %, more preferably in the scope of 0.02～0.5 weight % in solid state component.
The content of the even paint in the transparent coating is in solid state component during less than 0.01 weight %, though according to the thickness of transparent coating and difference produces defective etc., in addition the appearance degradation of transparent coating, can not get sufficient scratch resistance sometimes.
When the content of the even paint in the transparent coating surpassed 0.8 weight % in solid state component, outward appearance can further not improve yet, and film toughness becomes insufficient sometimes.
The thickness of transparent coating is preferably in the scope of 0.5～20 μ m.
The thickness of transparent coating can not get sufficient scratch resistance during less than 0.5 μ m sometimes.
When the thickness of transparent coating surpasses 20 μ m,, become insufficient with the adaptation of base material sometimes because the contraction generation crimping of film.
Embodiment
Below, specify the present invention based on embodiment.But the present invention is not limited to the scope of said embodiment record.
[embodiment 1]
The preparation of silicon-aluminum sol (1)
To with SiO 2The concentration of meter is the sodium silicate aqueous solution (SiO of 24 weight % 2/ Na 2O mol ratio 3.1) add pure water in, preparation is with SiO 2The concentration of meter is the dilution sodium silicate aqueous solution of 1.2 weight %.
In addition, with Zeo-karb to SiO 2The concentration of meter is the sodium silicate aqueous solution (SiO of 5 weight % 2/ Na 2O mol ratio 3.1) carry out dealkalize, preparation acidic silicic acid liquid is (with SiO 2The concentration of meter is 4.8 weight %, pH2.8).
Then, be to mix 166kg acidic silicic acid liquid in the dilution sodium silicate aqueous solution of 1.2 weight % to 601kg concentration (with SiO 2The concentration of meter is 4.8 weight %, pH2.8), 79 ℃ of following slakings 30 minutes, preparation kind of particle dispersion.
Then, Yi Bian stir the seed particles dispersion liquid, Yi Bian to wherein simultaneously adding 5135kg acidic silicic acid liquid continuously (with SiO 2The meter concentration be 4.8 weight %, pH2.8) with 185kg with Al 2O 3The concentration of meter is the sodium aluminate aqueous solution 15 hours of 0.6 weight %.
Then, with the ultra-filtration membrane washing, concentrate, preparation is with SiO 2Al 2O 3The concentration of meter is silica alumina particulate (1) aqueous dispersions of 30 weight %.
The pH of silica alumina particulate (1) aqueous dispersions is 9.1.In addition, the median size in the silica alumina particulate (1) is 12nm, Al 2O 3Content is 0.10 weight %, Na 2O content is 0.5 weight %.In addition, ionic concn counts 1 with the ion that is present in the silica alumina particulate (1), 500ppm, and the surface negative charge amount is 2.2 μ eq/m 2
Then, to SiO 2Al 2O 3Meter concentration is to add Zeo-karb (Mitsubishi Chemical's (strain) system: SK-1BH), become 2.0 to the pH of dispersion liquid, then the isolating ions exchange resin among silica alumina particulate (1) the aqueous dispersions 600kg of 30 weight %.(step (a1))
Then, add anionite-exchange resin (Mitsubishi Chemical's (strain) system: SA-20A), become 5.0 to the pH of dispersion liquid, isolating ions exchange resin then, preparation is with SiO 2Al 2O 3The concentration of meter is silica alumina particulate (1) aqueous dispersions of 27 weight %.(step (a2))
The specific surface area of the silica alumina particulate (1) of gained is 260m here 2/ g, the surface negative charge amount is 0.3 μ eq/m 2, Al 2O 3Content is 0.07 weight %, Na 2O content is 0.02 weight %.In addition, ionic concn is counted 100ppm with the ion that is present in the silica alumina particulate (1).
Then, be diluted to SiO 2Al 2O 3After the concentration of meter is 20 weight %, use ultrafiltrationmembrane process that the solvent exchange of 2000g silica alumina particulate (1) aqueous dispersions is methyl alcohol, preparation is with SiO 2Al 2O 3Meter concentration is the pure dispersion liquid of silica alumina particulate (1) of 20 weight %.(step (b))
The content of the water in the pure dispersion liquid of silica alumina particulate (1) is 0.5 weight %.
The mensuration of the negative charge amount of silica alumina particulate
It is 0.5 weight % (this moment, pH was 6.5) that the pure dispersion liquid of silica alumina particulate (1) of concentration 20 weight % is diluted to solid component concentration, measures the surface negative charge amount of silica alumina particulate (1), and the result is shown in the table.
Then, the pure dispersion liquid of 2000g silica alumina particulate (1) is adjusted to 25 ℃, to γ-(methyl) acryloxy propyl trimethoxy silicane (SHIN-ETSU HANTOTAI's chemistry (strain) system: KBM-503) 60g ((M that wherein adds as silicoorganic compound OC)=0.24 mole is with R 1-SiO (3)/2Count 3 weight %)).(step (c))
Then, stirred the pure dispersion liquid of silica alumina particulate (1) 0.5 hour down, make silicoorganic compound absorption at 25 ℃.(step (d))
Then, in the pure dispersion liquid of silica alumina particulate (1), adding 1.5g is ammoniacal liquor and the 7.8g pure water (8.78g water (mole number (M of 28 weight % in ammonia concentration H2O)=0.49, mol ratio (M H2O)/(M OC)=1.96): 0.42g ammonia (mole number (M NH3)=0.025, mol ratio (M NH3)/(M OC)=0.1).(step (e))
Then, dispersion liquid is adjusted to 50 ℃, slaking 19 hours.(step (f))
The mensuration of the negative charge amount of surface treatment silica alumina particulate
In the pure dispersion liquid of silica alumina particulate (1) of slaking gained, add entry, be diluted to solid component concentration 0.5 weight %.The pH of the dispersion liquid of this moment is 7.0.Use this dispersion liquid, measure the surface negative charge amount of surface treatment silica alumina particulate (1), the result is shown in the table.
Then, use the solvent exchange of the dispersion liquid that distillation method obtains slaking to be MIBK, concentrate simultaneously, the preparation solid component concentration is the silicon-aluminum sol (1) of 40 weight %.(step (g)) (step (h))
The viscosity of silicon-aluminum sol (1) is 5cp, and stability is 5 days.
Need to prove that the accelerated test below the stability of colloidal sol is used is measured.
Silicon-aluminum sol is left standstill under 90 ℃, use viscometer (eastern machine industry (strain) system: the BL type) measure to viscosity and surpass 10, the time of 000cp simultaneously.
Transparent coating forms the preparation with coating (1)
With 53g as 3 officials can be above organic resin 6 functional acrylate's resin dipentaerythritol acrylates (common prosperity company chemistry (strain) system: Lightacrylate DPE-6A), 5.9g as 2 officials can organic resin 1; The 6-hexanediyl ester (Japanese chemical drug (strain) system: Kayarad KS-HDDA), 0.4g as 1 official can silicone resin the acrylate-based silicone oil of single terminal methyl group (SHIN-ETSU HANTOTAI's chemical industry (strain) system: X-22-174DX), 75.5g propylene glycol monomethyl ether and 3.5g Photoepolymerizationinitiater initiater 2; 4; (BAS Japan (strain) system: Lucirin TPO) mix, the matrix of preparation solid component concentration 44 weight % forms composition solution (1) to 6-Three methyl Benzene formyl diphenyl phosphine oxide.
Then; With the 30.0g solid component concentration be the matrix of 44 weight % to form composition solution (1) and 30.0g solid component concentration be carrying out surface-treated silicon-aluminum sol (1) with silicoorganic compound and mixing of 40 weight %, the preparation solid component concentration is that the transparent coating formation of 42 weight % is with coating fluid (1).
The viscosity that transparent coating forms with coating fluid (1) is 3cp.And the stability that transparent coating forms with coating fluid (1) is 5 days.Need to prove that the accelerated test below the stability of coating fluid is used is measured.
Coating fluid is left standstill under 90 ℃, use viscometer (eastern machine industry (strain) system: the BL type) measure to viscosity and surpass 5, the time of 000cp simultaneously.
Have the manufacturing of the base material (1) of transparent coating
Use rod to be coated with method (excellent #12); At easy bonding PET film (Japan's spinning: Cosmoshine A-4300; Thick 188 μ m, total light penetration 92.0%, mist degree 0.7%) go up the formation of coating transparent coating with coating fluid (1); Drying is after 1 minute down at 80 ℃, and use is equipped with UV irradiation equipment (the Japanese battery system: UV irradiating unit CS30L21-3) with 600mJ/cm of high pressure mercury vapour lamp (120W/cm) 2Irradiation is solidified it, and preparation has the base material (1) of transparent coating.The thickness of the transparent coating of this moment is 5 μ m.
(Japanese electric look (strain) system: NDH-2000) the total light penetration and the mist degree of mensuration gained transparent coating, the result is shown in the table to use haze meter.
And then, estimating pencil hardness, scratch resistance, adaptation with following method and metewand, the result is shown in the table.
The mensuration of pencil hardness
Measure according to JIS-K-5400, use pencil hardness test device.
Need to prove; Even transparent coating of the present invention forms and uses coating also is stable coating fluid as high density, therefore, even filming of formation is exposed to high temperature following time in drying step; Also can suppress instabilityization; Fine and close transparent coating can be formed, therefore, the high transparent coating of pencil hardness can be obtained.That is, pencil hardness can be used as the stability indicator of coating.
The mensuration of scratch resistance
Use the #0000 steel wool, at load 500g/cm 2Lower slip 50 times, the surface of visual observation film is estimated with following benchmark, and the result is shown in the table.
Do not observe the scar of rib strip shaped: ◎
Observe the scar of a small amount of rib strip shaped: zero
Observe the scar of many rib strip shapeds: △
Pruned by integral body in the surface: *
Adaptation
On the surface that has the base material of transparent coating (1), give 11 parallel scars with cutter with the interval of 1mm in length and breadth; Make 100 grids; Bonding above that Cellophane tape (registered trademark); Then, tunicle is not stripped from and the quantity of residual grid is divided into following 4 stages through will peel off Cellophane tape (registered trademark) time, estimates adaptation.The result is shown in the table.
The quantity of residual grid is more than 95: ◎
The quantity of residual grid is 90～94: zero
The quantity of residual grid is 85～89: △
The quantity of residual grid is below 84: *
Outward appearance
For the base material that has transparent coating (1), visual observation depression and film are uneven, estimate according to following benchmark.
It is uneven not observe depression and film: ◎
It is uneven to observe depression and film a little: zero
It is uneven to observe depression and film significantly: △
It is uneven to observe a lot of depressions and film: *
[embodiment 2]
The preparation of silicon-aluminum sol (2)
Likewise prepare the seed particles dispersion liquid with embodiment 1.
Then, Yi Bian stir the seed particles dispersion liquid, Yi Bian to wherein simultaneously and add 5042.5kg acidic silicic acid liquid continuously (with SiO 2The meter concentration be 4.8 weight %, pH is 2.8) and 924.3kg with Al 2O 3The concentration of meter is the sodium aluminate aqueous solution 15 hours of 0.6 weight %.
Then, with ultra-filtration membrane washing, concentrated, preparation is with SiO 2Al 2O 3The concentration of meter is silica alumina particulate (2) aqueous dispersions of 30 weight %.
The pH of silica alumina particulate (2) aqueous dispersions is 9.1.In addition, the median size in the silica alumina particulate (2) is 12nm, Al 2O 3Content is 0.50 weight %, Na 2O content is 0.5 weight %.In addition, ionic concn counts 1 with the ion that is present in the silica alumina particulate (2), 550ppm, and the surface negative charge amount is 2.8 μ eq/m 2
Then, to 600kg with SiO 2Al 2O 3The concentration of meter be add in silica alumina particulate (2) aqueous dispersions of 30 weight % Zeo-karb (Mitsubishi Chemical's (strain) system: SK-1BH), become 2.0 to the pH of dispersion liquid, then, the isolating ions exchange resin.(step (a1))
Then, add anionite-exchange resin (Mitsubishi Chemical's (strain) system: SA-20A), become 5.0 to the pH of dispersion liquid, then, the isolating ions exchange resin, preparation is with SiO 2Al 2O 3The concentration of meter is silica alumina particulate (2) aqueous dispersions of 27 weight %.(step (a2))
The specific surface area of the silica alumina particulate (1) that here obtains is 269m 2/ g, the surface negative charge amount is 0.6 μ eq/m 2, Al 2O 3Content is 0.41 weight %, Na 2O content is 0.04 weight %.In addition, ionic concn is 120ppm in silica alumina particulate (1).
Then, be diluted to SiO 2Al 2O 3After the concentration of meter is 20 weight %, use ultrafiltrationmembrane process that the solvent exchange of 2000g silica alumina particulate (2) aqueous dispersions is methyl alcohol, preparation is with SiO 2Al 2O 3The concentration of meter is the pure dispersion liquid of silica alumina particulate (2) of 20 weight %.(step (b))
The content of the water in the pure dispersion liquid of silica alumina particulate (2) is 0.5 weight %.
Likewise measure the surface negative charge amount of silica alumina particulate (2) with embodiment 1, the result is shown in the table.
Then, pure dispersion liquid 2000g is adjusted to 25 ℃ with silica alumina particulate (2), to γ-(methyl) acryloxy propyl trimethoxy silicane (SHIN-ETSU HANTOTAI's chemistry (strain) system: KBM-503) 60g ((M that wherein adds as silicoorganic compound OC)=0.24 mole is with R 1-SiO (3)/2Count 3 weight %)).(step (c))
Then, stirred the pure dispersion liquid of silica alumina particulate (2) 0.5 hour down, make silicoorganic compound absorption at 25 ℃.(step (d))
Then, in the pure dispersion liquid of silica alumina particulate (2), adding 1.5g is ammoniacal liquor and the 7.8g pure water (8.78g water (mole number (M of 28 weight % in the concentration of ammonia H2O)=0.49, mol ratio (M H2O)/(M OC)=1.96): 0.42g ammonia (mole number (M NH3)=0.025, mol ratio (M NH3)/(M OC)=0.1).(step (e))
Then, dispersion liquid is adjusted to 50 ℃, slaking 19 hours.(step (f))
Then, likewise measure the surface negative charge amount of surface treatment silica alumina particulate (2) with embodiment 1, the result is shown in the table.
Then, use distillation method that solvent exchange is MIBK, concentrate simultaneously, the preparation solid component concentration is the silicon-aluminum sol (2) of 40 weight %.(step (g)) (step (h))
The viscosity of silicon-aluminum sol (2) is 5cp, and stability is 6 days.
Transparent coating forms the preparation with coating (2)
Except that in embodiment 1, using solid component concentration is the silicon-aluminum sol (2) of 40 weight %, and the transparent coating that likewise prepares solid component concentration and be 42 weight % forms with coating fluid (2).
The viscosity that transparent coating forms with coating fluid (2) is 5cp, and stability is 5 days.
Have the manufacturing of the base material (2) of transparent coating
Except that in embodiment 1, using transparent coating to form with the coating fluid (2), preparation likewise has the base material (2) of transparent coating.The thickness of the transparent coating of this moment is 5 μ m.
Measure total light penetration, mist degree, pencil hardness, scratch resistance, the adaptation of gained transparent coating, the result is shown in the table.
[embodiment 3]
The preparation of silicon-aluminum sol (3)
Likewise prepare the seed particles dispersion liquid with embodiment 1.
Then, Yi Bian stir the seed particles dispersion liquid, Yi Bian to wherein simultaneously and add 4580kg acidic silicic acid liquid continuously (with SiO 2The meter concentration be 4.8 weight %, pH2.8) with 4621.7kg with Al 2O 3The concentration of meter is the sodium aluminate aqueous solution 15 hours of 0.6 weight %.
Then, with ultra-filtration membrane washing, concentrated, preparation is with SiO 2Al 2O 3The concentration of meter is silica alumina particulate (3) aqueous dispersions of 30 weight %.
The pH of silica alumina particulate (3) aqueous dispersions is 9.1.In addition, the median size in the silica alumina particulate (3) is 13nm, Al 2O 3Content is 2.50 weight %, Na 2O content is 0.6 weight %.In addition, ionic concn is counted 1700ppm with the ion that is present in the silica alumina particulate (3), and the surface negative charge amount is 3.1 μ eq/m 2
Then, to 600kg with SiO 2Al 2O 3The concentration of meter be add in silica alumina particulate (3) aqueous dispersions of 30 weight % Zeo-karb (Mitsubishi Chemical's (strain) system: SK-1BH), become 2.0 to the pH of dispersion liquid, then, the isolating ions exchange resin.(step (a1))
Then, add anionite-exchange resin (Mitsubishi Chemical's (strain) system: SA-20A), become 5.0 to the pH of dispersion liquid, isolating ions exchange resin then, preparation is with SiO 2Al 2O 3The concentration of meter is silica alumina particulate (3) aqueous dispersions of 27 weight %.(step (a2))
The specific surface area of the silica alumina particulate (3) that here obtains is 282m 2/ g, the surface negative charge amount is 0.8 μ eq/m 2, Al 2O 3Content is 1.9 weight %, Na 2O content is 0.05 weight %.In addition, ionic concn is 115ppm in silica alumina particulate (3).
Then, be diluted to SiO 2Al 2O 3The concentration of meter is 20 weight %, uses ultrafiltrationmembrane process afterwards, is methyl alcohol with the solvent exchange of 2000g silica alumina particulate (3) aqueous dispersions, and preparation is with SiO 2Al 2O 3The concentration of meter is the pure dispersion liquid of silica alumina particulate (3) of 20 weight %.(step (b))
The content of the water in the pure dispersion liquid of silica alumina particulate (3) is 0.5 weight %.
Likewise measure the surface negative charge amount of silica alumina particulate (3) with embodiment 1, the result is shown in the table.
Then, the pure dispersion liquid of 2000g silica alumina particulate (3) is adjusted to 25 ℃, to γ-(methyl) acryloxy propyl trimethoxy silicane (SHIN-ETSU HANTOTAI's chemistry (strain) system: KBM-503) 60g ((M that wherein adds as silicoorganic compound OC)=0.24 mole is with R 1-SiO (3)/2Count 3 weight %)).(step (c))
Then, stirred the pure dispersion liquid of silica alumina particulate (3) 0.5 hour down, make silicoorganic compound absorption at 25 ℃.(step (d))
Then, in the pure dispersion liquid of silica alumina particulate (3), adding 1.5g is ammoniacal liquor and the 7.8g pure water (8.78g water (mole number (M of 28 weight % in ammonia concentration H2O)=0.49, mol ratio (M H2O)/(M OC)=1.96): 0.42g ammonia (mole number (M NH3)=0.025, mol ratio (M NH3)/(M OC)=0.1).(step (e))
Then, dispersion liquid is adjusted to 50 ℃, slaking 19 hours.(step (f))
Then, likewise measure the surface negative charge amount of surface treatment silica alumina particulate (3) with embodiment 1, the result is shown in the table.
Then, use distillation method that solvent exchange is MIBK, concentrate simultaneously, the preparation solid component concentration is the silicon-aluminum sol (3) of 40 weight %.(step (g)) (step (h))
The viscosity of silicon-aluminum sol (3) is 7cp, and stability is 6.5 days.
Transparent coating forms the preparation with coating (3)
Except that in embodiment 1, using solid component concentration is the silicon-aluminum sol (3) of 40 weight %, and the transparent coating that likewise prepares solid component concentration and be 42 weight % forms with coating fluid (3).
The viscosity that transparent coating forms with coating fluid (3) is 8cp, and stability is 6 days.
Have the manufacturing of the base material (3) of transparent coating
Except that in embodiment 1, using transparent coating to form with the coating fluid (3), preparation likewise has the base material (3) of transparent coating.The thickness of the transparent coating of this moment is 5 μ m.
Measure total light penetration, mist degree, pencil hardness, scratch resistance, the adaptation of gained transparent coating, the result is shown in the table.
[embodiment 4]
The preparation of silicon-aluminum sol (4)
Likewise prepare the seed particles dispersion liquid with embodiment 1.
Then, Yi Bian stir the seed particles dispersion liquid, Yi Bian to wherein simultaneously and add 25 continuously, 650kg acidic silicic acid liquid is (with SiO 2The meter concentration be 4.8 weight %, pH2.8) with 919kg with Al 2O 3The concentration of meter is the sodium aluminate aqueous solution 15 hours of 0.6 weight %.
Then, with ultra-filtration membrane washing, concentrated, preparation is with SiO 2Al 2O 3The concentration of meter is silica alumina particulate (4) aqueous dispersions of 30 weight %.
The pH of silica alumina particulate (4) aqueous dispersions is 9.1.In addition, the median size in the silica alumina particulate (4) is 25nm, Al 2O 3Content is 0.10 weight %, Na 2O content is 0.9 weight %.In addition, ionic concn is counted 2400ppm with the ion that is present in the silica alumina particulate (4), and the surface negative charge amount is 3.3 μ eq/m 2
Then, to 600kg with SiO 2Al 2O 3The concentration of meter be add in silica alumina particulate (4) aqueous dispersions of 30 weight % Zeo-karb (Mitsubishi Chemical's (strain) system: SK-1BH), become 2.0 to the pH of dispersion liquid, then, the isolating ions exchange resin.(step (a1))
Then, add anionite-exchange resin (Mitsubishi Chemical's (strain) system: SA-20A), become 5.0 to the pH of dispersion liquid, isolating ions exchange resin then, preparation is with SiO 2Al 2O 3The concentration of meter is silica alumina particulate (4) aqueous dispersions of 27 weight %.(step (a2))
The specific surface area of the silica alumina particulate (4) that here obtains is 120m 2/ g, the surface negative charge amount is 0.2 μ eq/m 2, Al 2O 3Content is 0.07 weight %, Na 2O content is 0.02 weight %.In addition, ionic concn is 230ppm in silica alumina particulate (4).
Then, be diluted to SiO 2Al 2O 3The concentration of meter is 20 weight %, uses ultrafiltrationmembrane process that the solvent exchange of 2000g silica alumina particulate (4) aqueous dispersions is methyl alcohol afterwards, and preparation is with SiO 2Al 2O 3The concentration of meter is the pure dispersion liquid of silica alumina particulate (4) of 20 weight %.(step (b))
The content of the water in the pure dispersion liquid of silica alumina particulate (4) is 0.5 weight %.
Likewise measure the surface negative charge amount of silica alumina particulate (4) with embodiment 1, the result is shown in the table.
Then, the pure dispersion liquid of 2000g silica alumina particulate (4) is adjusted to 25 ℃, to γ-(methyl) acryloxy propyl trimethoxy silicane (SHIN-ETSU HANTOTAI's chemistry (strain) system: KBM-503) 60g ((M that wherein adds as silicoorganic compound OC)=0.24 mole is with R 1-SiO (3)/2Count 3 weight %)).(step (c))
Then, stirred the pure dispersion liquid of silica alumina particulate (4) 0.5 hour down, make silicoorganic compound absorption at 25 ℃.(step (d))
Then, in the pure dispersion liquid of silica alumina particulate (4), adding 1.5g is ammoniacal liquor and the 7.8g pure water (8.78g water (mole number (M of 28 weight % in the concentration of ammonia H2O)=0.49, mol ratio (M H2O)/(M OC)=1.96): 0.42g ammonia (mole number (M NH3)=0.025, mol ratio (M NH3)/(M OC)=0.1).(step (e))
Then, dispersion liquid is adjusted to 50 ℃, slaking 19 hours.(step (f))
Then, likewise measure the surface negative charge amount of surface treatment silica alumina particulate (4) with embodiment 1, the result is shown in the table.
Then, use distillation method that solvent exchange is MIBK, concentrate simultaneously, the preparation solid component concentration is the silicon-aluminum sol (4) of 40 weight %.(step (g)) (step (h))
The viscosity of silicon-aluminum sol (4) is 17cp, and stability is 4 days.
Transparent coating forms the preparation with coating (4)
Except that in embodiment 1, using solid component concentration is the silicon-aluminum sol (4) of 40 weight %, and the transparent coating that likewise prepares solid component concentration and be 42 weight % forms with coating fluid (4).
The viscosity that transparent coating forms with coating fluid (4) is 20cp, and stability is 5 days.
Have the manufacturing of the base material (4) of transparent coating
Except that in embodiment 1, using transparent coating to form with the coating fluid (4), preparation likewise has the base material (4) of transparent coating.The thickness of the transparent coating of this moment is 5 μ m.
Measure total light penetration, mist degree, pencil hardness, scratch resistance, the adaptation of gained transparent coating, the result is shown in the table.
[embodiment 5]
The preparation of silicon-aluminum sol (5)
Likewise prepare the seed particles dispersion liquid with embodiment 1.
Then, Yi Bian stir the seed particles dispersion liquid, Yi Bian to wherein simultaneously and add 205 continuously, 200kg acidic silicic acid liquid is (with SiO 2The concentration of meter is 4.8 weight %, and pH2.8) with 7,354kg is with Al 2O 3The concentration of meter is the sodium aluminate aqueous solution 15 hours of 0.6 weight %.
Then, with ultra-filtration membrane washing, concentrated, preparation is with SiO 2Al 2O 3The concentration of meter is silica alumina particulate (5) aqueous dispersions of 30 weight %.
The pH of silica alumina particulate (5) aqueous dispersions is 9.1.In addition, the median size in the silica alumina particulate (5) is 45nm, Al 2O 3Content is 0.10 weight %, Na 2O content is 1.2 weight %.In addition, ionic concn counts 3 with the ion that is present in the silica alumina particulate (5), 600ppm, and the surface negative charge amount is 3.4 μ eq/m 2
Then, to 600kg with SiO 2Al 2O 3The concentration of meter be add in silica alumina particulate (5) aqueous dispersions of 30 weight % Zeo-karb (Mitsubishi Chemical's (strain) system: SK-1BH), become 2.0 to the pH of dispersion liquid, then, the isolating ions exchange resin.(step (a1))
Then, (Mitsubishi Chemical's (strain) system: SA-20A) pH to dispersion liquid becomes 5.0, and the isolating ions exchange resin prepares with SiO then to add anionite-exchange resin 2Al 2O 3The concentration of meter is silica alumina particulate (5) aqueous dispersions of 27 weight %.(step (a2))
The specific surface area of the silica alumina particulate (5) of gained is 68m here 2/ g, the surface negative charge amount is 0.1 μ eq/m 2, Al 2O 3Content is 0.09 weight %, Na 2O content is 0.23 weight %.In addition, ionic concn is 380ppm in silica alumina particulate (5).
Then, be diluted to SiO 2Al 2O 3The concentration of meter is 20 weight %, uses ultrafiltrationmembrane process afterwards, is methyl alcohol with the solvent exchange of 2000g silica alumina particulate (5) aqueous dispersions, and preparation is with SiO 2Al 2O 3The concentration of meter is the pure dispersion liquid of silica alumina particulate (5) of 20 weight %.(step (b))
The content of the water in the pure dispersion liquid of silica alumina particulate (5) is 0.5 weight %.
Likewise measure the surface negative charge amount of silica alumina particulate (5) with embodiment 1, the result is shown in the table.
Then, the pure dispersion liquid of 2000g silica alumina particulate (5) is adjusted to 25 ℃, to γ-(methyl) acryloxy propyl trimethoxy silicane (SHIN-ETSU HANTOTAI's chemistry (strain) system: KBM-503) 60g ((M that wherein adds as silicoorganic compound OC)=0.24 mole: with R 1-SiO (3)/2Count 3 weight %)).(step (c))
Then, stirred the pure dispersion liquid of silica alumina particulate (5) 0.5 hour down, make silicoorganic compound absorption at 25 ℃.(step (d))
Then, in the pure dispersion liquid of silica alumina particulate (5), adding 1.5g is ammoniacal liquor and the 7.8g pure water (8.78g water (mole number (M of 28 weight % in ammonia concentration H2O)=0.49, mol ratio (M H2O)/(M OC)=1.96): 0.42g ammonia (mole number (M NH3)=0.025, mol ratio (M NH3)/(M OC)=0.1).(step (e))
Then, dispersion liquid is adjusted to 50 ℃, slaking 19 hours.(step (f))
Then, likewise measure the surface negative charge amount of surface treatment silica alumina particulate (5) with embodiment 1, the result is shown in the table.
Then, use distillation method that solvent exchange is MIBK, concentrate simultaneously, the preparation solid component concentration is the silicon-aluminum sol (5) of 40 weight %.(step (g)) (step (h))
The viscosity of silicon-aluminum sol (5) is 25cp, and stability is 3 days.
Transparent coating forms the preparation with coating (5)
Except that in embodiment 1, using solid component concentration is the silicon-aluminum sol (5) of 40 weight %, and the transparent coating that likewise prepares solid component concentration and be 42 weight % forms with coating fluid (5).
The viscosity that transparent coating forms with coating fluid (5) is 32cp, and stability is 5 days.
Have the manufacturing of the base material (5) of transparent coating
Except that in embodiment 1, using transparent coating to form with the coating fluid (5), preparation likewise has the base material (5) of transparent coating.The thickness of the transparent coating of this moment is 5 μ m.
Measure total light penetration, mist degree, pencil hardness, scratch resistance, the adaptation of gained transparent coating, the result is shown in the table.
[embodiment 6]
The preparation of silicon-aluminum sol (6)
In embodiment 1, use distillation method that solvent exchange is MIBK, concentrate simultaneously, the preparation solid component concentration is the silicon-aluminum sol (6) of 60 weight %.(step (g)) (step (h))
The viscosity of silicon-aluminum sol (6) is 120cp, and stability is 3 days.
Transparent coating forms the preparation with coating (6)
With 53g as 3 officials can be above organic resin 4 functional acrylate's resin tetramethylol methane tetraacrylates (common prosperity society chemistry (strain) system: Lightacrylate PE-4A), 5.9g as 2 officials can organic resin 1; The 6-hexanediyl ester (Japanese chemical drug (strain) system: Kayarad KS-HDDA), 0.4g as 1 official can silicone resin the acrylate-based silicone oil of a terminal methyl (SHIN-ETSU HANTOTAI's chemical industry (strain) system: X-22-174DX), 33.4g propylene glycol monomethyl ether and 3.5g Photoepolymerizationinitiater initiater 2; 4; (BAS Japan (strain) system: Lucirin TPO) mix, the preparation solid component concentration is that the matrix of 64 weight % forms composition solution (2) to 6-Three methyl Benzene formyl diphenyl phosphine oxide.
Then; With the 30.0g solid component concentration be the matrix of 64 weight % to form composition solution (2) and 30.0g solid component concentration be carrying out surface-treated silicon-aluminum sol (6) with silicoorganic compound and mixing of 60 weight %, the preparation solid component concentration is that the transparent coating formation of 62 weight % is with coating fluid (6).
The viscosity that transparent coating forms with coating fluid (6) is 110cp, and stability is 3 days.
Have the manufacturing of the base material (6) of transparent coating
Use rod to be coated with method (excellent #10); At easy bonding PET film (Japan's spinning: Cosmoshine A-4300; Thick 188 μ m, total light penetration 92.0%, mist degree 0.7%) go up the formation of coating transparent coating with coating fluid (6); Drying is after 1 minute down at 80 ℃, and use is equipped with UV irradiation equipment (the Japanese battery system: UV irradiating unit CS30L21-3) with 600mJ/cm of high pressure mercury vapour lamp (120W/cm) 2Irradiation is solidified it, and preparation has the base material (6) of transparent coating.The thickness of the transparent coating of this moment is 5 μ m.
[embodiment 7]
The preparation of silicon-aluminum sol (7)
In embodiment 1, use distillation method that solvent exchange is MIBK, concentrate simultaneously, the preparation solid component concentration is the silicon-aluminum sol (7) of 70 weight %.(step (g)) (step (h))
The viscosity of silicon-aluminum sol (7) is 780cp, and stability is 2 days.
Transparent coating forms the preparation with coating (7)
With 53g as 3 officials can be above organic resin 6 functional acrylate's resin dipentaerythritol acrylates (common prosperity society chemistry (strain) system: Lightacrylate DPE-6A), 5.9g as 2 officials can organic resin 1; The 6-hexanediyl ester (Japanese chemical drug (strain) system: Kayarad KS-HDDA), 0.4g as 1 official can silicone resin the acrylate-based silicone oil of a terminal methyl (SHIN-ETSU HANTOTAI's chemical industry (strain) system: X-22-174DX), 25.4g propylene glycol monomethyl ether and 3.5g Photoepolymerizationinitiater initiater 2; 4; (BAS Japan (strain) system: Lucirin TPO) mix, the preparation solid component concentration is that the matrix of 74 weight % forms composition solution (3) to 6-Three methyl Benzene formyl diphenyl phosphine oxide.
Then; With the 30.0g solid component concentration be the matrix of 74 weight % to form composition solution (3) and 30.0g solid component concentration be carrying out surface-treated silicon-aluminum sol (7) with silicoorganic compound and mixing of 70 weight %, the preparation solid component concentration is that the transparent coating formation of 72 weight % is with coating fluid (7).
The viscosity that transparent coating forms with coating fluid (7) is 960cp, and stability is 1 day.
Have the manufacturing of the base material (7) of transparent coating
Use rod to be coated with method (excellent #9); At easy bonding PET film (Japan's spinning: Cosmoshine A-4300; Thick 188 μ m, total light penetration 92.0%, mist degree 0.7%) go up the formation of coating transparent coating with coating fluid (7); Drying is after 1 minute down at 80 ℃, and use is equipped with UV irradiation equipment (the Japanese battery system: UV irradiating unit CS30L21-3) with 600mJ/cm of high pressure mercury vapour lamp (120W/cm) 2Shine, it is solidified, preparation has the base material (7) of transparent coating.The thickness of the transparent coating of this moment is 5 μ m.
[embodiment 8]
Transparent coating forms the preparation with coating (8)
In embodiment 1, (nanmu originally changes into (strain) system: Disparlon # 1711), in addition, likewise preparing solid component concentration is the matrix formation composition solution (4) of 44 weight % as the even paint of the special silicon class of even paint further to mix 0.2g.
Then; With the 30.0g solid component concentration be the matrix of 44 weight % to form composition solution (4) and 30.0g and solid component concentration that embodiment 1 likewise prepares be carrying out surface-treated silicon-aluminum sol (1) with silicoorganic compound and mixing of 40 weight %, the transparent coating formation for preparing solid component concentration and be 42 weight % is with coating fluid (8).
The viscosity that transparent coating forms with coating fluid (8) is 3cp.In addition, transparent coating formation is 5 days with the stability of coating fluid (8).
Have the manufacturing of the base material (8) of transparent coating
Except that in embodiment 1, using transparent coating to form with the coating fluid (8), preparation likewise has the base material (8) of transparent coating.The thickness of the transparent coating of this moment is 5 μ m.
Measure total light penetration, mist degree, pencil hardness, scratch resistance, the adaptation of gained transparent coating, the result is shown in the table.
[comparative example 1]
The preparation of silicon-aluminum sol (R1)
Likewise prepare with ultra-filtration membrane washing with embodiment 1, after concentrating as raw material with SiO 2Al 2O 3The concentration of meter is silica alumina particulate (1) aqueous dispersions of 30 weight %.
Then, be diluted to SiO 2Al 2O 3The concentration of meter is 20 weight %, uses ultrafiltrationmembrane process that the solvent exchange of 2000g silica alumina particulate (1) aqueous dispersions is methyl alcohol afterwards, and preparation is with SiO 2Al 2O 3The concentration of meter is the pure dispersion liquid of silica alumina particulate (R1) of 10 weight %.(being equivalent to step (b))
The content of the water in the pure dispersion liquid of silica alumina particulate (R1) is 0.8 weight %.
Likewise measure the surface negative charge amount of silica alumina particulate (R1) with embodiment 1, the result is shown in the table.
Then, the pure dispersion liquid of 2000g silica alumina particulate (R1) is adjusted to 25 ℃, to γ-(methyl) acryloxy propyl trimethoxy silicane (SHIN-ETSU HANTOTAI's chemistry (strain) system: KBM-503) 60g ((M that wherein adds as silicoorganic compound OC)=0.24 mole is with R 1-SiO (3)/2Count 3 weight %)).(being equivalent to step (c))
Then, stirred the pure dispersion liquid of silica alumina particulate (R1) 0.5 hour down, make silicoorganic compound absorption at 25 ℃.(being equivalent to step (d))
Then, in the pure dispersion liquid of silica alumina particulate (R1), adding 1.5g is ammoniacal liquor and the 7.8g pure water (8.78g water (mole number (mole number (M of 28 weight % in ammonia concentration H2O)=0.49, mol ratio (M H2O)/(M OC)=1.96): 0.42g ammonia (mole number (M NH3)=0.025, mol ratio (M NH3)/(M OC)=0.1).(being equivalent to step (e))
Then, dispersion liquid is adjusted to 50 ℃, slaking 19 hours.(being equivalent to step (f))
Then, likewise measure the surface negative charge amount of surface treatment silica alumina particulate (R1) with embodiment 1, the result is shown in the table.
Then, use distillation method that solvent exchange is MIBK, concentrate simultaneously, the preparation solid component concentration is the silicon-aluminum sol (R1) of 40 weight %.(being equivalent to step (g)) (being equivalent to step (h))
The viscosity of silicon-aluminum sol (R1) is 240cp, and stability is 0.5 day.
Transparent coating forms the preparation with coating (R1)
Except that in embodiment 1, using solid component concentration is the silicon-aluminum sol (R1) of 20 weight %, and the transparent coating that likewise prepares solid component concentration and be 42 weight % forms with coating fluid (R1).
The viscosity that transparent coating forms with coating fluid (R1) is 360cp, and stability is 0.5 day.
Have the manufacturing of the base material (R1) of transparent coating
Except that in embodiment 1, using transparent coating to form with the coating fluid (R1), preparation likewise has the base material (R1) of transparent coating.The thickness of the transparent coating of this moment is 5 μ m.
Measure total light penetration, mist degree, pencil hardness, scratch resistance, the adaptation of gained transparent coating, the result is shown in the table.
[comparative example 2]
The preparation of silicon-aluminum sol (R2)
In comparative example 1, add γ-(methyl) acryloxy propyl trimethoxy silicane (SHIN-ETSU HANTOTAI's chemistry (strain) system: KBM-503) 120g ((M as silicoorganic compound OC)=0.48 mole is with R 1-SiO (3)/2Count 6 weight %)).(being equivalent to step (c))
Then, interpolation 1.5g is ammoniacal liquor and the 7.8g pure water (8.78g water (mole number (M of 28 weight % in the concentration of ammonia H2O)=0.49, mol ratio (M H2O)/(M OC)=1.00): 0.42g ammonia (mole number (M NH3)=0.025, mol ratio (M NH3)/(M OC)=0.05) (step (e)) in addition, likewise prepares the silicon-aluminum sol that solid component concentration is 40 weight % (R2).(being equivalent to step (g)) (being equivalent to step (h))
The viscosity of silicon-aluminum sol (R2) is 120cp, and stability is 1 day.
Need to prove, above-mentioned after step (f), likewise measure the surface negative charge amount of surface treatment silica alumina particulate (R2) with embodiment 1, the result is shown in the table.
Transparent coating forms the preparation with coating (R2)
Except that in embodiment 1, using solid component concentration is the silicon-aluminum sol (R2) of 40 weight %, and the transparent coating that likewise prepares solid component concentration and be 42 weight % forms with coating fluid (R2).
The viscosity that transparent coating forms with coating fluid (R2) is 230cp, and stability is 1 day.
Have the manufacturing of the base material (R2) of transparent coating
Except that in embodiment 1, using transparent coating to form with the coating fluid (R2), preparation likewise has the base material (R2) of transparent coating.The thickness of the transparent coating of this moment is 5 μ m.
Measure total light penetration, mist degree, pencil hardness, scratch resistance, the adaptation of gained transparent coating, the result is shown in the table.
[comparative example 3]
The preparation of silicon-aluminum sol (R3)
In embodiment 1, in step (c) afterwards, implement (step (e)) later step immediately, in addition, likewise prepare the silicon-aluminum sol that solid component concentration is 40 weight % (R3).
The viscosity of silicon-aluminum sol (R3) is 8cp, and stability is 4 days.
Need to prove that after the step in above-mentioned (f), likewise measure the surface negative charge amount of surface treatment silica alumina particulate (R3) with embodiment 1, the result is shown in the table.
Transparent coating forms the preparation with coating (R3)
Except that in embodiment 1, using solid component concentration is the silicon-aluminum sol (R3) of 40 weight %, and the transparent coating that likewise prepares solid component concentration and be 42 weight % forms with coating fluid (R3).
The viscosity that transparent coating forms with coating fluid (R3) is 5cp, and stability is 3 days.
Have the manufacturing of the base material (R3) of transparent coating
Except that in embodiment 1, using transparent coating to form with the coating fluid (R3), preparation likewise has the base material (R3) of transparent coating.The thickness of the transparent coating of this moment is 5 μ m.
Measure total light penetration, mist degree, pencil hardness, scratch resistance, the adaptation of gained transparent coating, the result is shown in the table.
[comparative example 4]
The preparation of organic silicon sol (R4)
Silicon sol (is waved catalyst day and changed into (strain) system: CATALOID SI-30, median size: 12nm, SiO 2Concentration 30 weight %, Al in the particle 2O 3Content is 0 weight %, Na 2O content is 0.4 weight %, pH9.3, and ionic concn: the ion to be present in the silicon dioxide microparticle is counted 1300ppm, and the surface negative charge amount is 1.9 μ eq/m 2) be diluted to SiO 2The concentration of meter is 20 weight %, uses ultrafiltrationmembrane process that the solvent exchange of 2000g silicon dioxide microparticle aqueous dispersions is methyl alcohol afterwards, and preparation is with SiO 2Meter concentration is the pure dispersion liquid of silicon dioxide microparticle (R4) of 20 weight %.(being equivalent to step (b))
The content of the water in the pure dispersion liquid of silicon dioxide microparticle (R4) is 0.5 weight %.
Likewise measure the surface negative charge amount of silicon dioxide microparticle (R4) with embodiment 1, the result is shown in the table.
Then, the pure dispersion liquid of 2000g silicon dioxide microparticle (R4) is adjusted to 25 ℃, to γ-(methyl) acryloxy propyl trimethoxy silicane (SHIN-ETSU HANTOTAI's chemistry (strain) system: KBM-503) 60g ((M that wherein adds as silicoorganic compound OC)=0.24 mole is with R 1-SiO (3)/2Count 3 weight %)).(being equivalent to step (c))
Then, stirred the pure dispersion liquid of silicon dioxide microparticle (R4) 0.5 hour down, make silicoorganic compound absorption at 25 ℃.(being equivalent to step (d))
Then, in the pure dispersion liquid of silicon dioxide microparticle (R4), adding 1.5g is ammoniacal liquor and the 7.8g pure water (8.78g water (mole number (M of 28 weight % in ammonia concentration H2O)=0.49, mol ratio (M H2O)/(M OC)=1.96): 0.42g ammonia (mole number (M NH3)=0.025, mol ratio (M NH3)/(M OC)=0.1).(being equivalent to step (e))
Then, dispersion liquid is adjusted to 50 ℃, slaking 19 hours.(being equivalent to step (f))
Then, likewise measure the surface negative charge amount of surface treatment silicon dioxide microparticle (R4) with embodiment 1, the result is shown in the table.
Then, use distillation method that solvent exchange is MIBK, concentrate simultaneously, the preparation solid component concentration is the silicon sol (R4) of 40 weight %.(being equivalent to step (g)) (being equivalent to step (h))
The viscosity of silicon sol (R4) is 360cp, and stability is 0.5 day.
Transparent coating forms the preparation with coating (R4)
Except that in embodiment 1, using solid component concentration is the silicon-aluminum sol (R4) of 40 weight %, and the transparent coating that likewise prepares solid component concentration and be 42 weight % forms with coating fluid (R4).
The viscosity that transparent coating forms with coating fluid (R4) is 450cp, and stability is 0.5 day.
Have the manufacturing of the base material (R4) of transparent coating
Except that in embodiment 1, using transparent coating to form with the coating fluid (R4), preparation likewise has the base material (R4) of transparent coating.The thickness of the transparent coating of this moment is 5 μ m.
Measure total light penetration, mist degree, pencil hardness, scratch resistance, the adaptation of gained transparent coating, the result is shown in the table.
[comparative example 5]
The preparation of organic silicon sol (R5)
Silicon sol (is waved catalyst day and changed into (strain) system: CATALOID SI-30, median size: 12nm, SiO 2Concentration 30 weight %, Al in the particle 2O 3Content is 0 weight %, Na 2O content is 0.4 weight %, pH9.3, and ionic concn: the ion to be present in the silicon dioxide microparticle is counted 1300ppm, and the surface negative charge amount is 1.9 μ eq/m 2) be diluted to SiO 2The concentration of meter is 20 weight %, in 600kg silicon dioxide microparticle (R5) aqueous dispersions, adds Zeo-karb (Mitsubishi Chemical's (strain) system: SK-1BH), become 2.0 to the pH of dispersion liquid, then the isolating ions exchange resin afterwards.(being equivalent to step (a1))
Then, add anionite-exchange resin (Mitsubishi Chemical's (strain) system: SA-20A), become 5.0 to the pH of dispersion liquid, isolating ions exchange resin then, preparation is with SiO 2Meter concentration is silicon dioxide microparticle (R5) aqueous dispersions of 27 weight %.(being equivalent to step (a2))
The specific surface area of the silicon dioxide microparticle of gained (R5) is 251m here 2/ g, the surface negative charge amount is 0.1 μ eq/m 2, Al 2O 3Content is 0 weight %, Na 2O content is 0.02 weight %.In addition, ionic concn is by being scaled 110ppm in the silicon dioxide microparticle (R5).
Then, be diluted to SiO 2The concentration of meter is 20 weight %, uses ultrafiltrationmembrane process that the solvent exchange of 2000g silicon dioxide microparticle (R5) aqueous dispersions is methyl alcohol afterwards, and preparation is with SiO 2Meter concentration is the pure dispersion liquid of silicon dioxide microparticle (R5) of 20 weight %.(being equivalent to step (b))
The content of the water in the pure dispersion liquid of silicon dioxide microparticle (R5) is 0.5 weight %.
Likewise measure the surface negative charge amount of silicon dioxide microparticle (R5) with embodiment 1, the result is shown in the table.
Then, the pure dispersion liquid of 2000g silicon dioxide microparticle (R5) is adjusted to 25 ℃, to γ-(methyl) acryloxy propyl trimethoxy silicane (SHIN-ETSU HANTOTAI's chemistry (strain) system: KBM-503) 60g ((M that wherein adds as silicoorganic compound OC)=0.24 mole is with R 1-SiO (3)/2Count 3 weight %)).(being equivalent to step (c))
Then, stirred the pure dispersion liquid of silicon dioxide microparticle (R5) 0.5 hour down, make silicoorganic compound absorption at 25 ℃.(being equivalent to step (d))
Then, in the pure dispersion liquid of silicon dioxide microparticle (R5), adding 1.5g is ammoniacal liquor and the 7.8g pure water (8.78g water (mole number (M of 28 weight % in ammonia concentration H2O)=0.49, mol ratio (M H2O)/(M OC)=1.96): 0.42g ammonia (mole number (M NH3)=0.025, mol ratio (M NH3)/(M OC)=0.1).(being equivalent to step (e))
Then, dispersion liquid is adjusted to 50 ℃, slaking 19 hours.(being equivalent to step (f))
Then, likewise measure the surface negative charge amount of surface treatment silicon dioxide microparticle (R5) with embodiment 1, the result is shown in the table.
Then, use distillation method that solvent exchange is MIBK, concentrate simultaneously, the preparation solid component concentration is the silicon dioxide gel (R5) of 40 weight %.(being equivalent to step (g)) (being equivalent to step (h))
The viscosity of silicon sol (R5) is 8cp, and stability is 4 days.
Transparent coating forms the preparation with coating (R5)
Except that in embodiment 1, using solid component concentration is the silicon-aluminum sol (R5) of 40 weight %, and the transparent coating that likewise prepares solid component concentration and be 42 weight % forms with coating fluid (R5).
The viscosity that transparent coating forms with coating fluid (R5) is 12cp, and stability is 4 days.
Have the manufacturing of the base material (R5) of transparent coating
Except that in embodiment 1, using transparent coating to form with the coating fluid (R5), preparation likewise has the base material (R5) of transparent coating.The thickness of the transparent coating of this moment is 5 μ m.
Measure total light penetration, mist degree, pencil hardness, scratch resistance, the adaptation of gained transparent coating, the result is shown in the table.
Figure BPA00001559827600481
[table 2]
Figure BPA00001559827600491
Figure BPA00001559827600501

Claims (19)

1. the method for manufacture of a silicon-aluminum sol is characterized in that, comprises the steps (a)～(f):
(a) spent ion exchange resin carries out the dispersive aqueous dispersions to the silica alumina particulate with solid component concentration and handles in the scope of 1～30 weight %, makes ion (remove H+, OH -Outside) concentration reaches in the silica alumina particulate and to be the step below the 50ppm, the median size of said silica alumina particulate is in the scope of 5～100nm, and the alumina content in the particle is with Al 2O 3Meter is in 0.01～5 weight % scope;
(b) solvent exchange with silica alumina particulate aqueous dispersions is the step of alcohol;
(c) in silica alumina particulate alcohol dispersion liquid, add the silicoorganic compound that following formula (1) is represented, as R n-SiO (4-n)/2Reach the step in the scope of 1～50 weight % of silica alumina particulate,
R n-SiX 4-n (1)
R is the nothing replacement or the substituted hydrocarbon radical of carbonatoms 1～10 in the formula, is same to each other or different to each other, and X is alkoxyl group, hydroxyl, halogen, the hydrogen of carbonatoms 1～4, and n is 1～3 integer;
(d) stir silica alumina particulate alcohol dispersion liquid on one side, Yi Bian make said silicoorganic compound be adsorbed on the step on the silica alumina particulate;
(e) add water and hydrolysis and use catalyzer, the step that silicoorganic compound are hydrolyzed;
(f) in 0.5～24 hour step of 40～120 ℃ of following slakings.
2. the method for manufacture of silicon-aluminum sol as claimed in claim 1 is characterized in that, said step (a) comprises the steps that (a1) reaches (a2):
(a1) handle with Zeo-karb, make pH become the step in 1.0～6.0 scope;
(a2): handle with anionite-exchange resin, make the pH of dispersion liquid be higher than pH, the step in 2.0～7.0 scope of the dispersion liquid in the said step (a1).
3. according to claim 1 or claim 2 the method for manufacture of silicon-aluminum sol is characterized in that, in said step (f) afterwards, carries out following step (g) and/or (h):
(g) be replaced into the step of organic solvent;
(h) spissated step.
4. like the method for manufacture of each described silicon-aluminum sol in the claim 1～3; It is characterized in that, the negative charge amount of the per unit surface-area of the silica alumina particulate of the silica alumina particulate aqueous dispersions that obtains in the said step (a) under the condition of pH2.0～7.0 at 0.1～1.5 μ eq/m 2Scope in.
5. like the method for manufacture of each described silicon-aluminum sol in the claim 1～4, it is characterized in that the mole number (M of the water in the said step (e) H2O) with the mole number (M of silicoorganic compound OC) mol ratio (M H2O)/(M OC) in 1～300 scope.
6. like the method for manufacture of each described silicon-aluminum sol in the claim 1～5, it is characterized in that the hydrolysis in the said step (e) uses catalyzer to be ammonia, the mole number (M of ammonia NH3) with the mol ratio (M of the mole number (Moc) of silicoorganic compound NH3)/(Moc) is in 0.1～12 scope.
7. like the method for manufacture of each described silicon-aluminum sol in the claim 1～6; It is characterized in that; Negative charge amount for the per unit surface-area of the silica alumina particulate of the silica alumina particulate aqueous dispersions that obtains in the said step (f); When using solid component concentration to be the dispersion liquid mensuration of 0.5 weight %, pH7.5 ± 1.5, at 0.5～2.0Micro-coulombs/cm 2Scope in.
8. like the method for manufacture of each described silicon-aluminum sol in the claim 1～7, it is characterized in that, the organic solvent in the said step (g) be selected from ethers, ester class, ketone, the alcohols more than a kind or 2 kinds.
9. like the method for manufacture of each described silicon-aluminum sol in the claim 1～8, it is characterized in that solid component concentration is in the scope of 20～70 weight %, viscosity is 1～10, in the scope of 000cp.
10. silicon-aluminum sol is that the alumina content of median size in the scope of 5～100nm, in the particle is with Al 2O 3Meter carried out the dispersion liquid of surface-treated silica alumina particulate in the scope of 0.01～5 weight % and with the silicoorganic compound of following formula (1) expression; It is characterized in that the per unit surface-area negative charge amount (Q of said surface treatment silica alumina particulate 1) with the per unit surface-area negative charge amount (Q that carries out the silica alumina particulate before the surface treatment with silicoorganic compound 2) ratio (Q 1)/(Q 2) in 0.2～0.8 scope,
R n-SiX 4-n (1)
R is the nothing replacement or the substituted hydrocarbon radical of carbonatoms 1～10 in the formula, is same to each other or different to each other, and X is alkoxyl group, hydroxyl, halogen, the hydrogen of carbonatoms 1～4, and n is 1～3 integer.
11. silicon-aluminum sol as claimed in claim 10 is characterized in that, said negative charge amount (Q 1) when using solid component concentration to be the dispersion liquid mensuration of 0.5 weight %, pH7.5 ± 1.5, at 0.5～2.0Micro-coulombs/cm 2Scope in.
12. forming, a transparent coating uses coating; It is characterized in that; By each described silicon-aluminum sol in the claim 1～11, matrix forms composition and dispersion medium is formed; Total solid component concentration in the scope of 30～70 weight %, the concentration that matrix forms composition in solid state component in the scope of 6～63 weight %, the concentration of silica alumina particulate in solid state component in the scope of 3～56 weight %.
13. transparent coating as claimed in claim 12 forms and uses coating, it is characterized in that, said matrix is formed into and is divided into silicon class matrix formation composition or organic resin matrix formation composition, contains polyfunctional acrylic ester resin or multifunctional silicone resin.
14. use coating like claim 12 or 13 described transparent coatings formation, it is characterized in that, also contain the silicon class stain control agent of counting 0.003～0.7 weight % with solid state component.
15. use coating like each described transparent coating formation in the claim 12～14, it is characterized in that, also contain the even paint of counting 0.003～0.56 weight % with solid state component.
16. form like each described transparent coating in the claim 12～15 and to use coating, it is characterized in that, said dispersion medium be selected from ethers, ester class, ketone, the alcohols more than a kind or 2 kinds.
17. a base material that has transparent coating is formed by base material and the transparent coating that is formed on the base material, it is characterized in that, said transparent coating is to use each described transparent coating in the claim 12～16 to form with coating formation.
18. the base material that has transparent coating as claimed in claim 17; It is characterized in that; The content of the silica alumina particulate in the said transparent coating in solid state component in the scope of 10～80 weight %, the content of matrix components in solid state component in the scope of 20～90 weight %.
19., it is characterized in that the thickness of said transparent coating is in the scope of 0.5～20 μ m like claim 17 or the 18 described base materials that have transparent coating.
CN201080051797.8A 2009-11-16 2010-11-15 Process for production of silica-alumina sol, silica-alumina sol, coating agent for formation of transparent coating film which comprises the sol, and substrate having transparent coating film attached thereto Active CN102666383B (en)

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