CN107235643A - The manufacture method of high antireflection reinforced glass - Google Patents
The manufacture method of high antireflection reinforced glass Download PDFInfo
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- CN107235643A CN107235643A CN201710193714.2A CN201710193714A CN107235643A CN 107235643 A CN107235643 A CN 107235643A CN 201710193714 A CN201710193714 A CN 201710193714A CN 107235643 A CN107235643 A CN 107235643A
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- refractive index
- coating liquid
- refraction
- silicon compound
- antireflection
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B27/00—Tempering or quenching glass products
- C03B27/02—Tempering or quenching glass products using liquid
- C03B27/03—Tempering or quenching glass products using liquid the liquid being a molten metal or a molten salt
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/73—Anti-reflective coatings with specific characteristics
- C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Abstract
The present invention relates to the manufacture method of high antireflection reinforced glass.Antireflection film is thermally formed with 100~500 DEG C after being coated to high index of refraction coating liquid, coated low-refraction coating liquid on the glass substrate, in ion exchange with carrying out chemical intensification treatment in metal salt fused solution with 380~500 DEG C；High index of refraction coating liquid contains (a) silicon compound, (b) is formed by zirconium oxide and/or titanium dioxide granule high index of refraction inorganic oxide particles and (c) metallo-chelate, (a) be 50/50~95/5 with the mass ratio of (b), (c) relative to (a) and (b) totally 100 parts by weight below 20 parts by weight；Low-refraction coating liquid contains (a), the hollow silica particle for having cavity inside (d) and described (c), (a) be 50/50~99/1 with the mass ratio of (d), (c) relative to (a) and (d) totally 100 parts by weight below 20 parts by weight.
Description
Technical field
The present invention relates to the strengthened glass for the anti-reflective function that height is assigned by the antireflection film being made up of multiple layers
Manufacture method.
Background technology
The strengthened glass for improving strength of glass is widely used in the purposes such as the glass pane in automobile, house, recently also by with
In purposes such as the display screens of various mobile devices such as whole face protection panels, digital camera, the mobile phone of electrostatic capacity type contact panel.
The display screen of the latter with the shape of strengthened glass it is small and complicated, it is necessary to cut off, end face process, perforate process etc.
Shape is processed.But, due to being difficult to the processing of these shapes after reinforcing, therefore glass substrate is processed into final system in advance
Intensive treatment is carried out after product shape.
It is used as the intensifying method of glass, it is known that using physical strengthening method, the chemical enhanced method using ion exchange of chilling,
Physical strengthening method is using glass that thickness is several more than mm as object, and the glass substrate for thickness of thin is not effective.Therefore,
For the thin glass of above-mentioned protection panels, display screen equal thickness, generally using chemical enhanced method.
Wherein, using the chemical enhanced method of ion exchange by by the small metal ion of ionic radius contained in glass
(such as sodium ion) is replaced and carried out with the bigger metal ion of ionic radius (such as potassium ion).That is, it is ionic radius is small
Metal ion uses the metal ion with the ionic radius bigger than its to replace, so that in glass surface formation compressive stress layers.
As a result, when the glass is destroyed, in addition to the power of key between saboteur, in addition it is also necessary to release the compression on surface
The power of stress, compared with common glass, its intensity is significantly improved.
On the other hand, the strengthened glass strengthened for the chemical treatment by using ion exchange, also will sometimes
Anti-reflective function, other functions are asked, particularly anti-reflective function is required in above-mentioned protection panels, various display screens etc..
In order to assign anti-reflective function, the antireflection film of low-refraction can be formed on surface.It is used as this kind of antireflection film
Formation means, it is known that be roughly divided into using evaporation method and using sol-gal process method.
Vapour deposition method needs the high device of cost, therefore industrially implements seldom.At present, coating contains subparticle
Coating liquid, the sol-gal process of antireflection film is formed by using the gelation of heating because production cost is low, production
Rate is also high, therefore as main flow.
It is used as the antireflection film formed by this kind of sol-gal process, it is known to such as hydrolytic condensation containing silicon compound
The antireflection film of thing, metallo-chelate and low refraction silica dioxide granule (referring to patent document 1).
But, for forming antireflection film for the surface of the strengthened glass obtained from by chemical treatment, existing must
The key subjects that must be solved.
As it was previously stated, the shape processing of strengthened glass is carried out before intensive treatment, and utilizing chemically treated reinforcing
In glass, it is necessary to the formation of antireflection film is carried out after intensive treatment.The reason is that formed antireflection film after can not make potassium from
Son penetrates into inside glass, thus becomes that intensive treatment can not be carried out.
However, due to shape processing has been carried out before the intensive treatment (utilizing the chemical treatment of ion exchange),
Therefore the formation of antireflection film is changed into carrying out after the shape processing of glass.Therefore, even if passing through the high collosol and gel of productivity ratio
Method formation antireflection film, it is also necessary to which the product after being processed to shape forms antireflection film one by one, therefore its productivity ratio is remarkably decreased,
The advantage that can carry out large-area treatment of sol-gal process has completely lost.
In order to solve above-mentioned problem, it is proposed that formed after antireflection film by being chemically treated the side to carry out glass reinforced
Method.
A kind of method is, utilizes contained inorganic particles, particle in the antireflection film formed on the surface and particle
Clearance space (hereinafter referred to as space) carries out ion exchange, the method strengthened to glass (patent document 2).But, the party
There are the following problems for method：The space that ion exchange can be carried out is difficult to control to.
In order to solve the above problems, it is proposed that following method：The space of particle and particle is not utilized but uses internal tool
There is the hollow particle in space, ion exchange (patent document 3) is carried out by the inner space.This method is due to advance using having
The particle of defined spatial volume, therefore compared with above-mentioned air-gap method, the condition setting of ion exchange is easy.But then,
The species of hollow inorganic particle is few, and industrialization preparation method is also limited, therefore the limitednumber of utilizable inorganic particle.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2002-221602 publications
Patent document 2：Japanese Unexamined Patent Publication 2002-234754 publications
Patent document 3：Japanese Unexamined Patent Publication 2011-88765 publications
The content of the invention
Problems to be solved by the invention
However, for antireflection film, in order to improve its antireflection property, it is necessary to be set in low-index layer and glass base
Two-layer structure provided with high refractive index layer between plate and not only Rotating fields of the low-index layer, in order to further improve it
Performance is, it is necessary to be set to be provided with the three-decker of middle index layer between high refractive index layer and glass substrate.
But, in order to show defined refractive index, it is necessary to be compounded refractive index in high refractive index layer, middle index layer and compare two
The high zirconia particles of silicon oxide particle (refractive index 2.10), titanium dioxide granule (refractive index 2.72).
However, for these high refractive index particles, hollow particle is difficult to obtain, therefore above-mentioned utilization can not be realized
The ion exchange of the inner space of grain, in the two-layer structure or three-decker during anti-reflection layer is said structure, with usual bar
After part formation anti-reflection layer, it is difficult to penetrate the glass reinforced processing of multiple layers of utilization ion exchange.
Present inventor etc. have extensively studied using the inner space of hollow particle and the mutual space of particle, pass through
The glass substrate that ion-exchange is formed with the antireflection film being made up of multiple layers to surface carries out glass reinforced method, as a result
It was found that, by controlling the composition and curing condition and then ion exchange conditions (intensive treatment condition) of antireflection film, can be had
The glass substrate for having the anti-reflective function of height and being strengthened, so far completes the present invention.
The solution used to solve the problem
That is, according to the present invention there is provided a kind of manufacture method of high antireflection reinforced glass,
Methods described glass substrate surface formed at least contain positioned at visual field side refractive index for less than 1.45 it is low
Index layer and positioned at glass substrate side refractive index be 1.55 antireflection film less than 2.00 high refractive index layer after,
Chemical intensification treatment using ion-exchange is carried out to the glass substrate for being formed with antireflection film, so that it is strong to manufacture high antireflection
Change glass, it is characterised in that
High index of refraction coating liquid is coated on the glass substrate, then, low-refraction coating liquid is coated to, then, with 100
~500 DEG C of temperature is thermally formed antireflection film, then, ion exchange with metal salt fused solution with 380~500 DEG C of temperature
Degree carries out chemical intensification treatment；
The high index of refraction coating liquid contains：
(a) silicon compound shown in following formula (1),
Rn-Si(OR1)4-n (1)
In formula (1), R is alkyl or alkenyl,
R1For alkyl or alkoxyalkyl,
N is 0~2 integer；
(b) the high index of refraction inorganic oxide particles formed by zirconium oxide and/or titanium dioxide granule；And,
(c) metallo-chelate,
The mass ratio (a/b) of above-mentioned silicon compound (a) and high index of refraction inorganic oxide particles (b) is 50/50~95/
5 scope, above-mentioned metallo-chelate (c) is total with inorganic oxide particles (b) relative to silicon compound (a) and high index of refraction
It is the scope below 20 parts by weight to measure 100 parts by weight；
Above-mentioned low-refraction coating liquid contains：
(a) silicon compound shown in above-mentioned formula (1)；
(d) it is internal that there is empty hollow silica particle；And,
(c) metallo-chelate,
The scope that the mass ratio (a/d) of above-mentioned silicon compound (a) and hollow silica particle (d) is 50/50~99/1,
Above-mentioned metallo-chelate (c) is 20 relative to the parts by weight of total amount 100 of silicon compound (a) and hollow silica particle (d)
Scope below parts by weight.
In the invention of the manufacture method of above-mentioned high antireflection reinforced glass, desirably：
1) antireflection film high refractive index layer substrate-side further have refractive index be 1.50 less than 1.90,
Refractive index is less than the middle index layer of high refractive index layer,
Refractive index coating liquid in being coated to before coated high index of refraction coating liquid, the middle refractive index is contained with coating liquid
Have：
(a) silicon compound shown in above-mentioned formula (1)；
(e) the middle refractive index inorganic oxide particles containing zirconium oxide and/or titanium dioxide granule；And,
(c) metallo-chelate,
The mass ratio (a/e) of above-mentioned silicon compound (a) and middle refractive index inorganic oxide particles (e) is 50/50~95/
5 scope, above-mentioned metallo-chelate (c) is total with inorganic oxide particles (b) relative to silicon compound (a) and middle refractive index
Scope of 100 parts by weight below 20 parts by weight is measured,
2) above-mentioned silicon compound is tetraethoxysilane,
3) carry out being thermally formed antireflection film with 200~300 DEG C of temperature,
4) chemical intensification treatment is carried out with 380~480 DEG C of temperature.
And then a kind of technical scheme is provided, it is characterised in that it is after above-mentioned antireflection film is formed and above-mentioned chemical enhanced
The shape processing of glass substrate is carried out before processing.
The effect of invention
The method according to the invention, can be after antireflection film be formed, by disposably handling to compound antireflection
The glass substrate progress of film is glass reinforced, industrial exceedingly useful, wherein, the compound antireflection film is that have sky containing inside
The index layer of the hollow silica particle in hole and containing the internal inorganic oxide particles that cavity is not present (hereinafter also referred to
Middle real inorganic oxide particles) index layer be laminated.As described above, hollow silica particle and the inorganic oxygen of middle reality
Glass reinforced mechanism of the compound particle based on ion exchange is different, therefore is difficult to carry out glass by single process so far
Reinforcing.
And then, in the present invention, due to can be in the stage before shape processing by the glass substrate as strengthened glass
Surface forms antireflection film, therefore its productivity ratio is high, and it is possible to have with low cost manufacture on the surface of strengthened glass anti-
The strengthened glass product of reflectance coating.Resulting strengthened glass has the antireflection film being made up of multilayer, therefore minimum reflectivity
Reduction, or it is excellent to the antireflection of the light of wide wavelength range.
This kind of strengthened glass product suitable is used for the thin product of glass substrate, the whole face of such as electrostatic capacity type contact panel
The purposes such as the display screen of the various mobile devices such as protection panels, digital camera, mobile phone.
Embodiment
The formation ＞ of ＜ antireflection films
In the present invention, when antireflection film is by constituting for three layers, according to middle index layer, high refractive index layer and low-refraction
The order stacking of layer, middle index layer is sealed at glass substrate.When antireflection film is by constituting for two layers, in the absence of middle refractive index
Layer, is laminated, high refractive index layer is sealed at glass substrate according to the order of high refractive index layer and low-index layer.
＜ glass substrates ＞
As glass substrate, as long as the glass substrate with the composition that can be strengthened using chemical intensification treatment,
Can be with using the glass substrate of various compositions, but desirably containing the smaller alkali metal ion of ionic radius, alkaline-earth metal
The glass of ion.For example, soda lime glass, alumina silicate glass containing alkali, containing alkali borosilicate glass etc. be it is suitable, this
Among a little, the glass containing sodium ion is most appropriate.Optimum is the glass of the sodium ion containing more than 5 weight %.
The thickness of the glass substrate is not particularly limited, it is however generally that, in order to effectively carry out aftermentioned chemical intensification treatment,
Preferably generally below 2mm scope.
The formation ＞ of ＜ low-index layers
Low-index layer is the layer that refractive index is less than 1.45, and the coated low refraction containing following compositions is gone forward side by side with coating liquid
Row is dried, heats and formed.That is, low refraction is with the composition of coating liquid：Contain
Silicon compound (a) shown in formula (1),
Rn-Si(OR1)4-n (1)
In formula (1), R is alkyl or alkenyl,
R1For alkyl or alkoxyalkyl,
N is 0~2 integer,
(d) the internal hollow silica particle with cavity and
(c) metallo-chelate,
The scope that the mass ratio (a/d) of above-mentioned silicon compound (a) and hollow silica particle (d) is 50/50~99/1,
Above-mentioned metallo-chelate (c) is 20 relative to the parts by weight of total amount 100 of silicon compound (a) and hollow silica particle (d)
Scope below parts by weight.
(a) silicon compound
It is good and performance binding agent of the fine and close, film of high intensity is acted on the adaptation of glass substrate for being formed
Composition, such as shown in above-mentioned formula (1).
If concrete example shows compound, as n=0 silicon compound, it can include：Tetramethoxy-silicane, tetrem
The tetraalkoxysilanes such as TMOS, tetrapropoxysilane；As n=1 silicon compound, it can include：Methyl trimethoxy oxygen
Base (ethyoxyl) silane, methyl triple phenoxyl silane, ethyl trimethoxy (ethyoxyl) silane, γ-(2- amino-ethyls) amino
Propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, γ-glycidoxypropyl group trimethoxy
The trialkoxy silanes such as silane, γ mercaptopropyitrimethoxy silane；As n=2 silicon compound, it can include：Diformazan
Base dimethoxysilane, dimethyldiethoxysilane, Cyclohexyl Methyl Dimethoxysilane, γ-chloropropyl dimethoxy
Base silane, γ-glycidoxypropyl dimethoxysilane, γ-methacryloyloxypropyl methyl dimethoxy silicon
Dialkoxy silicanes such as alkane etc..
In the present invention, in foregoing illustrative compound, from keep intensity angle, particularly suitable be n=0 and
N=1 silicon compound, wherein, tetraethoxysilane and γ-glycidoxypropyltrime,hoxysilane are due to that can form three-dimensional
The connected densification of mesh-shape, the film of high intensity and it is most appropriate.
(d) hollow silica particle
There is the empty particle formed by silica to be internal, be typically that its particle diameter (passes through laser diffraction and scattering method
The average grain diameter of the volume reference of measure) be the scope that 5~150nm, the thickness of outer shell are 1~15nm or so it is fine in
Hollow particle.Although using its interior void carry out ion exchange, be also to be formed refractive index be less than 1.45 layer, play it is excellent
Composition necessary to different antireflection ability.Therefore, desirably the refractive index of selection hollow silica particle for 1.20~
The hollow silica particle of 1.38 scope.
The hollow silica particle (d) is known for example, by Japanese Unexamined Patent Publication 2001-233611 publications etc., generally with
The scattered liquid status sale of the lower alcohols such as methanol, ethanol, propyl alcohol is scattered in, therefore preferably obtains, utilize commercially available product.
The mass ratio (a/d) of silicon compound (a) and hollow silica particle (d) is needed for 50/50~99/1.
The lower limit [1] of hollow silica particle in both proportionings is based on easily carrying out ion exchange, Neng Goujin
The viewpoint of row intensive treatment and determine, marresistance of the higher limit [50] based on resulting low-index layer and with height refraction
Rate layer adaptation viewpoint and determine.When i.e., less than lower limit, it is impossible to effective chemical intensification treatment is carried out, more than the upper limit
During value, the mechanical strength of low-index layer declines and easily peeled off from high refractive index layer.From the above point of view, mass ratio (a/
D) it is preferably 80/20~98/2.
(c) metallo-chelate
It is the composition with the function as crosslinking agent, makes the antireflection film to be formed finer and close, effectively suppresses compounding
The decline of film strength, hardness caused by above-mentioned hollow silica sol.
The metallo-chelate (c) is the metal-complexings such as the chelating agent and titanium, zirconium, aluminium using bidentate ligand as typical example
Compound.
Specifically, it can include：Triethoxy list (acetopyruvic acid) titanium, diethoxy are double (acetopyruvic acid)
Titanium, monosubstituted ethoxy three (acetopyruvic acid) titanium, four (acetopyruvic acid) titaniums, triethoxy list (oacetic acid) titanium, diethyl
Epoxide double (oacetic acid) titanium, monosubstituted ethoxy three (oacetic acid) titanium, (the ethyl second of list (acetopyruvic acid) three
Acid) the titanium chela such as titanium, double (acetopyruvic acids) double (oacetic acid) titaniums, single (oacetic acid) titanium of three (acetopyruvic acids)
Compound；
Triethoxy list (acetopyruvic acid) zirconium, diethoxy double (acetopyruvic acid) zirconium, (acetylacetone,2,4-pentanediones of monosubstituted ethoxy three
Acid) zirconium, four (acetopyruvic acid) zirconiums, triethoxy list (oacetic acid) zirconium, double (oacetic acid) zirconiums of diethoxy,
Monosubstituted ethoxy three (oacetic acid) zirconium, four (oacetic acid) zirconiums, list (acetopyruvic acid) three (oacetic acid)
The zirconium chelatings such as single (oacetic acid) zirconium of zirconium, double (acetopyruvic acids) double (oacetic acid) zirconiums, three (acetopyruvic acids)
Thing；
Diethoxy list (acetopyruvic acid) aluminium, monosubstituted ethoxy double (acetopyruvic acid) aluminium, diisopropoxy list (levulinics
Ketone acid) aluminium, the aluminium chelate compound such as monosubstituted ethoxy double (oacetic acid) aluminium, diethoxy list (oacetic acid) aluminium, etc..
Above-mentioned metallo-chelate (c) is relative to silicon compound (a) and the weight of total amount 100 of hollow silica particle (d)
It is preferably 0.01~20 parts by weight, particularly preferably 0.1~10 parts by weight below 20 parts by weight to measure part.The compounding amount is excessive
When, metallo-chelate is separated out in antireflection film, causes bad order.When the compounding amount is few, under antireflection film strength, hardness
Drop, the actual effect of the chemical intensification treatment of glass substrate becomes undesirable.
Above-mentioned essential component has been dissolved or dispersed in by above-mentioned low refraction with coating liquid generally for easily carrying out coated
Used in machine solvent.It is representational to use：The alcohol series solvents such as methanol, ethanol, isopropanol, ethyl cellosolve, ethylene glycol；
The ester series solvents such as ethyl acetate, butyl acetate, the ketone series solvent such as acetone, methyl ethyl ketone；The fragrant families such as toluene, dimethylbenzene are molten
Agent.Particularly preferably use alcohol series solvent.
The usage amount of organic solvent is that the viscosity for making low refraction with coating liquid is not producing sagging etc., the scope suitable for coating
Amount.In general, can be with so that total solid component concentration reaches that 0.1~20 weight % of gross weight amount has been used
Machine solvent.It should be noted that above-mentioned hollow silica particle (d) is dispersed in selling in the decentralized media such as alcohol series solvent
, therefore above-mentioned organic solvent amount is the value including the amount of the decentralized medium.
And then, can also be by aqueous acids such as aqueous hydrochloric acid solutions with suitable in order to promote hydrolysis, the condensation of silicon compound (a)
When amount be compounded in low refraction coating liquid.
Above-mentioned low refraction is coated on aftermentioned high refractive index layer and dried with coating liquid, is then heated and forms low
Index layer, is generally disposably implemented using the heat treatment of heating after applying layers and drying.
Coating method is not particularly limited, can be using the side such as dip coating, rolling method, die coating method, flow coat method, spray-on process
Method, from the viewpoint of exterior quality, film thickness monitoring, preferred dip coating.
The formation ＞ of ＜ high refractive index layers
High refractive index layer be refractive index for 1.55 less than 2.00 layer, high refraction of the coating containing following compositions use
Coating liquid is simultaneously dried, heats and formed.That is, high refraction is configured to coating liquid：Contain
Silicon compound (a) shown in above-mentioned formula (1),
(b) high index of refraction formed by zirconium oxide and/or titanium dioxide granule with inorganic oxide particles and
(c) metallo-chelate,
The mass ratio (a/b) of above-mentioned silicon compound (a) and high index of refraction inorganic oxide particles (b) is 50/50~95/
5 scope, above-mentioned metallo-chelate (c) is total with inorganic oxide particles (b) relative to silicon compound (a) and high index of refraction
It is the scope below 20 parts by weight to measure 100 parts by weight.
High refraction can directly use above-mentioned low folding with (a) silicon compound and (c) metallo-chelate used in coating liquid
Penetrate (a) silicon compound and (c) metallo-chelate illustrated in the part with coating liquid.
(b) high index of refraction inorganic oxide particles
The high index of refraction is come suitably to determine to use as follows with inorganic oxide particles：By refractive index be 2.10 and
Zirconia particles of the inside without cavity, the same internal refractive index without cavity are independent for 2.72 titanium dioxide granule
Using or mixing so that high refractive index layer turn into refractive index be 1.55 less than 2.00 layer.
Silicon compound (a) and the mass ratio (a/b) of high refraction inorganic oxide particles (b) are needed for 50/50~95/5.
High refraction in both proportioning be based on the lower limit [5] of inorganic oxide particles it is easy carry out ion exchange,
The viewpoint of intensive treatment can be carried out and determined, in order to form void among particles, it is necessary to amount more than hollow silica.On
Scratch resistance of the limit value [50] based on resulting high refractive index layer and determined with the viewpoint of the adaptation of glass substrate.That is, it is low
When lower limit, it is impossible to carry out effective chemical intensification treatment, during more than higher limit, the mechanical strength of high refractive index layer decline and
Easily peeled off from glass substrate.From the above point of view, mass ratio (a/b) is preferably 55/45~90/10.
The high index of refraction is usually dispersed in the decentralized media such as alcohol series solvent and sold with inorganic oxide particles (b), because
This is in the same manner as hollow silica particle (d), it is necessary to which the decentralized medium is considered as the organic solvent in coating liquid.
(c) metallo-chelate
Metallo-chelate (c) can be used and identical metallo-chelate in low-index layer.In addition, compounding amount is also same
The amount of sample.
High refraction coating liquid can suitably use organic solvent, aqueous acid in the same manner as low refraction coating liquid.To
The method being coated with glass substrate can also use same method, but preferably dip coating.
The formation ＞ of index layer in ＜
When antireflection film is by constituting for three layers, between high refractive index layer and glass substrate set refractive index be more than 1.50 and
Middle index layer less than 1.90.It should be noted that refractive index of index layer needs to be set to be necessarily less than to be laminated in this
The refractive index of high refractive index layer thereon.
Middle index layer is configured to：Comprising the high refraction coating liquid containing following compositions,
Silicon compound (a) shown in above-mentioned formula (1),
(e) the middle refractive index inorganic oxide particles that are formed by zirconium oxide and/or titanium dioxide granule and
(c) metallo-chelate,
The mass ratio (a/e) of above-mentioned silicon compound (a) and middle refractive index inorganic oxide particles (e) is 50/50~95/
5 scope.Mass ratio (a/e) is preferably 55/45~90/10.
The scope and its restriction reason of the mass ratio (a/e) are using the scope and its restriction reason of high refractive index layer as mark
It is accurate.In addition, also metallo-chelate (c), organic solvent, aqueous acid are suitably used with coating liquid as standard using low refraction, to glass
The method being coated with glass substrate also uses same method, but preferably dip coating.
Middle refraction is formed with (a) silicon compound, (e) used in coating liquid by zirconium oxide and/or titanium dioxide granule
Above-mentioned high refraction can be used directly with inorganic oxide particles and (c) metallo-chelate with being used in coating liquid in middle refractive index
Respective substance, the middle refractive index inorganic oxide particles (e) formed by zirconium oxide and/or titanium dioxide granule reflect in considering
Rate layer above-mentioned refractive index scope and refractive index it is smaller than high refractive index layer and determine its use and mixing ratio.On middle refraction
The decentralized medium of rate inorganic oxide particles (e), similarly needs to consider as organic solvent.
The formation ＞ of antireflection film on ＜ glass substrates
When antireflection film is two-layer structure, high refraction coating liquid and drying are coated with above-mentioned glass substrate, then,
Low refraction coating liquid and drying are coated with, then, the heat treatment using heating is carried out, is solidified, toasted.It is in antireflection film
During three-decker, before high refraction coating liquid is coated with, refraction coating liquid and drying in coating.
Drying process is not particularly limited, implemented 0.5~1 hour or so generally at a temperature of 70~100 DEG C.
In the present invention, in the heating condition disposably implemented after drying be extremely important, it is necessary to 100 DEG C~500
DEG C scope heated, implement solidification, baking processing.During for heating less than 100 DEG C, the hydrolysis of silicon compound (a) and
The condensation of appropriate intake metallo-chelate is not carried out fully, it is impossible to form the antireflection film of sufficient intensity.During more than 500 DEG C, water
Solution and condensation are excessively carried out, and silicon compound (a) almost becomes silica composition completely, it is impossible to carry out described later penetrating antireflection
The ion exchange of layer, intensive treatment becomes difficult.From the reason, particularly preferably 200 DEG C~300 DEG C of heating.
From the viewpoint of antireflection property and ion exchange, each thickness degree of obtained antireflection film is typically set to 50~
150nm scope.And then, preferred each thickness degree is located at 70~100nm scope.
《Shape is processed》
According to the above method, be formed with glass substrate the substrate of firm antireflection film carry out chemical intensification treatment it
It is preceding to carry out shape processing corresponding with purposes, it is machined such as cut-out, end face processing, perforate processing.That is, because entering
Row chemical intensification treatment and glass substrate is made after strengthened glass, it is difficult to carry out this kind of machining.Added by the shape
Work, the glass substrate for possessing antireflection film turns into final article shape.
《Chemical intensification treatment》
The substrate that firm antireflection film is formed with glass substrate whether carries out shape processing, afterwards equal implementationizations
Learn intensive treatment.By by the small metal ion of ionic radius contained in glass substrate be replaced as the big metal of ionic radius from
Son, so as to form compressive stress layers on surface, realizes the high intensity of glass substrate.Thus, it is possible to which obtaining surface has counnter attack
Penetrate the strengthened glass product of film.
On the chemical intensification treatment, specifically, the glass substrate with antireflection film is set to contain by impregnating contact
The ion exchange for having big metal ion metal salt fused solution, so that the small metal ion in glass substrate is replaced into big metal
Ion.For example, by making the sylvite fused solutions such as the glass substrate containing sodium ion and potassium nitrate, (ion exchange is melted with metal salt
Liquid) contact, so that the small sodium ion of ionic radius is replaced into the big potassium ion of ionic radius, form the reinforcing glass of high intensity
Glass.
In the present invention, in addition to the anti-reflection layer containing hollow silica particle, also exist and contain without interior
The zirconia particles in portion space, the anti-reflection layer of titanium dioxide granule, therefore ion exchange is carried out in order to penetrate two layers, in gold
The control of heating-up temperature in category salt fused solution becomes important, it is necessary to implement in the range of 380 DEG C~500 DEG C.Less than 380 DEG C
When, potassium nitrate can not be melted fully, and ion exchange becomes insufficient.During more than 500 DEG C, potassium nitrate starts to decompose, therefore chemistry
Intensive treatment will be with danger.It is therefore preferable that being 380 DEG C~480 DEG C of scope.Processing time is usually 3~16 hours left sides
It is right.
The high antireflection reinforced glass obtained by the present invention is not limited only to above-mentioned Rotating fields.For example, anti-in order to protect
Reflectance coating, can set external coating (overcoat layer) on the surface of antireflection film.As this kind of external coating, it can enumerate
Go out to assign abrasion performance, the organopolysiloxane based material of marresistance, the overlay of fluororesin system.
And then, it can set what the adhesive by acrylic acid series, rubber series, silicon-type was formed in the dorsal part of glass substrate
Adhesive phase.And then, the antireflection film of the present invention can also be formed on the surface and the back side of glass substrate.
Embodiment
Embodiment is exemplified below to illustrate the present invention, but the present invention is not by any restriction of these embodiments.In addition, real
Necessary to the combination for applying in example illustrated feature is entirely not the solution of the present invention.
The various composition used in following embodiment and comparative example and abbreviation and test method are as follows.
(a) silicon compound
TEOS：Tetraethoxysilane
(b), (e) inorganic oxide particles
ZrO2Particle：Zirconia particles (average grain diameter：61.9nm, solid state component：30 weight %, dispersion solvent：Methanol,
Refractive index：2.40)
TiO2Particle：Titanium dioxide granule (average grain diameter：108.8nm, solid state component：15 weight %, dispersion solvent：First
Alcohol, refractive index：2.71)
(c) metallo-chelate
AlAA：Double (oacetic acid) aluminium of single acetyl acetone
(d) hollow silica particle
Average grain diameter：40nm, refractive index：1.25 (use the solid state component using isopropanol as dispersion solvent to be 20 weight %
Silicon dioxide gel)
(f) other
Solvent：Isopropanol (IPA)
Hydrolyst：0.05N hydrochloric acid
Glass substrate：Soda-lime glass glass plate (50mm × 90mm × 1.1mm)
(1) light reflectance
" V-570 " testing machine manufactured using Japan Spectroscopy Corporation determines minimum reflectivity.
(2) case hardness
Using steel wool #0000 while applying 1kg/cm220, load one side double rubs test body surface is round, and (1 is past
Return/second, apart from 45mm/1 come and go), visually observe whether antireflection film surface produces cut, evaluated by following benchmark.
〇：Not it was observed that the change of antireflection film
△：There are the scratch of wire, but the stripping unconfirmed to antireflection film itself
×：Confirm the stripping of antireflection film
(3) compression stress value determines (strength of glass)
Use (having) folding it is former make manufactured " FSM-6000LE " determine chemically reinforced glass surface by refringence
Surface stress CS (MPa) caused by (due to ion exchange) and stress layer depth DOL (μm) ZCS and DOL values are bigger, represent strong
Change degree is bigger.When strengthening to soda-lime glass, as long as DOL values, which are 10 μm or so, to play work(sufficiently as strengthened glass
Energy.
Embodiment 1
Prepare the low refractions of following compositions with coating liquid and high refraction coating liquid.
Low refraction coating liquid：
Mix and prepare at room temperature.
High refraction coating liquid：
Mix and prepare at room temperature.
First, above-mentioned high refraction is coated on glass substrate (soda-lime glass) with coating liquid by dip coating, it is dry with 100 DEG C
Dry 0.5 hour.Next, being equally coated with low refraction coating liquid, dried 0.5 hour with 100 DEG C.Then, with 300 DEG C of heating 2
Hour, carry out being formed (solidification, baking) by two layers of antireflection film constituted.
Then, make the glass substrate for being formed with antireflection film in fused potassium nitrate and impregnated 16 hours with 390 DEG C, changed
Intensive treatment is learned, high antireflection reinforced glass is obtained.
5 glass specimens are made, light reflectance, strength of glass and case hardness is carried out according to the method described above respectively
Evaluate, its result is shown in table 1 together with the composition of coating liquid (antireflection film).It should be noted that on light reflectance
And strength of glass, show the average value of 5 samples.
Embodiment 2~6
It is same with embodiment 1 in addition to the low refraction coating liquid and high refraction coating liquid using the composition shown in table 1
Sample is implemented, and makes high antireflection reinforced glass, is equally measured.Show the result in table 1.
Embodiment 7
In example 2, impregnated 4 hours at 450 DEG C and carry out chemical intensification treatment, same processing, makes in addition
High antireflection reinforced glass, is equally measured.Show the result in table 1.
Embodiment 8
In embodiment 5, impregnated 4 hours at 450 DEG C and carry out chemical intensification treatment, same processing, makes in addition
High antireflection reinforced glass, is equally measured.Show the result in table 1.
Embodiment 9
In embodiment 5, the formation of antireflection film is heated 2 hours and carried out at 150 DEG C, in addition same processing, system
Make high antireflection reinforced glass, be equally measured.Show the result in table 1.
[table 1]
Embodiment 10
In embodiment 5, the formation of antireflection film is heated 2 hours and carried out at 450 DEG C, in addition same processing, system
Make high antireflection reinforced glass, be equally measured.Show the result in table 2.
Embodiment 11
Prepare the low refractions of following compositions with coating liquid and high refraction coating liquid.
Low refraction coating liquid：
Mix and prepare at room temperature.
High refraction coating liquid：
Mix and prepare at room temperature.
Implement similarly to Example 1, be coated with high refraction coating liquid, low refraction coating liquid successively on the glass substrate simultaneously
After drying, the formation of antireflection film is heated 2 hours and carried out at 500 DEG C, it is then small with 390 DEG C of dippings 16 in fused potassium nitrate
When, carry out chemical intensification treatment and obtain high antireflection reinforced glass.Show the result in table 2.
Comparative example 1~3
Using the high refraction of the composition shown in table 1 with coating liquid, low refraction coating liquid, carry out similarly to Example 1
Processing, attempts to carry out the making of high antireflection reinforced glass.
In comparative example 1, high refraction is set to the content of the zirconia particles in coating liquid more than the scope of the invention
The amount of the upper limit.In comparative example 2, formation (solidification, baking) temperature of antireflection film is set to 550 DEG C, will in comparative example 3
Form temperature and be set to 600 DEG C.Show the result in table 2.
In comparative example 2 and 3, CS, DOL can not be determined, it is known that unrealized glass reinforced.
[table 2]
Embodiment 12
In embodiment 1, using the high refraction of following compositions with coating liquid and middle refraction coating liquid, in the high refraction of coating
It is real similarly to Example 1 in addition by refraction coating liquid and drying in same condition coating before coating liquid
Apply, make the high antireflection reinforced glass with triple layer anti reflective film, be equally measured.Show the result in table 3.Even if understanding
It is to form by the glass substrate of three layers of antireflection film constituted, it is strong also to have carried out sufficient glass by the method for the present invention
Change.
High refraction coating liquid：
Mix and prepare at room temperature.
Middle refraction coating liquid：
Mix and prepare at room temperature.
[table 3]
Claims (6)
1. a kind of manufacture method of high antireflection reinforced glass,
Methods described forms the low refraction that the refractive index at least contained positioned at visual field side is less than 1.45 on the surface of glass substrate
Rate layer and positioned at glass substrate side refractive index be 1.55 antireflection film less than 2.00 high refractive index layer after, to shape
The chemical intensification treatment using ion-exchange is carried out into the glass substrate for having antireflection film, so as to manufacture high antireflection reinforcing glass
Glass, it is characterised in that
High index of refraction coating liquid is coated on the glass substrate, then, is coated to low-refraction coating liquid, then, with 100~
500 DEG C of temperature carries out being thermally formed antireflection film, then, ion exchange with metal salt fused solution with 380~500 DEG C
Temperature carries out chemical intensification treatment；
The high index of refraction coating liquid contains：
(a) silicon compound shown in following formula (1),
Rn-Si(OR1)4-n (1)
In formula (1), R is alkyl or alkenyl,
R1For alkyl or alkoxyalkyl,
N is 0~2 integer；
(b) the high index of refraction inorganic oxide particles formed by zirconium oxide and/or titanium dioxide granule；And,
(c) metallo-chelate,
The mass ratio (a/b) of the silicon compound (a) and high index of refraction inorganic oxide particles (b) is 50/50~95/5
Scope, total amount of the metallo-chelate (c) relative to silicon compound (a) and high index of refraction inorganic oxide particles (b)
100 parts by weight are the scope below 20 parts by weight,
The low-refraction coating liquid contains：
(a) silicon compound shown in the formula (1)；
(d) it is internal that there is empty hollow silica particle；And,
(c) metallo-chelate,
The scope that the mass ratio (a/d) of the silicon compound (a) and hollow silica particle (d) is 50/50~99/1, it is described
Metallo-chelate (c) is 20 weight relative to the parts by weight of total amount 100 of silicon compound (a) and hollow silica particle (d)
Scope below part.
2. the manufacture method of high antireflection reinforced glass according to claim 1, it is characterised in that antireflection film is rolled in height
Penetrate rate layer glass substrate side further have refractive index be 1.50 less than 1.90, refractive index be less than high refractive index layer
Middle index layer,
Before coated high index of refraction coating liquid, refractive index coating liquid in being coated to,
The middle refractive index coating liquid contains：
(a) silicon compound shown in the formula (1)；
(e) the middle refractive index inorganic oxide particles formed by zirconium oxide and/or titanium dioxide granule；And,
(c) metallo-chelate,
The mass ratio (a/e) of the silicon compound (a) and middle refractive index inorganic oxide particles (e) is 50/50~95/5
Scope, total amount of the metallo-chelate (c) relative to silicon compound (a) and middle refractive index inorganic oxide particles (e)
100 parts by weight are the scope below 20 parts by weight.
3. the manufacture method of high antireflection reinforced glass according to claim 1 or 2, wherein, the silicon compound is four
Ethoxysilane.
4. the manufacture method of the high antireflection reinforced glass according to any one of claims 1 to 3, it is characterised in that
Carry out being thermally formed antireflection film with 200~300 DEG C of temperature.
5. the manufacture method of the high antireflection reinforced glass according to any one of Claims 1 to 4, it is characterised in that
Chemical intensification treatment is carried out with 380~480 DEG C of temperature.
6. the manufacture method of the high antireflection reinforced glass according to any one of Claims 1 to 5, it is characterised in that
The shape processing of glass substrate is carried out after the antireflection film is formed and before the chemical intensification treatment.
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| JP2016063685A JP6606451B2 (en) | 2016-03-28 | 2016-03-28 | Manufacturing method of high antireflection tempered glass |
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| JP7268006B2 (en) * | 2018-04-19 | 2023-05-02 | フクビ化学工業株式会社 | Antireflection plate |
| CN117425632A (en) * | 2021-08-23 | 2024-01-19 | 福美化学工业株式会社 | Anti-reflection glass |
| WO2023063221A1 (en) * | 2021-10-12 | 2023-04-20 | フクビ化学工業株式会社 | Optical member |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1950197A (en) * | 2004-04-06 | 2007-04-18 | 帝人杜邦薄膜日本有限公司 | Antireflective film |
| CN101772470A (en) * | 2007-08-03 | 2010-07-07 | 日本电气硝子株式会社 | Hardened glass substrate and method for manufacturing the same |
| CN102574735A (en) * | 2009-10-20 | 2012-07-11 | 福美化学工业株式会社 | Method for producing antireflection reinforced glass |
| CN103842856A (en) * | 2011-08-01 | 2014-06-04 | 福美化学工业株式会社 | Anti-reflective film and anti-reflective plate |
| CN104118994A (en) * | 2013-04-23 | 2014-10-29 | 旭硝子株式会社 | Glass substrate with reflective films on both sides, and process for its production |
| WO2016037753A1 (en) * | 2014-09-12 | 2016-03-17 | Schott Ag | Method for producing a coated, chemically prestressed glass substrate having anti-fingerprint properties, and the produced glass substrate |
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| JP4100863B2 (en) * | 2000-10-23 | 2008-06-11 | 触媒化成工業株式会社 | Photoelectric cell |
| WO2011149694A1 (en) * | 2010-05-26 | 2011-12-01 | Corning Incorporated | Ion-exchanging an ar coated glass and process |
| JP2014091743A (en) * | 2012-10-31 | 2014-05-19 | Olympus Corp | Coating material, optical coating film and optical element |
| JP2017132644A (en) * | 2014-06-06 | 2017-08-03 | 旭硝子株式会社 | Chemically strengthened glass sheet with functional film, manufacturing method, and article thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1950197A (en) * | 2004-04-06 | 2007-04-18 | 帝人杜邦薄膜日本有限公司 | Antireflective film |
| CN101772470A (en) * | 2007-08-03 | 2010-07-07 | 日本电气硝子株式会社 | Hardened glass substrate and method for manufacturing the same |
| CN102574735A (en) * | 2009-10-20 | 2012-07-11 | 福美化学工业株式会社 | Method for producing antireflection reinforced glass |
| CN103842856A (en) * | 2011-08-01 | 2014-06-04 | 福美化学工业株式会社 | Anti-reflective film and anti-reflective plate |
| CN104118994A (en) * | 2013-04-23 | 2014-10-29 | 旭硝子株式会社 | Glass substrate with reflective films on both sides, and process for its production |
| WO2016037753A1 (en) * | 2014-09-12 | 2016-03-17 | Schott Ag | Method for producing a coated, chemically prestressed glass substrate having anti-fingerprint properties, and the produced glass substrate |
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