CN103781739A - Process for producing cover glass for potable appliance - Google Patents

Process for producing cover glass for potable appliance Download PDF

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Publication number
CN103781739A
CN103781739A CN201280043503.6A CN201280043503A CN103781739A CN 103781739 A CN103781739 A CN 103781739A CN 201280043503 A CN201280043503 A CN 201280043503A CN 103781739 A CN103781739 A CN 103781739A
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ion
glass
fused salt
fused
additive
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今井贡
桥本和明
杉原理
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Hoya Corp
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Hoya Corp
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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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
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Abstract

The invention provides a process for producing a cover glass for portable appliances. The process comprises an ion-exchange step in which a glass article of a lithium-containing composition is brought into contact with a salt melt that contains an alkali metal element having a larger ionic radius than lithium, which is contained in the glass, to thereby cause ion exchange between some of the lithium contained in the glass article and the alkali metal contained in the salt melt. At least one additive selected from the group consisting of NaF, KF, K3AlF6, Na2CO3, NaHCO3, K2CO3, KHCO3, Na2SO4, K2SO4, KAl(SO4)2, Na3PO4 and K3PO4 is added to the salt melt, and the ion-exchange step is conducted so that the additive is in a solid state.

Description

The manufacture method of protective glass for portable equipment
Technical field
The present invention relates to for mobile phone or PDA(palm PC), the manufacture method of the portable equipment protective glass of the portable equipment such as portable game machine.
Background technology
In order to improve the intensity of glasswork, conventionally carry out chemical enhanced processing.This chemical enhanced processing refers to: contact with glasswork by the chemical enhanced salt that makes melting, make the relatively little alkali metal of ionic radius in ionic radius in chemical enhanced salt relatively large alkali metal and glass carry out ion-exchange, on the top layer of glasswork, soak into the alkali metal that above-mentioned ionic radius is larger, make glass article surface produce the processing of stress under compression.For example in glass, exist in the alkali-metal situations such as Li, Na, K, by with there is the more basic metal of heavy ion radius and replace mutually (for the Li in glass, Na, the K larger with ionic radius replace, for the Na in glass, the K larger with ionic radius replaces), improve the stress under compression of surface layer of glass, can improve the intensity of glasswork, improve shock-resistance.
, in the past known, if carry out so chemical enhanced processing, for example Li ion that can produce stripping from glass is accumulated in fused salt, causes the Li ionic concn in fused salt to raise gradually, thereby makes ion-exchange be difficult to the problem of carrying out.
In patent documentation 1, disclose: using KNO 3, K 2sO 4, KCl fused salt mixt when soda-lime glass is carried out to chemical enhanced processing, by adding as rich K in this fused salt mixt +the known special clay particle of hectorite of ion, can be by the Na separating out from soda-lime glass +the concentration of ion in fused salt mixt maintains lower level.In addition, in this patent documentation 1, except above-mentioned hectorite, as the material of regeneration intensive treatment liquid, can illustrate the clay such as wilkinite or polynite and/or silicate, borate, the glassiness and non-vitreous aluminosilicate, can fix the solid gums of proton and/or alkalimetal ion etc.
Prior art document
Patent documentation 1: Japanese Patent Publication 46-39117 communique
Summary of the invention
The problem that invention will solve
But, the unexposed mechanism for the intensive treatment liquid of regenerating in above-mentioned patent documentation 1, according to the kind difference of the kind of used glass or fused salt, comprise regeneration insufficient or react with water or for the immiscible material of the acid, the alkali that wash, with the water of washing and invade the material that the material etc. of glass surface cannot use.
In recent years, as the glasswork of having implemented chemical enhanced processing, for example, can enumerate protective glass that portable equipment uses etc.
In the past; in the portable equipment such as mobile phone or PDA, portable game machine; its display frame is generally used the acrylic resin board of transparent excellence and light weight; but in recent years, thinly also there is the protective glass that the aspects such as high strength and surface smoothness, protectiveness (weathering resistance, didirtresistance), outward appearance, feeling of high class all form than the glass material of acrylic resin board excellence in the past and replace acrylic resin board in the past even if mostly use.
In recent years, the portable equipment of touch panel formula occupies main flow.In touch panel mode; mainly such as, carry out the operation of portable equipment by the regulation position (icon that picture is shown etc.) of pressing display frame; but owing to repeatedly pressing continually; therefore; require the intensity of the display frame that improves this touch panel function of reply; therefore, even if require slim, light weight, large picture (big area) also to there is the protective glass of sufficient intensity.
Under these circumstances; even if apply the renovation process of the chemical enhanced treatment solution as disclosed in above-mentioned patent documentation 1; also likely make fertile absorber be attached on glass surface; intensity non-uniformity strengthens; existence is difficult to the problem of the chilled glass that obtains stability of characteristics, even if be particularly difficult to solve desired slim, the light weight of the protective glass can stably manufactured using in touch panel formula portable equipment as main flow in recent years, large picture (big area) and also have the problem of the goods of abundant intensity.
The present invention completes in order to solve such problem in the past, and its object is to provide the manufacture method of a kind of portable equipment protective glass, in the life-span that it can keep more longways fused salt in chemical enhanced processing, can obtain the chilled glass goods of stability of characteristics.The present invention provides a kind of manufacture method of the portable equipment protective glass that is applicable to the middle protective glasses that use such as touch panel formula portable equipment especially.
Solve the means of problem
The inventor conducts in-depth research in order to solve above-mentioned problem, found that, the invention with following technical scheme can solve above-mentioned problem.
, the present invention has following technical scheme.
(scheme 1)
The manufacture method of protective glass for a kind of portable equipment; comprise ion-exchange process; the glasswork of described ion-exchange process by making the composition that contains Li contacts with the fused salt fused solution that contains ionic radius and be greater than the alkali metal of Li contained in this glass; basic metal in Li in described glasswork and described fused salt fused solution is carried out to ion-exchange; it is characterized in that
To be selected from NaF, KF, K 3alF 6, Na 2cO 3, NaHCO 3, K 2cO 3, KHCO 3, Na 2sO 4, K 2sO 4, KAl (SO 4) 2, Na 3pO 4, K 3pO 4in at least one additive add in described fused salt fused solution, described additive carries out described ion-exchange process with solid state.
(scheme 2)
The manufacture method of protective glass for a kind of portable equipment; comprise ion-exchange process; the glasswork of described ion-exchange process by making the composition that contains Na contacts with the fused salt fused solution that contains ionic radius and be greater than the alkali metal of Na contained in this glass; basic metal in Na in described glasswork and described fused salt fused solution is carried out to ion-exchange; it is characterized in that
To be selected from KCl, KBr, KF, K 3alF 6, K 2cO 3, KHCO 3, K 2sO 4, KAl (SO 4) 2, K 3pO 4in at least one additive add in described fused salt fused solution, described additive carries out described ion-exchange process with solid state.
(scheme 3)
The manufacture method of protective glass for a kind of portable equipment; comprise ion-exchange process; the glasswork of described ion-exchange process by making the composition that contains Li contacts with the fused salt fused solution that contains ionic radius and be greater than the alkali metal of Li contained in this glass; basic metal in Li in described glasswork and described fused salt fused solution is carried out to ion-exchange; it is characterized in that
Additive is added in described fused salt fused solution, the fusing point of described additive is higher than the Heating temperature of described fused salt fused solution, and with react the compound of this Li separated out as solid in described fused salt fused solution to the Li in described fused salt fused solution by the stripping from glass of described ion-exchange process, described additive carries out described ion-exchange process with solid state.
(scheme 4)
The manufacture method of protective glass for portable equipment as described in scheme 1～3 any one, is characterized in that, described ion-exchange is low temperature modification ion-exchange.
(scheme 5)
The manufacture method of protective glass for portable equipment as described in scheme 1～4 any one; it is characterized in that; select described additive as follows: even if the precipitate precipitateing in described fused salt fused solution by described ion-exchange process is attached to glass article surface, also can remove the precipitate that is attached to this glass article surface by cleaning glass goods after described ion-exchange process.
(scheme 6)
The manufacture method of protective glass for portable equipment as described in scheme 1～5 any one, is characterized in that, selects described additive, makes to precipitate into precipitate in described fused salt fused solution by described ion-exchange process different from the proportion of described fused salt fused solution.
(scheme 7)
The manufacture method of protective glass for portable equipment as described in scheme 3～6 any one, is characterized in that, described additive is the compound that contains alkali metal component.
(scheme 8)
The manufacture method of protective glass for portable equipment as described in scheme 7, is characterized in that, in described additive, contained alkali metal component comprises the composition identical with basic metal contained in described fused salt fused solution.
(scheme 9)
The manufacture method of protective glass for portable equipment as described in scheme 1～8 any one; it is characterized in that; in the refrigerating work procedure or washing procedure of chemical enhanced glasswork after treatment, when glasswork contacts with the aqueous solution, the PH of the aqueous solution on glass article surface is less than 10.
Invention effect
Manufacture method according to portable equipment according to the present invention with protective glass, in the life-span that it can keep more longways fused salt in chemical enhanced processing, can obtain the portable equipment protective glass of the stability of characteristics that intensity non-uniformity etc. is little.Even if particularly can obtain being applicable to requiring slim, light weight, large picture (big area) also to there is the chilled glass of the stability of characteristics of the protective glass of the touch panel formula portable equipment etc. of abundant intensity.
Accompanying drawing explanation
Figure 1A is the front elevation that represents the fixture structure using in 4 pliability tests;
Figure 1B is the side elevational view that represents the fixture structure using in 4 pliability tests.
Embodiment
Below, describe embodiments of the present invention in detail.
One of embodiments of the present invention are the manufacture method of a kind of portable equipment protective glass; as described in such scheme 1; comprise ion-exchange process; the glasswork of described ion-exchange process by making the composition that contains Li contacts with the fused salt fused solution that contains ionic radius and be greater than the alkali metal of Li contained in this glass; basic metal in Li in described glasswork and described fused salt fused solution is carried out to ion-exchange; it is characterized in that, will be selected from NaF, KF, K 3alF 6, Na 2cO 3, NaHCO 3, K 2cO 3, KHCO 3, Na 2sO 4, K 2sO 4, KAl (SO 4) 2, Na 3pO 4, K 3pO 4in at least one additive add in described fused salt fused solution, described additive carries out described ion-exchange process with solid state.
In addition; second object of embodiment of the present invention is the manufacture method of a kind of portable equipment protective glass; as described in such scheme 2; comprise ion-exchange process; the glasswork of described ion-exchange process by making the composition that contains Na contacts with the fused salt fused solution that contains ionic radius and be greater than the alkali metal of Na contained in this glass; basic metal in Na in described glasswork and described fused salt fused solution is carried out to ion-exchange, it is characterized in that, will be selected from KCl, KBr, KF, K 3alF 6, K 2cO 3, KHCO 3, K 2sO 4, KAl (SO 4) 2, K 3pO 4in at least one additive add in described fused salt fused solution, described additive carries out described ion-exchange process with solid state.
Key character of the present invention is, can keep muchly the life-span of fused salt in chemical enhanced processing, can obtain the chilled glass goods (portable equipment protective glass) of stability of characteristics.It is characterized in that the stabilization of the characteristic of the long lifetime of fused salt and chilled glass goods.
As mentioned above, so-called this chemical enhanced processing refers to that the chemical enhanced salt by making melting contacts with glasswork, alkali metal relatively little ionic radius in alkali metal relatively large ionic radius in chemical enhanced salt and glass is carried out to ion-exchange, on the top layer of glasswork, soak into the alkali metal that above-mentioned ionic radius is larger, produce the processing of stress under compression at glass article surface.
For example,, in the situation that containing Li, Na, K as alkali-metal glass, by being immersed in for example KNO 3and NaNO 3fused salt mixt fused solution in, a part for basic ion less ionic radius is replaced into its large basic metal of ratio of ionic radii, carry out thus chemical enhanced.Be explained, the size order of ionic radius is Li +<Na +<K +.
If the glasswork of the composition that contains Li is carried out to ion-exchange in the fused salt fused solution that contains Na and/or K, Li ion stripping from glass.And, if the Li ion in fused salt fused solution increases, the Li ion being incorporated in Na, K and the fused salt fused solution in the glass in glass by ion-exchange becomes equilibrium state, even cost more times, Na, the K ion of fused salt can not enter into glass yet.
Therefore, in the past, the Li ionic concn in the fused salt fused solution as the chemical enhanced ion of obstruction need to be replaced with fused salt fused solution new fused solution before reaching a certain numerical value.In the past in the situation that, the fused salt fused solution of new system that not only must the large storage capacity of keeping, and also the strengthening degree that produces glass also changes with together with Li ionic concn in fused salt fused solution, cannot obtain the problem of the uniform chilled glass of characteristic.
In order to solve in the past such problem, in the present invention, use additive, described additive in the Heating temperature of fused salt fused solution (temperature of fused salt fusing), to carry out at the temperature of ion-exchange be solid, react to the Li ion (or Na ion) in fused salt fused solution with stripping from glass, for using this Li ion (or Na ion) outside precipitate is discharged to system, i.e. (outside liquid state) beyond fused salt fused solution.As such additive, using for example at KNO 3and NaNO 3fused salt mixt fused solution or KNO 3or NaNO 3the salt of Heating temperature (ion-exchange temperature) lower Na, the K for solid of independent fused salt fused solution (for example, carbonate) situation under, in fused salt fused solution, although the carbonate of these Na, K is solid, but there is replacement(metathesis)reaction in the Na, the K that cause the Li ion that exists in fused salt fused solution and carbonate, generates Li 2cO 3, can remove precipitation with solid form.
As mentioned above, although to carry out chemical enhanced situation as alkali-metal glass and be illustrated as example containing Li, Na, K, but Li is not entered glass and contains Na and the glass of K or the glass that contains Na carry out in the situation of ion-exchange, for example, as the composition (host) of fused salt, use KNO 3, as additive, the carbonate that adds K is K 2cO 3.
That is, now, chemical enhanced obstruction ion becomes Na ion, therefore, makes Na ion selectivity as carbonate deposition, from reaction system, removes.By the way, Na 2cO 3fusing point be 851 ℃, K 2cO 3fusing point be 891 ℃, therefore, by carry out ion-exchange below this temperature, can make Na 2cO 3or K 2cO 3from fused salt fused solution, separate out with solid form as precipitate.
In fused salt fused solution, do not add while carrying out chemical enhanced processing such additive (previous methods), Na ion is accumulated in fused salt fused solution gradually, turns back in glass, and strengthening reaction becomes and is difficult to carry out.
The present invention can be applicable to carry out chemical enhanced at least one glasswork as alkali-metal composition that contains Li and Na.Except the glass of the Li of containing described above, Na, K, contain Na and K glass, glass that also can be applicable to the glass that contains Li, the glass that contains Li and Na, the glass that contains Li and K, contains Na etc. chemical enhanced.
As mentioned above, fused salt for chemical enhanced various glass forms according to the composition of each glass and difference, in addition, in the present invention, for compared with keeping longways the life-span of fused salt and making chemical enhanced stability keep material certain and additive that add also different, but for example for the glasswork containing the composition of Li, generally speaking, additive is added in fused salt fused solution, the fusing point of described additive is than the Heating temperature of fused salt fused solution (ion-exchange temperature) height, and with by ion-exchange process, the Li from glass stripping to fused salt fused solution reacts the compound of this Li is separated out as solid in fused salt fused solution, this additive carries out above-mentioned ion-exchange process with solid state.
And then, it is desirable to, preferably can be by this product and/or additive being dissolved in to the material that in water for example, washing is removed, in addition, particularly preferably reacting and the material of the fused salt host of regenerating by the obstruction ion of additive and stripping from glass.
In the present invention, as the additive adding in fused salt fused solution, for example, can preferably enumerate: the carbonate of Na, K, phosphoric acid salt, vitriol, fluorochemical etc.
Below, enumerate the main concrete example of the preferably combination of glass reinforced salt composition in the present invention and additive, but the present invention is not limited thereto.
The glass that contains Li as basic metal, the glass that contains Li and Na, the glass that contains Li and K, contain Li, Na and K glass chemical enhanced in, the composition of fused salt host can preferably use for example NaNO 3, KNO 3, NaNO 3and KNO 3mixing salt in any, for these any fused salts, as additive, can preferably use and for example be selected from NaF, KF, K 3alF 6, Na 2cO 3, NaHCO 3, K 2cO 3, KHCO 3, Na 2sO 4, K 2sO 4, KAl (SO 4) 2, Na 3pO 4, K 3pO 4in at least one additive.
In addition, in the case of the glass composition containing Li not, the glass that contains Na as basic metal, contain Na and K glass chemical enhanced in, the composition of fused salt host can preferably use for example KNO 3, for this fused salt, as additive, can preferably use and for example be selected from KCl, KBr, KF, K 3alF 6, K 2cO 3, KHCO 3, K 2sO 4, KAl (SO 4) 2, K 3pO 4in at least one additive.
In addition, in the present invention, in above-mentioned additive, most preferably above-mentioned alkali-metal carbonate, particularly preferably vitriol, more preferably phosphoric acid salt, secondly preferred fluorinated thing.Wherein, from order not cause damage and/or can not carry out chilled glass goods ion-exchange and invade the viewpoint of this glass article surface and consider, preferably sulfuric acid salt, carbonate, phosphoric acid salt due to washing carrying out the chemical enhanced groove of ion-exchange.
In addition, in the selection of above-mentioned additive, preferably select to have the additive of following performance: in the time removing the chemical enhanced fused salt of chemical enhanced processing postadhesion on protective glass surface (for example, in the time contacting with the water of refrigerating work procedure (also referred to as thermal shocking operation) or chemical enhanced washing procedure after treatment etc. that the temperature of chemical enhanced glass substrate after treatment is declined), by becoming compared with the little basic metal reaction product that for example Li separates out as solid in fused salt fused solution with reacting of above-mentioned additive the material that forms neutral solution on protective glass surface to the ionic radius in fused salt fused solution by ion-exchange process stripping from glass.Its reason is, in the time that above-mentioned reaction product contacts with water, for example, while becoming strong basicity, likely causes glass surface etched and make surfaceness deteriorated.
As mentioned above, for example, containing Li as in alkali-metal glass chemical enhanced, as above-mentioned additive, for example, can use vitriol, the carbonate etc. of Na and/or K, wherein, in the case of adding the vitriol of Na and/or K, as shown in following chemical equation, cause the Li ion of the stripping from glass existing in fused salt fused solution (as LiNO in fused salt fused solution 3exist) with the Na of above-mentioned vitriol, the replacement(metathesis)reaction of K, generate Li 2sO 4.
2LiNO 3+Na 2SO 4→Li 2SO 4+2NaNO 3
2LiNO 3+K 2SO 4→Li 2SO 4+2KNO 3
Li now 2sO 4although separate out as solid in fused salt fused solution; but while contact with water in refrigerating work procedure and/or the washing procedure etc. of chemical enhanced protective glass after treatment, dissolve and become neutrality; on protective glass surface, form neutral solution (PH=7 left and right); therefore; can not make the surfaceness of protective glass deteriorated, thereby preferably.
On the other hand, in the case of adding the carbonate of Na and/or K, as shown in following chemical equation, cause the Li ion of the stripping from glass existing in fused salt fused solution (as LiNO in fused salt fused solution 3exist) with the Na of above-mentioned carbonate, the replacement(metathesis)reaction of K, generate Li 2cO 3.
2LiNO 3+Na 2CO 3→Li 2CO 3+2NaNO 3
2LiNO 3+K 2CO 3→Li 2CO 3+2KNO 3
Li now 2cO 3although separate out as solid in fused salt fused solution; but while contact with water in refrigerating work procedure and/or the washing procedure etc. of chemical enhanced protective glass after treatment, dissolve and become strong basicity; on protective glass surface, form strong alkali solution (PH>10); therefore; likely make the surfaceness of protective glass deteriorated, or corrode chemical enhanced groove (being generally stainless material).Particularly local deteriorated in the situation that in protective glass surface upper surface roughness, likely in the face on protective glass surface, produce the inhomogeneous of surfaceness, and may produce inhomogeneous by the face of the inhomogeneous light transmission causing of surfaceness.
Therefore, containing Li as in alkali-metal glass chemical enhanced, consider from the viewpoint of the surfaceness of chemical enhanced protective glass after treatment, as above-mentioned additive, particularly preferably use the vitriol of Na and/or K.Wherein, while using the vitriol of K, as shown in above-mentioned chemical equation, generate KNO 3, therefore, K ion when can supplementing along with chemical enhanced carrying out and in the fused salt fused solution reducing, thereby preferably.
In addition, according to above reason, preferably, in the refrigerating work procedure or washing procedure of chemical enhanced protective glass after treatment, when protective glass contacts with the aqueous solution, the PH of the lip-deep aqueous solution of protective glass is less than 10.
Be explained, in the case of adding the carbonate of Na and/or K in fused salt fused solution, before contacting with water in refrigerating work procedure and/or washing procedure etc., make the solution of glass surface become neutral region during it is contacted with weak acid and/or buffered soln, can suppress to follow the deteriorated of etched local surfaces roughness, thereby preferably.
In addition, for the addition of additive, the amount of separating out as solid precipitate as long as the ion in can be using stripping from glass to fused salt fused solution, and can not hinder the amount of reinforcing degree downwards when precipitating or swim in a large number etc.In addition, for example, as the addition manner of additive,, can before ion-exchange, add carrying out, in addition, for example, in the situation that multiple glassworks being carried out to ion-exchange by batch processing, also can in every batch processing or every several batch processing, add additive.Be explained, as the structure of chemical enhanced groove that carries out ion-exchange, for example, the intermittent type strengthening groove that multiple glass is carried out changing after primary ions exchange glass can be adopted, also continuous transport glass can be adopted and the continous way strengthening groove that carries out ion-exchange.
As described above, in the present invention, important point is, add the fusing point of the additive in fused salt fused solution to higher than the Heating temperature of fused salt fused solution, this additive carries out ion-exchange process with solid state, and, by add this additive in fused salt fused solution, and react the compound of this Li is separated out as solid in fused salt fused solution compared with for example Li of little basic metal to the ionic radius in fused salt fused solution by ion-exchange process stripping from glass.In the present invention, by add above-mentioned additive in fused salt fused solution, prevent that the chemical enhanced less alkalimetal ion of ionic radius of the obstruction of stripping is present in fused salt fused solution as ion from glass, therefore, can make the compound of this ion separate out as solid, can suppress these and hinder accumulating of ion.
In addition, contain Li in chemical enhanced glass in the case of carrying out, the easily stripping in fused salt fused solution compared with Na ion etc. of Li ion, therefore, the glass of the present invention to the composition that contains Li chemical enhanced effective especially.
Be explained; particularly preferably select such additive; it makes: even if the precipitate of separating out in fused salt fused solution by ion-exchange process is attached to the surface of glasswork (portable equipment protective glass), and also can be by glasswork being washed to remove the precipitate that is attached to this glass article surface after ion-exchange process.Therefore, preferably precipitate is dissolved in the material in such as water, acid or weak base etc.
In addition, particularly preferably selection makes the precipitate additive different from the proportion of fused salt fused solution of separating out in fused salt fused solution by ion-exchange process.This is because by the cause of easily removing precipitate from fused salt fused solution with filtrations such as strainers.
Particularly preferably determine the composition of fused salt and the composition of additive, make above-mentioned precipitate be trapped in the bottom of the chemical enhanced groove that carries out ion-exchange or be suspended in fused salt fused solution with non-suspended state in fused salt fused solution.In the case of determining that the composition of fused salt and additive, so that precipitate is trapped in chemical enhanced groove, can prevent that above-mentioned precipitate is attached to the surface of the goods that carried out ion-exchange.In addition, in the case of determine the composition of fused salt and additive so that precipitate be suspended in fused salt fused solution in, easily remove above-mentioned precipitate.
In addition, as the addition manner of additive, for example, can add in fused salt fused solution with powder shaped, in addition, for example, also can add with bulk form such as particles.Particularly the viewpoint of reaction table area of the alkalimetal ion from the composition of the glass fused salt fused solution with stripping and the viewpoint of processing ease are considered, more preferably add with the bulk of 5～50g.In addition, also can adopt fused salt fused solution to be made as circulating, in the way of circulation path, strainer be set and trap the structure of above-mentioned precipitate.
In addition, the additive using in the present invention preferably contains the compound of alkali metal component, and especially, particularly preferably in additive, contained alkali metal component contains the composition identical with basic metal contained in fused salt fused solution.Although alkali metal component contained in additive may not be identical with basic metal contained in fused salt fused solution, but identical in the situation that, by the ion-exchange of the alkalimetal ion in the alkalimetal ion in glass and fused salt fused solution, can supplement the alkalimetal ion in the fused salt fused solution reducing with alkalimetal ion contained in additive, be therefore preferred.If this is elaborated, from glass, stripping, to alkalimetal ion and additive generation solid state reaction in fused salt fused solution, becomes precipitate.Now, from additive, discharge alkalimetal ion.Carry out by the alkalimetal ion discharging being made as in advance with glass the ion that alkalimetal ion in the fused salt fused solution of ion-exchange is identical from this additive, can supplement the alkalimetal ion in the fused salt fused solution reducing due to ion-exchange., as mentioned above, keep certain viewpoint to consider from renewable fused salt host and by the alkalimetal ion concentration fused salt, more preferably identical ion.Now, fused salt can semi-permanently use principle, does not need to change fused salt, as long as append as required and often remove the degree of unwanted reaction product.
As described above, in the present invention, can suppress to accumulate and hinder produced by ion-exchange chemical enhanced compared with little alkalimetal ion by the ionic radius of ion-exchange process stripping from glass, therefore, the life-span of fused salt can be kept more longways, the replacing number of times of fused salt can be reduced significantly.As mentioned above, can substantially not change fused salt.In addition, can not produce as the change in concentration by the obstruction ion in fused salt in the past and the bad phenomenon that causes the strengthening degree of glass to change, therefore, the ununiformity of intensity is less, can stably manufacture the chilled glass goods with uniform properties.
The present invention is specially adapted to the manufacture of portable equipment protective glass.Protective glass stronger intensity of requirement compared with other glasswork for portable equipment, in order to improve intensity, chemical enhanced processing is absolutely necessary.
Consider from the reply slimming of handheld device and the viewpoint of the light-weighted market requirement in recent years; this portable equipment is preferably the scope of for example 0.3mm～1.5mm left and right with the thickness (thickness of slab) of protective glass, the scope of more preferably 0.5mm～0.7mm left and right.
Form portable equipment and be preferably unbodied alumina silicate glass with the glass of protective glass.The intensity of the glass substrate being made up of this alumina silicate glass after chemical enhanced is very good.As this alumina silicate glass, can use and contain by oxide compound conversion SiO 2: 58～75 % by weight, Al 2o 3: 0～20 % by weight, Li 2o:0～10 % by weight, Na 2o:4～20 % by weight, ZrO 2: 5.5 % by weight～15 % by weight are as the alumina silicate glass of principal constituent.In addition, as other preference, can enumerate the alumina silicate glass with following composition: convert by oxide compound, SiO 2: 63～70mol%, Al 2o 3: 4～11mol%, Li 2o:5～11mol%, Na 2o:6～14mol%, K 2o:0～2mol%, TiO 2: 0～5mol%, ZrO 2: 0～2.5mol%, RO:2～15mol%, wherein, RO=MgO+CaO+SrO+BaO, MgO:0～6mol%, CaO:1～9mol%, SrO:0～3mol%, BaO:0～2mol%, other: 0～3mol%, above-mentioned SiO 2with above-mentioned Al 2o 3poor (the SiO of molar ratio (mol%) separately 2-Al 2o 3) be more than 56.5mol%.
As mentioned above, at portable equipment with improving intensity in protective glass, must carry out chemical enhanced processing with substrate to protective glass.
As the method for chemical enhanced processing, preference as being no more than the temperature province of second-order transition temperature, for example, carries out the low temperature modification ion exchange method of ion-exchange etc. at the temperature of 300 degree～500 degree Celsius.
The detailed content of the chemical enhanced processing (ion-exchange process) in the present invention is described above.This chemical enhanced processing is by loading multiple protective glasses and it is carried out in impregnated in heating and melting to have the fused salt fused solution of chemical enhanced salt (chemical enhanced treatment solution) on the general substrate holder also referred to as shelf etc.After chemical enhanced processing, can also comprise protective glass is taken out from fused salt fused solution with the state still loading on substrate holder, direct impregnation in water-soluble liquid bath so that the temperature of protective glass decline refrigerating work procedure.
The intensity of the protective glass after chemical enhanced improves and shock-resistance excellence, therefore, is applicable to apply impacts, presses and protective glass that the high-intensity portable equipment of needs uses.Particularly in the present invention, can stably manufacture by the chemical enhanced intensity inequality causing and reduce and the uniform portable equipment protective glass of characteristic.
Embodiment
Below, enumerate specific embodiment and be described more specifically the present invention.Be explained, the present invention is not limited to following embodiment.
(embodiment 1)
Cut off manufacturing procedure, (2) chemical enhanced operation via following (1) sheet glass, manufacture the portable equipment protective glass of the present embodiment.
(1) sheet glass cuts off manufacturing procedure
First, the sheet glass of the significantly size of the thickness 0.5mm that the alumina silicate glass of manufacturing by glass tube down-drawing or float glass process is formed cuts off, and makes the protective glass (protective glass substrate) of prescribed level (long limit 10cm × minor face 5cm).As this alumina silicate glass, use and contain SiO 2: 58～75 % by weight, Al 2o 3: 5～23 % by weight, Li 2o:3～10 % by weight, Na 2o:4～13 % by weight, ZrO 2: the chemical enhanced glass of using of 5.5～15 % by weight.The cut-out of this sheet glass is undertaken by mechanical workout.
(2) chemical enhanced operation
Then, implement chemical enhanced to above-mentioned protective glass.Chemical enhanced use saltpetre (KNO 3) as fused salt, and the ratio of preparing using addition as 70g/4.5kg fused salt host weight is added the sodium carbonate (Na as additive 2cO 3) fused salt fused solution, this fused salt fused solution is heated to 360～380 ℃, above-mentioned protective glass is flooded approximately 2～4 hours, carry out chemical enhanced processing.Processing number is 100.
Be immersed in successively pure water, IPA, IPA(steam drying by having completed chemical enhanced protective glass) each rinse bath in, carry out ultrasonic washing dry.
Manufacture like this protective glass for portable equipment (100) of the present embodiment.Be explained, the precipitate of separating out in the fused salt fused solution after above-mentioned chemical enhanced operation completes reflected by XRD(X ray) analyze,, there is in a large number Quilonum Retard in results verification.
100 protective glasses manufacturing are evaluated to its intensity inequality.Particularly, 4 flexural strengths (unit: MPa) of the protective glass major surfaces that uses 4 bending methods mensuration are measured, obtained the ratio that intensity is protective glass more than 500MPa.
At this, 4 bending methods are described.
4 pliability tests are implemented test based on JIS standard R1602.4 pliability tests refer to; test film (in this case protective glass) is placed on two fulcrums of configuration at a certain distance; be divided into and be positioned at two applied loads equidistant from the central left and right between fulcrum, the maximum stress in bend when destroying is measured as 4 flexural strengths.
In the present embodiment, use rotary-type 4 the pliability test fixtures as shown in Figure 1A, Figure 1B.On pedestal 2, be provided with the supporting member 3,3 of two the roller shapes in left and right of configuration at a certain distance, above supporting member, dispose pinblock 4, be provided with the supporting member 5,5 of two the roller shapes in left and right of configuration at a certain distance at the downside of pinblock 4.On two supporting members 3,3 on pedestal 2, place test film 1, and pinblock 4 is declined from top, thus, be divided into 2 points of the supporting member 5,5 that is positioned at the pinblock 4 equidistant from the central left and right between the fulcrum of supporting member 3,3, to test film 1 applied load.The material of above-mentioned fixture is used SUS material.In addition, be made as 5～10mm/min the constant airspeed when load of pinblock 4.
The calculating formula that is related to of flexural strength is used following formula to calculate.
4 flexural strengths [MPa]=3P(L 1-L 2)/2wt 2
At this, P represents: the ultimate load [N] when rupture test sheet, L 1represent: the distance [mm] of (between the fulcrum of supporting member 3,3) between outside fulcrum, L 2represent: the distance [mm] of (between the fulcrum of supporting member 5,5) between inner fulcrum, w represents: the minor face width [mm] of test film, t represents: the thickness [mm] of test film.Be explained the long hem width degree L of test film 3be made as than above-mentioned L 1long distance.
In addition, confirm to have or not dirt settling on protective glass (after above-mentioned washing) surface by visual inspection.
Above acquired results is gathered and is shown in following table 1.
(embodiment 2)
In the chemical enhanced operation of embodiment 1, add sodium phosphate (Na with the ratio of " addition 70g/4.5kg fused salt host weight " 3pO 4) as adding the additive in fused salt fused solution to, in addition, operation, implements chemical enhanced operation similarly to Example 1, manufactures protective glass (100) for portable equipment.
(embodiment 3)
In the chemical enhanced operation of embodiment 1, add potassium sulfate (K with the ratio of " addition 70g/4.5kg fused salt host weight " 2sO 4) as adding the additive in fused salt fused solution to, in addition, operation, implements chemical enhanced operation similarly to Example 1, manufactures protective glass (100) for portable equipment.
(embodiment 4)
In the chemical enhanced operation of embodiment 1; add Potassium monofluoride (KF) as the additive adding in fused salt fused solution using the ratio of " addition 70g/4.5kg fused salt host weight "; in addition; operation similarly to Example 1; implement chemical enhanced operation, manufacture protective glass (100) for portable equipment.
(embodiment 5)
Use saltpetre and SODIUMNITRATE (mol ratio=8:2) as fused salt fused solution, in addition, operation, implements chemical enhanced operation similarly to Example 1, manufactures protective glass (100) for portable equipment.
To the protective glass obtaining in above embodiment 2～5, also having or not of valence ununiformity, surface attachments similarly to Example 1, its result is gathered and is shown in following table 1.
(comparative example 1)
In the chemical enhanced operation of embodiment 1, in fused salt fused solution, do not use additive, in addition, operation, implements chemical enhanced operation similarly to Example 1, manufactures protective glass (100) for portable equipment.
(comparative example 2)
In the chemical enhanced operation of embodiment 1; add hectorite as the additive adding in fused salt fused solution using the ratio of " addition 70g/4.5kg fused salt host weight "; in addition; operation similarly to Example 1; implement chemical enhanced operation, manufacture protective glass (100) for portable equipment.
To the protective glass obtaining in above comparative example 1,2, also having or not of valence ununiformity, surface attachments similarly to Example 1, its result is gathered and is shown in following table 1.
[table 1]
Figure BDA0000473892740000161
(embodiment 6)
Use the glass that represents to have following composition with % by weight: SiO 2: 58～66%, Al 2o 3: 13～19%, Li 2o:3～4.5%, Na 2o:6～13%, K 2o:0～5%, R 2o:10～18%, (wherein, R 2o=Li 2o+Na 2o+K 2o), MgO:0～3.5%, CaO:0～7%, SrO:0～2%, BaO:0～2%, RO:2～10%, (wherein, RO=MgO+CaO+SrO+BaO), TiO 2: 0～2%, CeO 2: 0～2%, Fe 2o 3: 0～2%, MnO:0～1%, wherein, TiO 2+ CeO 2+ Fe 2o 3the scope of+MnO=0.01～3%, in addition, with embodiment 1 and the same operation of comparative example 1,2, manufactures portable equipment protective glass.Then, evaluate 4 flexural strengths and surface attachments, obtained the result same with embodiment 1 and comparative example 1,2.
In an embodiment of the present invention, carry out continuously the chemical enhanced processing of 100 protective glasses, do not carry out the replacing of fused salt on the way, as shown in the result of above-mentioned table 1, all can obtain the protective glass that intensity non-uniformity is little.In addition, equal surface attachments that has gained protective glass unconfirmed.According to the present invention, in chemical enhanced processing, can keep more longways the life-span (the deteriorated of fused salt lacked) of fused salt, can stably manufacture the enhanced protection glass that intensity non-uniformity is little, the uniform portable equipment of characteristic is used.
On the other hand, do not add in the comparative example 1 of additive in fused salt fused solution, the intensity non-uniformity of the protective glass obtaining is large.Particularly, in the 50th later goods, intensity non-uniformity is large, and does not obtain the desired high strength of portable equipment protective glass.Think its reason be because, carry out continuously the chemical enhanced processing of 100 protective glasses, but fused salt is deteriorated on the way, cannot carry out for chemical enhanced ion-exchange process.In addition, in the comparative example 2 at interpolation hectorite (clay) as additive, fused salt fused solution becomes suspended state, even if also there is a large amount of surface attachments on the protective glass after washing, result cannot directly be used.In addition, intensity non-uniformity is also large than the result of the embodiment of the present invention, can not obtain the uniform chilled glass of characteristic.
(embodiment 7)
In the chemical enhanced operation of embodiment 1, carry out taking out from fused salt fused solution having completed chemical enhanced protective glass the refrigerating work procedure that the temperature of protective glass is declined.Coolingly in air, carry out at first, then, make protective glass be immersed in quenching in water.After cooling, carry out the washing of the dirt settling for removing protective glass.Except carrying out above refrigerating work procedure, operation, implements chemical enhanced operation similarly to Example 1.Add additive in fused salt fused solution to similarly to Example 1, use sodium carbonate with identical addition.
Manufacture thus protective glass for portable equipment (100).
(embodiment 8)
As the additive adding in fused salt fused solution, use salt of wormwood (addition is identical with embodiment 7), in addition, operation, implements chemical enhanced operation similarly to Example 7, manufactures protective glass (100) for portable equipment.
(embodiment 9)
As the additive adding in fused salt fused solution, use sodium sulfate (addition is identical with embodiment 7), in addition, operation, implements chemical enhanced operation similarly to Example 7, manufactures protective glass (100) for portable equipment.
(embodiment 10)
As the additive adding in fused salt fused solution, use potassium sulfate (addition is identical with embodiment 7), in addition, operation, implements chemical enhanced operation similarly to Example 7, manufactures protective glass (100) for portable equipment.
To the portable equipment protective glass obtaining in above embodiment 7～10, operation, evaluates having or not of 4 flexural strengths, surface attachments similarly to Example 1.In addition; to the portable equipment protective glass obtaining, major surfaces is divided into 5 deciles, is divided into 2 deciles along short side direction along long side direction, be divided into thus 10 regions; measure the surfaceness of each regional center portion, evaluate the homogeneity of the deviation of the surfaceness of 10 points.As evaluation result, the inhomogeneous amplitude of 00 presentation surface roughness Ras is in 0.30nm ± 0.05nm, and the inhomogeneous amplitude of zero presentation surface roughness Ra is in 0.30nm ± 0.10nm.These results are gathered and are shown in following table 2.
Be explained, surface roughness Ra represents by the arithmetic average roughness Ra according to JIS B0601:2001 regulation, by for example Scanning Probe Microscopy (atomic force microscope of Japanese Veeco company system; AFM) nanoscope is measured, and by calculating according to the method for JIS R1683:2007 regulation.In embodiment 7～10, in the square mensuration region of 1 μ m × 1 μ m, the arithmetic average roughness Ra while using the resolving power determination with 512 × 128 pixels measures.
[table 2]
? Additive kind 4 flexural strengths Surface attachments Uniformity of surface roughness
Embodiment 7 Sodium carbonate 100% Nothing ○
Embodiment 8 Salt of wormwood 100% Nothing ○
Embodiment 9 Sodium sulfate 100% Nothing ○○
Embodiment 10 Potassium sulfate 100% Nothing ○○
From the result of above-mentioned table 2; by adding as the Na of additive or the vitriol of K (embodiment 9 in fused salt fused solution; 10); with the situation (embodiment 7 of carbonate that adds Na or K; 8) compare, can obtain the protective glass of whole surface uniform (the ununiformity amplitude of surfaceness is little).Think that this is because as mentioned above, in refrigerating work procedure and/or washing procedure after chemical enhanced, it is neutral that protective glass surface is, the deteriorated cause of local surfaces roughness in the face that does not occur to be caused by etching action.Can confirm in addition, by obtaining whole the protective glass on surface uniformly, can suppress the ununiformity of the light transmission being caused by the ununiformity of surfaceness, suppress the decline as the texture of protective glass.

Claims (9)

1. the manufacture method of a portable equipment use protective glass; comprise ion-exchange process; the glasswork of described ion-exchange process by making the composition that contains Li contacts with the fused salt fused solution that contains ionic radius and be greater than the alkali metal of Li contained in this glass; basic metal in Li in described glasswork and described fused salt fused solution is carried out to ion-exchange; it is characterized in that
To be selected from NaF, KF, K 3alF 6, Na 2cO 3, NaHCO 3, K 2cO 3, KHCO 3, Na 2sO 4, K 2sO 4, KAl (SO 4) 2, Na 3pO 4, K 3pO 4in at least one additive add in described fused salt fused solution, described additive carries out described ion-exchange process with solid state.
2. the manufacture method of a portable equipment use protective glass; comprise ion-exchange process; the glasswork of described ion-exchange process by making the composition that contains Na contacts with the fused salt fused solution that contains ionic radius and be greater than the alkali metal of Na contained in this glass; basic metal in Na in described glasswork and described fused salt fused solution is carried out to ion-exchange; it is characterized in that
To be selected from KCl, KBr, KF, K 3alF 6, K 2cO 3, KHCO 3, K 2sO 4, KAl (SO 4) 2, K 3pO 4in at least one additive add in described fused salt fused solution, described additive carries out described ion-exchange process with solid state.
3. the manufacture method of a portable equipment use protective glass; comprise ion-exchange process; the glasswork of described ion-exchange process by making the composition that contains Li contacts with the fused salt fused solution that contains ionic radius and be greater than the alkali metal of Li contained in this glass; basic metal in Li in described glasswork and described fused salt fused solution is carried out to ion-exchange; it is characterized in that
Additive is added in described fused salt fused solution, the fusing point of described additive is higher than the Heating temperature of described fused salt fused solution, and with react the compound of this Li separated out as solid in described fused salt fused solution to the Li in described fused salt fused solution by the stripping from glass of described ion-exchange process, described additive carries out described ion-exchange process with solid state.
4. the manufacture method of protective glass for the portable equipment described in claim 1～3 any one, is characterized in that, described ion-exchange is low temperature modification ion-exchange.
5. the manufacture method of protective glass for the portable equipment described in claim 1～4 any one; it is characterized in that; select described additive as follows: even if the precipitate precipitateing in described fused salt fused solution by described ion-exchange process is attached to glass article surface, also can remove the precipitate that is attached to this glass article surface by cleaning glass goods after described ion-exchange process.
6. the manufacture method of protective glass for the portable equipment described in claim 1～5 any one; it is characterized in that; select described additive, make to precipitate into precipitate in described fused salt fused solution by described ion-exchange process different from the proportion of described fused salt fused solution.
7. the manufacture method of protective glass for the portable equipment described in claim 3～6 any one, is characterized in that, described additive is the compound that contains alkali metal component.
8. the manufacture method of protective glass for portable equipment claimed in claim 7, is characterized in that, in described additive, contained alkali metal component comprises the composition identical with basic metal contained in described fused salt fused solution.
9. the manufacture method of protective glass for the portable equipment described in claim 1～8 any one; it is characterized in that; in the refrigerating work procedure or washing procedure of chemical enhanced glasswork after treatment, when glasswork contacts with the aqueous solution, the PH of the aqueous solution on glass article surface is less than 10.
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