[go: up one dir, main page]

WO2020218253A1 - Procédé d'extension de durée de vie pour composition de sel fondu, procédé de fabrication de verre chimiquement renforcé, agent auxiliaire de verre et matière première pour verre - Google Patents

Procédé d'extension de durée de vie pour composition de sel fondu, procédé de fabrication de verre chimiquement renforcé, agent auxiliaire de verre et matière première pour verre Download PDF

Info

Publication number
WO2020218253A1
WO2020218253A1 PCT/JP2020/017085 JP2020017085W WO2020218253A1 WO 2020218253 A1 WO2020218253 A1 WO 2020218253A1 JP 2020017085 W JP2020017085 W JP 2020017085W WO 2020218253 A1 WO2020218253 A1 WO 2020218253A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
molten salt
auxiliary agent
salt composition
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/017085
Other languages
English (en)
Japanese (ja)
Inventor
健二 今北
治夫 相澤
祐輔 藤原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to CN202310645447.3A priority Critical patent/CN116768494B/zh
Priority to CN202080030666.5A priority patent/CN113727953B/zh
Priority to JP2021516107A priority patent/JPWO2020218253A1/ja
Publication of WO2020218253A1 publication Critical patent/WO2020218253A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • 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
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight

Definitions

  • the present invention relates to a method for extending the life of a molten salt composition, a method for producing chemically tempered glass, a glass auxiliary agent, and a raw material for glass.
  • the chemically strengthened glass is immersed in the molten salt composition, and alkali metal ions having a small ionic radius in the chemically strengthened glass are exchanged with alkali metal ions having a large ionic radius in the molten salt composition. As a result, a compressive stress layer is formed on the surface of the chemically strengthened glass, and the chemically strengthened glass is obtained.
  • the molten salt composition after this treatment contains a sufficient amount of alkali metal ions having a large ionic radius, it can be used as it is for the chemical strengthening treatment of a new chemically strengthening glass.
  • the chemical strengthening treatment reduces the amount of ions having a large ionic radius in the molten salt composition and increases the amount of ions having a small ionic radius, so that the number of times the molten salt composition can be used is limited.
  • Patent Document 1 discloses a technique for adding Li-absorbing glass for chemical strengthening to a molten salt composition.
  • Patent Document 2 a heterogeneous anion Na salt or K salt is added to the molten salt composition, and an ion having a small ionic radius in the molten salt composition is removed from the system as a solid precipitate by reaction with these. The technology for discharging is disclosed.
  • the chemical strengthening time is also required to be shortened, and in order to shorten the strengthening time, strengthening at a higher temperature is required. Since the glass network is cut due to the increase in pH and the accompanying decrease in transparency of the glass becomes more remarkable as the glass is strengthened at a high temperature, an auxiliary agent in which the pH is less likely to increase than the conventional Li absorbent is required.
  • the method for extending the life of the molten salt composition of the present invention is a method for extending the life of the molten salt composition, which comprises a step of adding a glass auxiliary to the molten salt composition used for the chemical strengthening treatment of the chemically strengthened glass.
  • the glass auxiliary agent has a total content of SiO 2 and Al 2 O 3 of 60% or more in terms of mass% based on the oxide.
  • the glass aid is expressed in terms of mass% based on oxides, SiO 2 , Al 2 O 3 , Na 2 O, P 2 O 5 , B 2 O. 3, the total content of MgO and K 2 O may be 95% or more.
  • the glass auxiliary agent has a Li 2 O content of 3% or less and a Na 2 O content of 3% or less in terms of mass% based on the oxide. It may be 5% or more. In one aspect of the method for extending the life of the molten salt composition of the present invention, the glass auxiliary agent has a Li 2 O content of 3% or less and a K 2 O content of 3% or less in terms of mass% based on the oxide. It may be 5% or more. In one aspect of the method for extending the life of the molten salt composition of the present invention, the water content of the glass auxiliary agent may be 5% or less.
  • the glass auxiliary agent may be in the form of a plate. In one aspect of the method for extending the life of the molten salt composition of the present invention, the glass auxiliary agent may be granular. In one aspect of the method for extending the life of the molten salt composition of the present invention, the chemically strengthened glass may contain 1% or more of Li 2 O in terms of mass% based on oxides. In one aspect of the method for extending the life of the molten salt composition of the present invention, the chemically strengthened glass may contain 1% or more of Na 2 O in terms of mass% based on oxides.
  • the molten salt composition may contain a nitrate.
  • One aspect of the method for extending the life of the molten salt composition of the present invention further comprises a step of taking out a glass auxiliary agent that has absorbed Li and / or Na from the molten salt composition, and the step is to add glass to the molten salt composition. It may be carried out within 24 hours from the step of adding the auxiliary agent.
  • a glass auxiliary having a total content of SiO 2 and Al 2 O 3 of 60% or more is immersed in a molten salt composition in terms of mass% based on oxides.
  • the glass auxiliary agent is expressed in terms of mass% based on oxides, SiO 2 , Al 2 O 3 , Na 2 O, P 2 O 5 , B 2 O 3 , the total content of MgO and K 2 O may be 95% or more.
  • the glass auxiliary agent of the present invention is a glass auxiliary agent used to extend the life of the molten salt composition by absorbing Li ions and / or Na ions contained in the molten salt composition used for the chemical strengthening treatment of glass.
  • the total content of SiO 2 and Al 2 O 3 is 60% or more in terms of mass% based on the oxide.
  • One aspect of the glass auxiliary agent of the present invention is the content of SiO 2 , Al 2 O 3 , Na 2 O, P 2 O 5 , B 2 O 3 , Mg O and K 2 O in terms of mass% based on oxides. The total of may be 95% or more.
  • the raw material of the glass of the present invention has a total content of SiO 2 , Na 2 O, and Li 2 O of 95% or more in terms of mass% based on oxide, and the content of Li 2 O and Na 2 O.
  • the total of the glass is 15% or more.
  • the method for extending the life of the molten salt composition of the present invention can suppress an increase in pH of the molten salt composition.
  • the indication of "%" in the content of the component of the glass means the mass% based on the oxide.
  • a numerical range is indicated by using “to” in the present specification, it means a range including the numerical values before and after the numerical value as the lower limit value and the upper limit value.
  • “chemically strengthened glass” refers to glass after being chemically strengthened, and “chemically strengthened glass” refers to glass before being chemically strengthened.
  • the glass auxiliary agent of the present embodiment reduces the concentration of small alkali metal ions contained in the molten salt composition used for the chemical strengthening treatment of the chemically strengthening glass, and also increases the concentration of large alkali metal ions. It is a glass aid used to extend the life of the molten salt composition.
  • the small alkali metal is Li when the molten salt composition is used for Li-Na exchange and / or Li-K exchange, and the molten salt composition is used for Na-K exchange. When it is used, it means Na.
  • the large alkali metal is Na when the molten salt composition is used for Li—Na exchange, and the molten salt composition is used for Li—K exchange and / or Na—K exchange. If it is used, it means K.
  • the glass auxiliary agent of the present embodiment has a total content (total amount) of SiO 2 and Al 2 O 3 of 60% or more in terms of mass% based on oxides. Further, the glass auxiliary agent of the present embodiment has a total content of SiO 2 , Al 2 O 3 , Na 2 O, P 2 O 5 , B 2 O 3 , Mg O and K 2 O of 95% or more. Is preferable.
  • the glass auxiliary agent of the present embodiment is in a glass state and the total amount of SiO 2 and Al 2 O 3 is relatively large at 60% or more, the reaction with water in the molten salt is small, and the pH of the molten salt composition is low. Can be suppressed from rising.
  • the total amount of SiO 2 and Al 2 O 3 of the glass aid of the present embodiment is preferably 65% or more.
  • the pH of the molten salt composition after the addition of the glass auxiliary agent of the present embodiment is preferably substantially neutral from the viewpoint of suppressing the decrease in transparency of the glass due to OH ⁇ .
  • the pH of the molten salt composition after the addition of the glass auxiliary agent is preferably less than 7.9, more preferably 7.5 or less, still more preferably 7.0 or less.
  • the pH of the molten salt composition after the addition of the glass auxiliary is generally 5.0 or higher.
  • the glass auxiliary agent of the present embodiment has a total content of SiO 2 , Al 2 O 3 , Na 2 O, P 2 O 5 , B 2 O 3 , Mg O and K 2 O in the glass composition of 95% or more. This is preferable because the effect of extending the life of the molten salt composition is particularly high and the elution of ions that inhibit chemical strengthening is particularly small, as described below.
  • the large alkali metal ions in the glass auxiliary and the small alkali metal ions in the molten salt composition are exchanged (ion exchange).
  • the small alkali metal ions in the molten salt composition are absorbed by the glass auxiliary agent, and the large alkali metal ions in the glass auxiliary agent are released into the molten salt composition, so that the life of the molten salt composition is extended. It will be extended.
  • trivalent or pentavalent ions function as a network modifier for glass auxiliaries, but large ions with an atomic number of more than 20 are difficult to move in the Si skeleton, and if such an element is present, Since the movement of alkali metal ions in the glass aid is inhibited, the amount of ion exchange is reduced. Further, divalent ions such as CaO and SrO do not significantly reduce the amount of ion exchange of the glass auxiliary agent, but when eluted in the molten salt composition, they stay on the surface of the chemically strengthened glass. Inhibits chemical strengthening treatment.
  • Non-Patent Document 1 ions such as CaO and SrO inhibit the chemical strengthening treatment.
  • SiO 2 , Al 2 O 3 , Na 2 O, P 2 O 5 which are components composed of elements having an atomic weight of less than 20.
  • B 2 O 3 , Mg O and K 2 O are preferably total content of 95% or more.
  • the total content of the glass aids of the present embodiment SiO 2 , Al 2 O 3 , Na 2 O, P 2 O 5 , B 2 O 3 , MgO and K 2 O, is more preferably 96% or more. , More preferably 98% or more, and the upper limit is not particularly limited and may be 100%. The preferred range of the content of each of these components will be described below.
  • the optimum composition of glass auxiliaries can be broadly classified into two types depending on the method of use.
  • One is a composition that prioritizes chemical durability over the amount of small alkali metal ions absorbed and the amount of large alkali metal ions released, that is, the amount of ion exchange. Due to the excellent chemical durability, the reaction with water in the molten salt composition is reduced, and the pH increase of the molten salt composition is suppressed. Therefore, more auxiliary agents can be added to the molten salt composition than before, and the life extension effect is improved as compared with the conventional one. On the other hand, some compositions prioritize the amount of ion exchange over chemical durability. By increasing the amount of ion exchange per unit amount of auxiliary agent, the life extension effect is improved as compared with the conventional case.
  • an intermediate composition can also be used.
  • the optimum composition of the glass auxiliary agent differs depending on whether the small alkali metal ion to be ion-exchanged is Li or Na. The details will be described below.
  • first composition when the small alkali metal ion is Li, a preferable range of the composition of the glass auxiliary agent (hereinafter, also referred to as “first composition”) in which chemical durability is prioritized will be described.
  • SiO 2 is a component that constitutes the skeleton of the glass auxiliary agent.
  • the content of SiO 2 of the glass auxiliary agent of the first composition is preferably 52% or more, more preferably 54% or more, still more preferably 57% or more.
  • the content of SiO 2 of the glass auxiliary agent having the first composition is preferably 95% or less, more preferably 92% or less, still more preferably 90% or less. is there.
  • Na 2 O is an essential component for Li-Na ion exchange.
  • the content of Na 2 O in the glass aid of the first composition is preferably 5% or more, more preferably 9% or more, still more preferably 11% or more.
  • the Na 2 O content of the glass aid having the first composition in which chemical durability is prioritized is preferably 25% or less, more preferably 22% or less, still more preferably 20% or less.
  • Al 2 O 3 is a component that inhibits ion exchange of alkali metal ions, but is also a component that improves chemical durability.
  • Glass auxiliaries first composition so long as the content of Al 2 O 3 of the glass aids in the first composition with the effects may be 0%, but the present invention also containing Al 2 O 3 Good. If the glass aids in the first composition containing Al 2 O 3 preferably has a rate of content of Al 2 O 3 to the content of Na 2 O (Al 2 O 3 / Na 2 O) is less For example, 2.0 or less is preferable, 1.5 is more preferable, and 1.1 or less is further preferable.
  • the content of Al 2 O 3 is preferably 40% or less, more preferably 30% or less, still more preferably 20% or less.
  • the total amount of SiO 2 and Al 2 O 3 is preferably 65% or more, more preferably 70% or more, still more preferably 75% or more.
  • the total amount of SiO 2 and Al 2 O 3 is preferably 95% or less, more preferably 92% or less, still more preferably 90% or less.
  • P 2 O 5 and B 2 O 3 are not essential components, they may be contained in the glass auxiliary having the first composition. If the content of these components is too high, the chemical durability tends to deteriorate. Therefore, the content of these components is preferably 10% or less, more preferably 5% or less, still more preferably 2% or less, respectively. is there.
  • the lower limit of the content of these components is not particularly limited and may be 0%, but for the purpose of improving the meltability of the glass, it is preferably 0.1% or more, more preferably 0.5% or more. More preferably, it is 1.0% or more.
  • MgO, K 2 O is not an essential component, may be contained in the glass aids in the first composition. If the content of these components is too high, the chemical durability tends to deteriorate. Therefore, the content of these components is preferably 15% or less, more preferably 10% or less, still more preferably 7% or less, respectively. is there.
  • the lower limit of the content of these components is not particularly limited and may be 0%, but for the purpose of improving the meltability of the glass, it is preferably 1% or more, more preferably 3% or more, still more preferably 5. % Or more.
  • the glass auxiliary agent having the first composition contains a large amount of Li 2 O, ion exchange between Na ions in the glass auxiliary agent and Li ions in the molten salt is less likely to occur. Therefore, in the glass auxiliary agent having the first composition, the Li 2 O content is preferably 3% or less in order to secure a sufficient ion exchange amount.
  • the content of Li 2 O of the glass auxiliary agent of the first composition is more preferably 2% or less, still more preferably 1% or less. Further, the lower limit of the content of Li 2 O of the glass auxiliary agent having the first composition is not particularly limited and may be 0%.
  • the glass auxiliary having the second composition can not only exchange ions with small alkali metal ions as Na, but also ion exchange with small alkali metal ions as Li.
  • SiO 2 , P 2 O 5 , B 2 O 3 , and Mg O have the same composition as the first composition and are omitted.
  • Al 2 O 3 is a component that inhibits ion exchange of alkali metal ions, but is also a component that improves chemical durability.
  • the content of Al 2 O 3 of the glass aids in the second composition may be 0%, but the glass auxiliaries second composition so long as the effects of the present invention is containing Al 2 O 3 May be good. If the glass aids in the second composition containing Al 2 O 3 is preferably the proportion of the Al 2 O 3 content to the content of K 2 O (Al 2 O 3 / K 2 O) is less For example, 2.0 or less is preferable, 1.5 is more preferable, and 1.1 or less is further preferable.
  • the content of Al 2 O 3 is preferably 40% or less, more preferably 30% or less, still more preferably 20% or less.
  • the total amount of SiO 2 and Al 2 O 3 is preferably 65% or more, more preferably 70% or more, still more preferably 75% or more.
  • the total amount of SiO 2 and Al 2 O 3 is preferably 95% or less, more preferably 92% or less, still more preferably 90% or less.
  • Li 2 O is a component that is exchanged for Na ions in the molten salt composition.
  • the glass aid containing a large amount of Li 2 O releases Li ions into the molten salt composition when it absorbs Na ions in the molten salt composition.
  • Li ions in the molten salt composition are unfavorable components because they have the effect of shortening the life of the molten salt composition. Therefore, the content of Li 2 O in the glass auxiliary agent having the second composition is preferably small, specifically 3% or less, more preferably 1.5% or less, still more preferably 0.5% or less. is there.
  • the glass aid of the second composition does not have to contain Li 2 O.
  • the Na 2 O content of the glass auxiliary agent having the second composition is preferably 2% or more, more preferably 5% or more, still more preferably 10% or more.
  • the lower limit of the Na 2 O content of the glass auxiliary agent having the second composition is not particularly limited and may be 0%.
  • Na 2 O is an essential component for Li-Na ion exchange.
  • the content of Na 2 O in the glass auxiliary agent having the third composition is preferably 20% or more, more preferably 25% or more, still more preferably 30% or more.
  • the content of Na 2 O in the glass auxiliary agent having the third composition is preferably 45% or less, more preferably 40% or less, still more preferably 35% or less.
  • Al 2 O 3 is a component that inhibits ion exchange of alkali metal ions, but is also a component that improves chemical durability.
  • the content of Al 2 O 3 of the glass aids in the third composition is preferably 0%, glass auxiliaries third composition so long as the effects of the present invention is containing Al 2 O 3 May be good. If the glass aids in the third composition containing Al 2 O 3 preferably has a rate of content of Al 2 O 3 to the content of Na 2 O (Al 2 O 3 / Na 2 O) is less For example, 0.3 or less is preferable, 0.2 is more preferable, and 0.1 or less is further preferable.
  • the total amount of SiO 2 and Al 2 O 3 is preferably 60% or more, more preferably 65% or more.
  • the total amount of SiO 2 and Al 2 O 3 is preferably 80% or less, more preferably 75% or less, still more preferably 70% or less.
  • P 2 O 5 and B 2 O 3 are not essential components, they may be contained in a glass auxiliary having a third composition. If the content of these components is too high, the chemical durability tends to deteriorate. Therefore, the content of these components is preferably 10% or less, more preferably 5% or less, still more preferably 2% or less, respectively. is there.
  • the lower limit of the content of these components is not particularly limited and may be 0%, but for the purpose of improving the meltability of the glass, it is preferably 0.1% or more, more preferably 0.5% or more. More preferably, it is 1.0% or more.
  • MgO, K 2 O is not an essential component, may be contained in the glass aids in the third composition. If the content of these components is too high, the chemical durability tends to deteriorate. Therefore, the content of these components is preferably 10% or less, more preferably 5% or less, still more preferably 3% or less, respectively. is there.
  • the lower limit of the content of these components is not particularly limited and may be 0%, but for the purpose of improving the meltability of the glass, it is preferably 0.1% or more, more preferably 0.5% or more. More preferably, it is 1% or more.
  • the glass auxiliary agent having the third composition it is preferable that the Li 2 O content is 3% or less in order to secure a sufficient ion exchange amount.
  • the content of Li 2 O of the glass auxiliary agent having the third composition is more preferably 2% or less, still more preferably 1 or less.
  • the lower limit of the content of Li 2 O of the glass auxiliary agent having the third composition is not particularly limited and may be 0%.
  • the composition of the glass auxiliary agent (hereinafter, also referred to as “fourth composition”) in which the amount of ion exchange is prioritized when the small alkali metal ion is Na will be described.
  • the glass aid having the fourth composition can not only exchange ions with small alkali metal ions as Na, but also ion exchange with small alkali metal ions as Li.
  • SiO 2 , P 2 O 5 , B 2 O 3 , and Mg O have the same composition as the third composition and are omitted.
  • K 2 O is an essential component for Na—K ion exchange and also contributes to K—Li ion exchange.
  • the content of K 2 O of the glass aids in the fourth composition is preferably 20% or more, more preferably 25% or more, more preferably 30% or more.
  • the content of K 2 O is in excess of, the chemical durability tends to deteriorate.
  • Fourth K 2 O content of the glass aids compositions preferably 45% or less, more preferably 40% or less, more preferably 35% or less.
  • Al 2 O 3 is a component that inhibits ion exchange of alkali metal ions, but is also a component that improves chemical durability.
  • the content of Al 2 O 3 of the glass aids in the fourth composition may be 0%, but the glass auxiliaries fourth composition so long as the effects of the present invention is containing Al 2 O 3 May be good. If the glass aids fourth composition containing Al 2 O 3 is preferably the proportion of the Al 2 O 3 content to the content of K 2 O (Al 2 O 3 / K 2 O) is less For example, 0.3 or less is preferable, 0.2 is more preferable, and 0.1 or less is further preferable.
  • the total amount of SiO 2 and Al 2 O 3 is preferably 60% or more, more preferably 65% or more.
  • the total amount of SiO 2 and Al 2 O 3 is preferably 80% or less, more preferably 75% or less, still more preferably 70% or less.
  • Li 2 O is a component that is exchanged for Na ions in the molten salt composition.
  • the glass aid containing a large amount of Li 2 O releases Li ions into the molten salt composition when it absorbs Na ions in the molten salt composition.
  • Li ions in the molten salt composition are unfavorable components because they have the effect of shortening the life of the molten salt composition. Therefore, the content of Li 2 O of the glass auxiliary agent having the fourth composition is preferably small, specifically 3% or less, more preferably 1.5% or less, still more preferably 0.5% or less. is there.
  • the glass auxiliary having the fourth composition does not have to contain Li 2 O.
  • the glass auxiliary agent having the fourth composition it is preferable that the Na 2 O content is 30% or less in order to secure a sufficient ion exchange amount.
  • the content of Na 2 O in the glass auxiliary agent having the fourth composition is more preferably 25% or less, still more preferably 20 or less.
  • the glass auxiliary agent may have the effect of prolonging the life of the molten salt by ion exchange between the Na ion in the glass auxiliary agent and the Li ion in the molten salt composition. is there.
  • the Na 2 O content of the glass auxiliary agent having the fourth composition is preferably 2% or more, more preferably 5% or more, still more preferably 10% or more.
  • the lower limit of the Na 2 O content of the glass auxiliary agent having the fourth composition is not particularly limited and may be 0%.
  • the glass auxiliary agent of the present embodiment may contain other components as long as the effects of the present invention are exhibited.
  • the glass auxiliary agent of the present embodiment may contain N, F, S, Cl and the like.
  • compositions of the glass auxiliary agent of the present embodiment include, for example, the following compositions (A) and (B).
  • Composition (A) In terms of oxide-based mass% display, SiO 2 52-90%, Al 2 O 3 0-40%, MgO 15% or less, K 2 O 15% or less, Li 2 O less than 3%, Na 2 O 5-25%, B 2 O 3 10% or less, Contains 10% or less of P 2 O 5 A glass aid having a total oxide content of 95% or more and a total content of SiO 2 and Al 2 O 3 of 65% to 95%.
  • Composition (B) In terms of oxide-based mass% display, SiO 2 55-75%, 20-45% Na 2 O, Al 2 O 3 / Na 2 O is 0.3 or less, MgO less than 10%, K 2 O 10% or less, Li 2 O less than 3%, B 2 O 3 10% or less, Contains 10% or less of P 2 O 5 A glass aid having a total content of SiO 2 and Na 2 O of 95% or more and a total content of SiO 2 and Al 2 O 3 of 60 to 80%.
  • the water content of the glass auxiliary agent of the present embodiment is preferably low, preferably 5% or less, more preferably 1% or less, still more preferably. Is 0.1% or less.
  • the shape of the glass auxiliary agent of the present embodiment is not particularly limited, and may be, for example, plate-like, flake-like, or granular (powder-like), or may have another shape. It is preferable that the glass auxiliary agent has a plate shape because it can be easily removed from the molten salt composition.
  • the thickness is preferably 0.3 mm or more, more preferably 0.5 mm or more, still more preferably 1.0 mm or more. If the plate thickness becomes too thick, the amount of alkali metal ion absorbed decreases, so the plate thickness is preferably 5.0 mm or less.
  • the plate thickness is more preferably 3.0 mm or less, still more preferably 2.0 mm or less.
  • the glass auxiliary agent is granular because it is easy to handle.
  • the particle size is preferably 0.3 mm or more, more preferably 0.5 mm or more, still more preferably 1.0 mm or more.
  • the particle size is preferably 5.0 mm or less.
  • the particle size is more preferably 3.0 mm or less, still more preferably 2.0 mm or less.
  • the particle size in the present specification indicates the average diameter of the grains.
  • the method for extending the life of the molten salt composition of the present embodiment includes a step of adding the above-mentioned glass auxiliary agent of the present embodiment to the molten salt composition used for the chemical strengthening treatment of glass.
  • the increase in pH of the molten salt composition can be sufficiently extended.
  • the life extension method of the present embodiment may be carried out during the chemical strengthening treatment, or may be carried out while the chemical strengthening treatment is not performed. That is, the glass auxiliary agent may be added to the molten salt composition in which the chemically strengthening glass is immersed, or the glass auxiliary agent may be added to the molten salt composition in which the chemically strengthening glass is not immersed.
  • the glass auxiliary agent When the glass auxiliary agent is added, it may be spread in a tempered furnace, put in and out of a case, or put into a tempered glass cassette as a part of glass.
  • the glass auxiliary added to the molten salt composition gradually reduces the amount of ion exchange and the effect of extending the life of the molten salt composition, and in that case, it is preferably taken out from the molten salt composition. That is, it is preferable that the method for extending the life of the present embodiment includes a step of extracting the glass auxiliary agent that has absorbed a small alkali metal (Li and / or Na) from the molten salt composition. In order to improve the productivity of the chemically strengthened glass, it is preferable that the life extension method of the present embodiment is performed in a short time.
  • the step of taking out the glass auxiliary agent absorbing a small alkali metal from the molten salt composition is preferably performed within 24 hours from the step of adding the glass auxiliary agent to the molten salt composition. It is more preferably performed within 10 hours, and even more preferably within 5 hours.
  • the amount of the glass auxiliary agent added to the molten salt composition is not particularly limited, and the total amount of the molten salt composition, the content of small alkali metal ions, the desired treatment time, etc. It may be adjusted as appropriate.
  • the temperature of the molten salt composition in the method for extending the life of the present embodiment may be a temperature at which the exchange of small alkali metal ions in the molten salt composition and large alkali metal ions in the glass auxiliary agent proceeds, but ion exchange From the viewpoint of promotion, 350 ° C. or higher is preferable, 400 ° C. or higher is more preferable, and 420 ° C. or higher is even more preferable.
  • the temperature of the molten salt composition is preferably 500 ° C. or lower, more preferably 475 ° C. or lower, and even more preferably 460 ° C. or lower.
  • the molten salt composition whose life is extended by the method of the present embodiment may contain a large alkali metal ion (Na ion and / or K ion), and the type thereof is not particularly limited, but is generally nitrate (nitrate). Contains sodium and / or potassium nitrate).
  • a large alkali metal ion Na ion and / or K ion
  • the type thereof is not particularly limited, but is generally nitrate (nitrate). Contains sodium and / or potassium nitrate).
  • the chemically strengthened glass chemically strengthened by the molten salt composition whose life is extended by the method of the present embodiment will be described.
  • the chemically strengthened glass may contain Li 2 O and / or Na 2 O, and various glasses can be used as long as the glass has a composition capable of being strengthened by molding or chemical strengthening treatment.
  • the chemically strengthened glass include aluminosilicate glass, soda lime glass, borosilicate glass, lead glass, alkaline barium glass, aluminosophyllic acid glass and the like.
  • SiO 2 is 50 to 80%
  • Al 2 O 3 is 2 to 25%
  • Li 2 O is 0.1 to 20%
  • Na 2 O is 0.
  • K 2 O 0 - 10% of MgO 0 - 15% of CaO 0 - 5% of P 2 O 5 0 ⁇ 5% , the B 2 O 3 0 ⁇ 5% , Y the 2 O 3 glass can be used as a glass for chemical strengthening containing 0-5% and ZrO 2 0-5%.
  • a chemically strengthened glass that has high CS and large DOL by chemical strengthening treatment and has particularly high strength
  • the content of the small alkali metal (Li 2 O and / or Na 2 O) of the chemically strengthened glass chemically strengthened by the molten salt composition whose life is extended by the method of the present embodiment is, for example, 1% or more. It may be 3% or more, or 5% or more.
  • the thickness and shape of the chemically strengthened glass are not particularly limited.
  • the chemically strengthened glass may have various shapes such as a flat plate shape having a uniform plate thickness, a shape having a curved surface on at least one of the front surface and the back surface, and a three-dimensional shape having a bent portion and the like.
  • shape processing according to the application for example, mechanical processing such as cutting, end face processing, and drilling processing may be performed.
  • a specific shape of the chemically strengthened glass for example, a plate shape having a thickness of 0.3 mm to 2.0 mm can be mentioned.
  • the method for producing chemically tempered glass of the present embodiment is a method of recovering the glass auxiliary used in the method for extending the life of the molten salt composition and using it as a material for producing chemically tempered glass. That is, in the method for producing chemically strengthened glass of the present embodiment, a glass auxiliary having a total content of SiO 2 and Al 2 O 3 of 60% or more is used as a molten salt composition in terms of mass% based on oxides.
  • the glass auxiliary agent includes a step of taking out from the glass, a step of manufacturing a chemically strengthened glass using the taken out glass auxiliary agent as a material, and a step of subjecting the chemically strengthened glass to a chemical strengthening treatment. It is preferable that the total content of SiO 2 , Al 2 O 3 , Na 2 O, P 2 O 5 , B 2 O 3 , Mg O and K 2 O is 95% or more in terms of mass% based on the oxide. ..
  • the glass auxiliary agent after being used in the method for extending the life of the molten salt composition of the present embodiment contains a large amount of small alkali metals.
  • the glass auxiliary agent is added to the molten salt composition to remove the small alkali metal contained in the molten salt composition. Absorb by glass aid. The detailed description will be omitted because it overlaps with the description of the life extension method of the present embodiment described above.
  • the step of taking out the glass auxiliary agent absorbing the small alkali metal (Li and / or Na) from the molten salt composition in the production method of the present embodiment is the step of taking out the small alkali metal (Li and / or Na) in the above-described method of extending the life of the present embodiment. Or, it is the same as the step of taking out the glass auxiliary agent which has absorbed Na) from the molten salt composition.
  • the method for producing the chemically strengthened glass in the process of producing the chemically strengthened glass using the taken-out glass auxiliary agent (glass auxiliary after use) as a material is not particularly limited, but for example, the used glass according to a desired composition.
  • Examples of the method for forming the molten glass into a plate shape include a float method.
  • Glass auxiliaries after use include SiO 2 , Al 2 O 3 , MgO, Na 2 O, K 2 O, Li 2 O, ZrO 2 , TiO 2 , ZnO, B 2 O 3 , P 2 O 5, etc. It is preferably composed of components contained in the tempering glass.
  • the used glass auxiliary contains a component that is not contained in the chemically strengthened glass, it is difficult to use the used glass auxiliary as a raw material (raw material) for the chemically strengthened glass. Further, when the used glass auxiliary is used as a raw material for chemically strengthened glass, it is preferable that the type (number of components) of the components contained in the used glass auxiliary is small.
  • the process of mixing with other glass materials becomes complicated when used as a raw material, which imposes a load on the process.
  • the composition of the glass auxiliary agent after use as a raw material for chemically strengthening glass glass having a total of SiO 2 , Na 2 O, and Li 2 O of 95% or more is preferable.
  • the total content of Na 2 O and Li 2 O is preferably 15% or more, more preferably 20% or more, still more preferably 25% or more.
  • the chemical strengthening treatment method in the step of chemically strengthening the chemically strengthening glass is also not particularly limited, and the type, temperature, treatment time, etc. of the molten salt composition to be used may be appropriately adjusted according to the desired compressive stress profile. ..
  • ppm represents “mass ppm”.
  • Glass plates having the compositions shown in columns 1 and 2 of glass in Table 1 were produced by the float method.
  • the obtained glass plates were pulverized and classified, and those that passed through the 2 mm mesh and did not pass through the 1 mm mesh were collected to obtain granular glasses 1 and 2.
  • Glass 3-8) The raw materials were prepared so as to have the glass composition shown in Glasses 3 to 8 in Table 1, and the glass was melted by heating at 1600 to 1700 ° C. for 30 minutes, and then rapidly cooled by a rollout machine to crush the obtained glass.
  • Glass 1 was classified to obtain granular glasses 3 to 8.
  • the stress profile of the obtained chemically strengthened glass was measured using a measuring machine SLP1000 manufactured by Orihara Seisakusho Co., Ltd., which applied scattered photoelasticity manufactured by Orihara Seisakusho Co., Ltd. CS and DOL were read from the obtained stress profile. The results are shown in the "CS before addition” column and the "DOL before addition” column in Table 3.
  • Glass A SiO 2 66.2%, Al 2 O 3 11.2%, Li 2 O 10.4%, Na 2 O 5.6%, K 2 O 1.5%, MgO 3.1%, CaO 0.2%, ZrO 2 1.3%, Y 2 O 3 0.5%
  • Glass B SiO 2 64.4%, Al 2 O 3 8.0%, Na 2 O 12.5%, K 2 O 4.0%, MgO 10.5%, CaO 0.1%, SrO 0.1%, BaO 0.1%, ZrO 2 0.5%
  • Table 4 shows the results of examining the properties of glasses 1 to 8 as Li absorbers in the same procedure as in Experimental Examples 1 to 3.
  • the amount of the glass auxiliary added was 17% by mass with respect to the molten salt.
  • the immersion temperature and time of the glass auxiliary agent were 450 ° C. and 48 hours.
  • Other test conditions were the same as in Experimental Examples 1 to 3.
  • Table 5 shows the results of examining the characteristics of the granular and flake-shaped glass 4 as a Li absorber in the same procedure as in Experimental Example 1.
  • the amount of the glass auxiliary added was 5% by mass with respect to the molten salt, and the immersion time of the Li absorber was changed from 12 hours to 96 hours.
  • the immersion temperature was set to 450 ° C. for the granular glass auxiliary agent, and the immersion temperature was set to 410 ° C. for the flake-shaped glass auxiliary agent.
  • Table 5 shows the amount of Li trap and the pH value of the molten salt after the addition of the glass aid.
  • Table 6 shows the results of examining the characteristics of the granular and flake-shaped glass 4 as a Li absorber in the same procedure as in Experimental Example 12.
  • the immersion temperature of the glass auxiliary agent was fixed at 410 ° C.
  • the immersion time was fixed at 48 hours
  • the amount of the glass auxiliary agent added was changed from 1.15 to 5% by mass.
  • Table 6 shows the amount of Li trap and the pH value of the molten salt after the addition of the glass aid.
  • the water content of the flake-shaped glass 4 was measured, the water content was 0.16.
  • Table 7 summarizes the CS and DOL before and after the addition of the glass auxiliary agent when the “glass A” was strengthened and the glass auxiliary agent was added in the same procedure as in Experimental Example 1.
  • the molten salt 600 g of NaNO 3 containing a small amount of LiNO 3 so as to have a Li concentration (3000 ppm) was melted at 380 ° C., and the thickness of “Glass A” was 0.55 mm.
  • the strengthening of "glass A” was carried out by immersing the "glass A” in a molten salt at 410 ° C. for 4 hours.
  • Granular glass 11 was used as the glass auxiliary agent, and the glass auxiliary agent was immersed in the molten salt composition at 410 ° C. for 24 hours.
  • the other conditions were the same as in Experimental Example 1.
  • Tables 5 and 6 compare the granular glass auxiliary agent (Li absorbent) and the flake-shaped glass auxiliary agent (Li absorbent) using the glass 4, and Table 5 shows the addition amount. It was fixed and the immersion time was changed. In Table 6, the strengthening time was fixed and the addition amount was changed. In each table, the amount of Li trap was not significantly different between the granular glass and the flake-shaped glass. In addition, the pH after addition was almost neutral in all experiments.
  • Experimental Examples 15-18 the Na absorption effect was examined.
  • Experimental Examples 15 to 17 are Examples, and Experimental Example 18 is a Comparative Example.
  • (First chemical strengthening treatment step) 600 g of KNO 3 containing a small amount of NaNO 3 was heated to 380 ° C. and melted so as to have the amount of Na concentration (5400 ppm) shown in the column of “Na amount before addition” in Table 8.
  • a plate having a thickness of 2.0 mm of "Glass B” was immersed at 435 ° C. for 1 hour to obtain chemically strengthened glass.
  • the stress profile of the obtained chemically strengthened glass was measured using a measuring machine FSM6000LE manufactured by Orihara Seisakusho Co., Ltd.
  • CS and DOL were read from the obtained stress profile. The results are shown in the "CS before addition” column and the "DOL before addition” column in Table 8.

Landscapes

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

Abstract

La présente invention concerne un procédé d'extension de durée de vie pour une composition de sel fondu, ledit procédé comprenant une étape d'ajout d'un agent auxiliaire de verre à une composition de sel fondu utilisée pour le traitement de renforcement chimique du verre pour le renforcement chimique. En termes de % en masse sur une base d'oxyde, la teneur totale en SiO2 et Al2O3 dans l'agent auxiliaire de verre est supérieure ou égale à 60 %.
PCT/JP2020/017085 2019-04-26 2020-04-20 Procédé d'extension de durée de vie pour composition de sel fondu, procédé de fabrication de verre chimiquement renforcé, agent auxiliaire de verre et matière première pour verre Ceased WO2020218253A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202310645447.3A CN116768494B (zh) 2019-04-26 2020-04-20 熔融盐组合物的寿命延长方法、化学强化玻璃的制造方法、玻璃助剂和玻璃的原材料
CN202080030666.5A CN113727953B (zh) 2019-04-26 2020-04-20 熔融盐组合物的寿命延长方法、化学强化玻璃的制造方法、玻璃助剂和玻璃的原材料
JP2021516107A JPWO2020218253A1 (fr) 2019-04-26 2020-04-20

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019086234 2019-04-26
JP2019-086234 2019-04-26

Publications (1)

Publication Number Publication Date
WO2020218253A1 true WO2020218253A1 (fr) 2020-10-29

Family

ID=72942749

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/017085 Ceased WO2020218253A1 (fr) 2019-04-26 2020-04-20 Procédé d'extension de durée de vie pour composition de sel fondu, procédé de fabrication de verre chimiquement renforcé, agent auxiliaire de verre et matière première pour verre

Country Status (3)

Country Link
JP (1) JPWO2020218253A1 (fr)
CN (1) CN113727953B (fr)
WO (1) WO2020218253A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113371987A (zh) * 2021-06-23 2021-09-10 万津实业(赤壁)有限公司 电子玻璃返修的方法
CN115108721A (zh) * 2022-05-30 2022-09-27 河北光兴半导体技术有限公司 用于制备高铝硅酸盐玻璃的组合物、高铝硅酸盐玻璃及其制备方法和应用
JP2022171448A (ja) * 2021-04-30 2022-11-11 Ａｇｃ株式会社 溶融塩組成物の組成回復方法及び化学強化ガラスの製造方法
CN117756416A (zh) * 2023-12-26 2024-03-26 成都光明光电股份有限公司 离子筛材料及其制造方法
JP2025501821A (ja) * 2022-12-23 2025-01-24 重慶▲シン▼景特種玻璃有限公司 耐高温性および高温安定性を有するイオンふるい、その調製方法および使用

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115806394B (zh) * 2022-12-13 2025-07-25 成都光明光电股份有限公司 盐浴添加剂及其制造方法
CN116409928B (zh) * 2023-03-24 2025-08-15 湖南旗滨新材料有限公司 离子吸收玻璃制品及制备方法和含锂微晶玻璃的离子强化工艺

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996024559A1 (fr) * 1995-02-10 1996-08-15 Asahi Glass Company Ltd. Verre resistant aux rayures
JP4410354B2 (ja) * 1999-10-29 2010-02-03 Ｈｏｙａ株式会社 化学強化用Ｌｉ吸収ガラス、及び該化学強化用Ｌｉ吸収ガラスを用いた化学強化ガラスの製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05270866A (ja) * 1992-03-25 1993-10-19 Nippon Sheet Glass Co Ltd イオン交換処理方法
KR20130098877A (ko) * 2010-06-03 2013-09-05 아사히 가라스 가부시키가이샤 유리 기판 및 그의 제조 방법
WO2014045978A1 (fr) * 2012-09-18 2014-03-27 旭硝子株式会社 Sel fondu pour renforcement du verre, procédé de fabrication de verre renforcé, et procédé d'allongement de durée de vie de sel fondu pour renforcement du verre
JP5655980B2 (ja) * 2012-09-18 2015-01-21 旭硝子株式会社 ガラス化学強化用溶融塩の再生方法及び強化ガラスの製造方法
JP2018095532A (ja) * 2016-12-16 2018-06-21 セントラル硝子株式会社 ガラスの化学強化処理用溶融塩及び化学強化ガラス物品の製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996024559A1 (fr) * 1995-02-10 1996-08-15 Asahi Glass Company Ltd. Verre resistant aux rayures
JP4410354B2 (ja) * 1999-10-29 2010-02-03 Ｈｏｙａ株式会社 化学強化用Ｌｉ吸収ガラス、及び該化学強化用Ｌｉ吸収ガラスを用いた化学強化ガラスの製造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022171448A (ja) * 2021-04-30 2022-11-11 Ａｇｃ株式会社 溶融塩組成物の組成回復方法及び化学強化ガラスの製造方法
JP7663017B2 (ja) 2021-04-30 2025-04-16 Ａｇｃ株式会社 溶融塩組成物の組成回復方法及び化学強化ガラスの製造方法
CN113371987A (zh) * 2021-06-23 2021-09-10 万津实业(赤壁)有限公司 电子玻璃返修的方法
CN115108721A (zh) * 2022-05-30 2022-09-27 河北光兴半导体技术有限公司 用于制备高铝硅酸盐玻璃的组合物、高铝硅酸盐玻璃及其制备方法和应用
JP2025501821A (ja) * 2022-12-23 2025-01-24 重慶▲シン▼景特種玻璃有限公司 耐高温性および高温安定性を有するイオンふるい、その調製方法および使用
CN117756416A (zh) * 2023-12-26 2024-03-26 成都光明光电股份有限公司 离子筛材料及其制造方法

Also Published As

Publication number Publication date
CN113727953B (zh) 2023-06-27
JPWO2020218253A1 (fr) 2020-10-29
CN113727953A (zh) 2021-11-30
CN116768494A (zh) 2023-09-19

Similar Documents

Publication Publication Date Title
WO2020218253A1 (fr) Procédé d'extension de durée de vie pour composition de sel fondu, procédé de fabrication de verre chimiquement renforcé, agent auxiliaire de verre et matière première pour verre
JP7184073B2 (ja) 化学強化用ガラス
CN111936439B (zh) 电子设备盖板用微晶玻璃制品和微晶玻璃
CN115385571B (zh) 化学强化玻璃以及化学强化用玻璃
KR102004007B1 (ko) 화학 강화 유리 및 그 제조 방법
CN110482876A (zh) 化学强化组合物、化学强化方法及化学强化玻璃
JP3187321B2 (ja) 化学強化用ガラス組成物および化学強化ガラス物品
CN109206021B (zh) 用于玻璃强化的盐浴及其制备方法、强化玻璃和原料玻璃
CN101591139A (zh) 显示装置用玻璃板
JP2017149644A (ja) ３Ｄ成形のためのイオン交換可能なＬｉ含有ガラス組成物
CN104487392A (zh) 用于离子交换的铝硅酸盐玻璃
JP7172790B2 (ja) 化学強化ガラスの製造方法、溶融塩組成物及び溶融塩組成物の寿命延長方法
JP2001229526A (ja) 化学強化用ガラス組成物からなる磁気ディスク基板および磁気ディスク媒体。
JP7722372B2 (ja) ガラスおよび化学強化ガラス
CN116332504A (zh) 玻璃、化学强化玻璃和包含化学强化玻璃的电子设备
CN114956577A (zh) 一种高强度透明微晶玻璃及其制备方法
CN105813995A (zh) 化学强化用玻璃和进行了化学强化处理的玻璃
JP4410354B2 (ja) 化学強化用Ｌｉ吸収ガラス、及び該化学強化用Ｌｉ吸収ガラスを用いた化学強化ガラスの製造方法
JPS62270439A (ja) 化学強化用ガラス
JP2977068B2 (ja) 化学強化用ガラス
CN113135655A (zh) 一种可快速离子交换的含硼铝硅酸盐玻璃
JP7295228B2 (ja) 耐衝撃応力特性を備えた保護ガラス板
JP7524797B2 (ja) 化学強化ガラスの製造方法
CN116768494B (zh) 熔融盐组合物的寿命延长方法、化学强化玻璃的制造方法、玻璃助剂和玻璃的原材料
JP2021042116A (ja) 結晶化ガラスおよび強化結晶化ガラス

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20796271

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021516107

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20796271

Country of ref document: EP

Kind code of ref document: A1