JPH101329A - Glass composition for chemical strengthening and chemically strengthed glass article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a glass compsn. for chemical strengthening not contg. ZrO2 , having a melting temp. and a working temp. fit for float foaming and ensuring satisfactory water and weather resistance after chemical strengthening treatment. SOLUTION: This glass compsn. has a compsn. consisting of, by weight, 58-66% SiO2 , 13-19% Al2 O3 , 3-4.5% Li2 O, 6-13% Na2 O, 0-5% K2 O, 10-18% R2 O (R2 O=Li2 O+Na2 O+K2 O), 0-3.5% MgO, 1-7% CaO, 0-2% SrO, 0-2% BaO, 2-10% RO (RO=MgO+CaO+SrO+BaO), 0-2% TiO, 0-2% CeO2 , 0-2% Fe2 O3 , 0-1% MnO (0.01<=TiO2 +CeO2 +Fe2 O3 +MnO<=3%) and 0.05-0.5% SO3 .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a chemically strengthened glass composition and a chemically strengthened glass article obtained by chemically strengthening the glass composition.

[0002]

2. Description of the Related Art In general, a chemically strengthened glass article is immersed in a molten salt containing a monovalent metal ion having a larger ionic radius than a monovalent metal ion contained in a glass composition, so that the metal ion in the glass and the molten metal ion are melted. It is produced by exchanging with metal ions in the salt.

As one of the uses of such chemically strengthened glass articles, they have been used as substrates for information recording media, particularly as magnetic disk substrates. For such magnetic disk drive applications, matching between the thermal expansion of glass and the thermal expansion of a metal jig for fixing is required, and weather resistance that can withstand long-term storage and use in a harsh environment, that is, high temperature and high humidity. Is required. Further, in the application of the magnetic disk substrate, the thickness used is becoming thinner. At the same time, it is desired that the surface of the magnetic disk substrate be flattened in order to increase the recording density. Therefore, it is advantageous to form the magnetic disk substrate by a float method suitable for it.

At present, as such a chemically strengthened glass substrate, a glass substrate having a soda lime composition formed by a float method is used after being chemically strengthened. However, when the glass substrate is subjected to a chemical strengthening treatment, the weather resistance is significantly deteriorated, so that there is a problem in use in a high-temperature and high-humidity environment.

By the way, as a chemically strengthened glass having excellent weather resistance, US Pat. No. 4,156,755 describes a lithium-containing ion exchange strengthened glass. The publication, paragraph 7, the 2-15 line, in weight percent, 59-63% of SiO _2, 10 to 13% of Na ₂ O, 4 to 5.5% of L
i ₂ O, 15 to 23 percent of Al ₂ O _3, containing 2-5% of _{ZrO 2, Al 2 O 3 +} ZrO 2 is 19~25%, Na ₂ O /
A glass composition having a ZrO ₂ of 2.2 to 5.5 is disclosed.

A method for producing a tempered glass is described, for example, in Japanese Patent Application Laid-Open No. Sho 62-187140.
64 to 70% SiO ₂ , 14 to 20% Al ₂ O ₃ ,
6% of Li ₂ O, 7 to 10% of Na ₂ O, 0 to 4% of M
gO, discloses a method for manufacturing a tempered glass containing 0 to 1.5% of ZrO _2.

However, the above-mentioned US Pat. No. 4,156,755
And the glass compositions shown in the examples of JP-A-62-187140 require high temperatures for melting and molding,
It is not easy to manufacture by the float method.

Another chemically strengthened glass is disclosed in
No. 32431, and the publication, No. 2
Item, 62-75% SiO 2 by weight% in left 2-7 rows
₂ , 4-12% Na ₂ O, 4-10% Li ₂ O, 5-
It contains 15% Al ₂ O ₃ , and has a weight ratio of Na ₂ O / ZrO ₂ of 0.5 to 2.0, and further contains Al ₂ O ₃ / ZrO _2.
A chemically tempered glass article wherein the weight ratio of ₂ is 0.4 to 2.5 is disclosed. The composition disclosed in the above publication contains a large amount of ZrO ₂ , and when manufactured using a melting furnace, crystals of ZrO ₂ are easily precipitated in the furnace, and there is a problem in quality.

Japanese Patent Publication No. 47-1312 discloses a lithium or sodium aluminosilicate glass sheet and a method for producing the same as a chemically strengthened glass suitable for windshields of automobiles, aircrafts and the like. The publication, on the right 29-34 row third term, particularly suitable glass composition, the oxide basis weight inner part, 2~6% Li ₂ O, 5~10
_{% Na 2 O, 15~25% Al} 2 O 3 and 60% to 70%
Consists SiO _2, is at least 95 wt% of _{Li 2 O, Na 2 O,} Al 2 O 3 and total compositions of SiO _2,
There is a description. Examples included in the composition range described in Item 3, Table 3, Table 3 of the publication require high temperatures for melting and molding, and it is difficult to produce high-quality glass by float molding. .

Further, a method for producing a tempered glass and a tempered glass are disclosed in British Patent No. 13222510. As one object of the above publication, the first section, lines 61 to 75, describe the process of Froucault process, Penn.
vernon or Pittsburgh pros
It is an object of the present invention to provide a composition capable of producing a glass sheet by ess, Colburn process. The conditions of the glass composition for this purpose are a strain point of 450 to 550 ° C, a working temperature of 980 to 1150 ° C, and a liquidus temperature of 1100 ° C. There is a description as follows. The compositions of the examples described in the publication are as follows:
There were problems that the working temperature was high, the liquidus temperature was higher than the working temperature, and it was not suitable for molding by the float method, and the weather resistance of the chemically strengthened glass was poor.

[0011]

Therefore, the present invention has a melting temperature and a working temperature suitable for float molding without containing ZrO ₂ which is a problem in the case of manufacturing using a melting furnace. An object of the present invention is to provide a glass composition for chemical strengthening that has good water resistance and weather resistance after the tempering treatment. Another object of the present invention is to provide a glass composition for chemical strengthening having an expansion coefficient that can be used in combination with a metal product.

[0012]

Means for Solving the Problems The present invention has been made based on the above prior art problems and requirements, expressed in terms of _{weight%, SiO 2 58~66%, Al} 2 O 3 13~19 %, Li ₂ O 3 to 4.5%, Na ₂ O 6 to 13%, K ₂ O 0 to 5%, R ₂ O 10 to 18%, where R ₂ O = Li ₂ O + Na ₂ O + K ₂ O ) MgO 0 to 3.5%, CaO 1 to 7%, SrO 0 to 2%, BaO 0 to 2%, RO 2 to 10%, (where RO = MgO + CaO + SrO + BaO) TiO ₂ 0 to 2%, CeO ₂₀ ２2%, Fe ₂ O ₃ ２0%, MnO １1%, (provided that TiO ₂ + CeO ₂ + Fe ₂ O ₃ + MnO = 0.
(01-3%).

Further, the average linear thermal expansion in the temperature range of 50 to 350 ° C. is preferably at least 80 × 10 ⁻⁷ / K.

[0014] expressed in terms of _{weight%, SiO 2 60~66%, Al} 2 O 3 15~18%, Li 2 O 3~ 4.5%, Na 2 O 7.5~12.5%, K ₂ O 0 to 2%, (however, Li ₂ O + Na ₂ O + K ₂ O = 11 to 17%) MgO 0.5 to 3%, CaO 2.5 to 6%, SrO 0 to 2%, BaO 0 to 2% (However, MgO + CaO + SrO + BaO = 3-9
_{%) TiO 2 0~ 2%,} CeO 2 0~ 2%, Fe 2 O 3 0~ 2%, MnO 0~ 1%, ( provided _{that, TiO 2 + CeO 2 + Fe} 2 O 3 + MnO = 0.
(01-3%).

Further, the average linear thermal expansion in the temperature range of 50 to 350 ° C. is preferably at least 84 × 10 ⁻⁷ / K.

Furthermore, in the above-mentioned glass composition for chemical strengthening, the melting temperature of the glass composition (10 ² poise)
Is a glass composition for chemical strengthening having a temperature of 1550 ° C. or less, a working temperature (a temperature having a viscosity of 10 ⁴ poise) of 1100 ° C. or less, and the liquidus temperature of the working temperature or less. is there.

Further, the melting temperature (temperature having a viscosity of 10 ² poise) of the glass composition is 1540 ° C. or less, and the working temperature (temperature having a viscosity of 10 ⁴ poise) is 10 ° C.
It is preferable that the temperature is not higher than 55 ° C. and the liquidus temperature is not higher than the working temperature.

Further, the present invention comprises the above-mentioned glass composition for chemical strengthening, wherein Li ions and / or
Alternatively, the chemically strengthened glass article is characterized in that Na ions are replaced by monovalent metal ions having an ionic radius larger than that of Li ions, and have compressive stress near the surface.

The reasons for limiting the composition of the chemically strengthened glass article of the present invention will be described below. SiO ₂ is a main component for forming glass and is an essential component.
If the proportion is less than 58%, the water resistance after ion exchange deteriorates. On the other hand, if it exceeds 66%, the viscosity of the glass melt becomes too high, making melting and molding difficult, and the expansion coefficient becomes too small. For this reason, the range of SiO ₂ is preferably 58 to 66%, more preferably 60 to 66%.
Is preferred.

Al ₂ O ₃ increases the ion exchange rate.
It is an essential component for improving the water resistance after ion exchange. If the ratio is less than 13%, the effect is insufficient. On the other hand, if it exceeds 19%, the viscosity of the glass melt becomes too high, making melting and molding difficult, and
Expansion coefficient is too small. Therefore, the range of Al ₂ O ₃ is preferably 13 to 19%, and more preferably 15 to 19%.
% Is preferred.

Li ₂ O is an essential component for performing ion exchange and also a component for enhancing solubility.
If the proportion is less than 3%, sufficient surface compression stress after ion exchange cannot be obtained, and the solubility is poor. On the other hand, if it exceeds 4.5%, the water resistance after ion exchange deteriorates and the liquidus temperature rises, making molding difficult. For this reason, Li ₂
The range of O 2 is preferably 3 to 4.5%.

Na ₂ O is a component that enhances solubility. If the ratio is less than 6%, the effect is insufficient. On the other hand, if it exceeds 13%, the water resistance after ion exchange deteriorates. Therefore, the range of Na ₂ O is preferably from 6 to 13%, more preferably from 7.5 to 12.5%.

K ₂ O is a component that enhances solubility, but is not an essential component because the surface compressive stress after ion exchange decreases. For this reason, the range of K ₂ O is preferably 5% or less, more preferably 2% or less.

Further, when the total R ₂ O of Li ₂ O + Na ₂ O + K ₂ O is less than 9%, the viscosity of the glass melt becomes too high, so that melting and molding become difficult and the expansion coefficient becomes too small. On the other hand, if it exceeds 18%, the water resistance after ion exchange deteriorates. For this reason, the range of the total R ₂ O of Li ₂ O + Na ₂ O + K ₂ O is preferably 9 to 18%, and more preferably 10 to 18%.
~ 17% is preferred.

MgO is a component that enhances solubility.
If it exceeds 3.5%, the liquidus temperature rises and molding becomes difficult. For this reason, MgO is preferably 3.5% or less, more preferably 0.5 to 3%.

CaO is a component that enhances solubility and is an essential component for adjusting the ion exchange rate.
If the ratio is less than 1%, the effect is not sufficient. on the other hand,
If it exceeds 7%, the liquidus temperature rises and molding becomes difficult.
For this reason, the range of CaO is preferably 1 to 7%, and more preferably 2.5 to 6%.

SrO and BaO are components that enhance solubility and are effective components for lowering the liquidus temperature.
However, since the density of glass increases and the cost of raw materials increases, SrO and BaO each contain 2%.
% Or less, more preferably 1% or less.

Further, MgO + CaO + SrO + BaO
If the total RO is less than 2%, the viscosity of the glass melt becomes too high, making melting and molding difficult. If it exceeds 10%, the liquidus temperature rises and molding becomes difficult. For this reason, MgO
The range of the total RO of + CaO + SrO + BaO is 2
-10% is preferable, and 3-9% is more preferable.

Fe_TwoO_ThreeIs Fe in the glass melt²⁺And Fe³⁺
Are in equilibrium, and these ions transmit light in the melt.
The transmittance, particularly the transmittance in the infrared region, is greatly affected. All iron to Fe
_TwoO_Three Above 2%, the absorption in the infrared region increases.
Control the glass temperature distribution during melting and forming
No longer possible, resulting in poor quality. Therefore, the total iron is F
e_TwoO_ThreeIs preferably 2% or less.

TiO ₂ , CeO ₂ and MnO are composed of Fe ²⁺ and Fe ²⁺
It is an effective component for changing the equilibrium state of ³⁺ and for changing the light transmittance by interacting. However, if the content is excessive, the quality of the glass base material is deteriorated and the cost of raw materials is increased. Therefore, the range of TiO ₂ is preferably 3% or less, and more preferably 2% or less. Further, the range of CeO ₂ and MnO is preferably 1% or less.

The glass composition for chemical strengthening of the present invention contains, in addition to the above components, Ni as long as the properties of the present invention are not impaired.
Coloring agents such as O, Cr ₂ O ₃ , CoO, and SO ₃ , As
A fining agent such as ₂ O ₃ and Sb ₂ O ₃ can be contained.

Of these, SO ₃ is derived from sulfate used as a fining agent. When sulfate is used as a fining agent, the fining effect is not sufficient if the residual amount in the glass is less than 0.05%. . On the other hand, even if the residual amount exceeds 0.5%, the refining effect is the same, and the SOx contained in the exhaust gas at the time of melting the glass increases, which is not environmentally preferable. Therefore, SO ₃ remaining in the glass is 0.05%
~ 0.5% is preferred.

Further, As, which is generally used as a fining agent,
_The content of ₂ O ₃ and Sb ₂ O ₃ is preferably 1% or less due to its toxicity, and is preferably not more than the amount mixed with impurities, that is, 0.1% or less.

In addition, highly volatile B ₂ O ₃ , ZnO, P ₂
O ₅ , PbO, etc. erode the bricks of the glass melting furnace and also deteriorate the quality such as volatile components aggregating on the ceiling of the furnace and dropping on the glass together with the bricks. The content is preferably set to 0.1% or less.

Using the glass composition for chemical strengthening of the present invention, a molten and formed substrate is disc-processed,
A magnetic disk substrate can be obtained by chemical strengthening and precision polishing. In this case, it is necessary to match the expansion coefficient with the metal fixing jig. At this time, 50-35
The average coefficient of thermal expansion in the temperature range of 0 ° C. is 80 × 10 ^-7
/ K or more, more preferably 84 × 10 ⁻⁷ / K or more.

In order to melt high-quality glass, the viscosity of the glass is preferably 1550 ° C. or lower, more preferably 1540 ° C. or lower, having a melting temperature of 10 ² poise. Also, to form a sheet with high flatness,
In particular, when forming by the float method, the working temperature, ie, 1
It is preferable that the temperature having a viscosity of 0 ⁴ poise is 1100 ° C. or lower, and the liquidus temperature is lower than the working temperature.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION

Examples Five types of compositions according to the present invention,
Table 1 shows the properties of the glass.

[0038]

[Table 1]

First, a first embodiment will be described. Batches were prepared using common glass raw materials such as silica, alumina, lithium carbonate, and sodium carbonate so as to have the composition shown in Table 1. The prepared batch was melted at 1450 ° C. for 4 hours using a platinum crucible and poured out onto an iron plate. After holding this glass in a furnace at 500 ° C. for 30 minutes, the furnace was turned off and allowed to cool to room temperature to obtain a sample glass.

As a characteristic of the sample glass, the melting temperature (lo
gη = 2), working temperature (TW: temperature of logη = 4), liquidus temperature (TL), difference between working temperature and liquidus temperature (TW−TL), and strain point (logη = 14.5). temperature)
Table 1 shows the measurement results.

The viscosity in the high temperature range was measured by a platinum ball pull-up type automatic viscosity measuring device, and the strain point was measured by a beam bending type viscosity measuring device.

The liquidus temperature was measured as follows. The sample glass was crushed and passed through a 2380 μm sieve,
The glass particles remaining on the 00 μm sieve were immersed in ethanol, ultrasonically cleaned, and dried in a thermostat. 25 g of the above glass particles were placed on a platinum boat having a width of 12 mm, a length of 200 mm, and a depth of 10 mm so as to have a substantially constant thickness, and kept in a gradient furnace at 900 to 1150 ° C. for 2 hours. 40 devitrification occurred inside
Observation was performed with an optical microscope at × 2, and the highest temperature that occurred was defined as the liquidus temperature.

Table 1 shows the measurement results of surface stress, surface stress layer depth, and water resistance as characteristics after ion exchange. For ion exchange, the glass is immersed in a mixed molten salt of reagent first grade sodium nitrate 40% and reagent first grade potassium nitrate 60%,
The test was carried out at 380 ° C. for 1 hour. The surface stress and the depth of the surface stress layer were measured using a polarizing microscope after preparing a thin piece of glass subjected to ion exchange treatment. Water resistance was measured by cutting the sample glass into 50 x 100 x 2 mm, ion-exchanging the mirror-polished plate, placing this plate in a plastic bag with 20 ml of purified water, holding at 60 ° C for 120 hours, and then placing the plate in purified water. The amount of the eluted glass component was measured and determined as the amount of elution per unit area.

In Examples 2 to 5, sample glasses were prepared in the same manner as in Example 1, and the properties of the glass and the properties after ion exchange were measured in the same manner as in Example 1.

In each embodiment, the melting temperature was 1
A glass composition having a working temperature of 550 ° C. or lower, a working temperature of 1100 ° C. or lower, and a liquidus temperature lower than the working temperature was obtained. Therefore, it was found that this glass composition was low in occurrence of devitrification, striae and streaks, obtained high-quality glass, and excellent in solubility and moldability. Furthermore, it was confirmed that molding by the float method was possible. Of course, since ZrO ₂ is not contained, ZrO
Crystal of O ₂ can not be precipitated.

Further, it was found that the weight loss in the water resistance test after ion exchange was as excellent as 1 μg / cm ² or less.

(Comparative Examples) On the other hand, Table 2 shows the characteristics of the composition and the glass of the four comparative examples not included in the present invention.

[0048]

[Table 2]

Comparative Examples 1, 2, 3, and 4 are compositions not included in the scope of the present invention. A sample glass was prepared in the same manner as in Example 1, and the properties of the glass and the properties after ion exchange were measured. However, the ion exchange was performed by immersing the glass in a mixed molten salt of 40% of the first grade sodium nitrate and 60% of the first grade potassium nitrate, and keeping the glass at 380 ° C. for 3 hours.

Comparative Example 1 has the composition described in Example 18 of US Pat. No. 4,156,755 and has a melting point of 161.
Since the temperature is as high as 5 ° C., it is not easy to produce high-quality glass with less occurrence of devitrification, striae and streaks.

Comparative Example 2 has the composition described in Example 1 of JP-A-62-187140 and has a melting point of 159.
Since the temperature is as high as 0 ° C. or higher, it is not easy to produce high-quality glass with less occurrence of devitrification, striae and streaks.

Comparative Example 3 has the composition described in Example 4 of JP-A-5-32431 and has a higher liquidus temperature than the working temperature, so that it is difficult to form glass.

Comparative Example 4 has the composition described in Example 6 of British Patent No. 13222510 and has a melting point of 1555.
Since the temperature is as high as not less than ° C., it is not easy to produce high-quality glass with less occurrence of devitrification, striae and streaks.

Comparative Example 5 is the above-mentioned commercially available soda-lime glass, and a sample glass was prepared in the same manner as in Example 1,
The properties of the glass and the properties after ion exchange were measured. However, the ion exchange was performed by immersing the glass in a molten salt of potassium nitrate of the first grade and holding it at 470 ° C. for 3 hours. The weight loss in the water resistance test after ion exchange was 20 μg /
cm ² , elution more than 20 times that of Examples of the present invention, and poor water resistance.

(Application Example) A sheet obtained by melting the glass compositions for chemical strengthening of Examples 1 to 5 and forming the sheet into a sheet is
It was processed into a donut shape having an outer diameter of 65 x an inner diameter of 20 mm. Further, after rough polishing, chemical strengthening was performed and precision polishing was performed to obtain a predetermined plate thickness to produce a magnetic disk substrate.

Further, the composition of Example 3 was melted and molded by a float method to prepare a substrate. A magnetic disk substrate was produced from the raw plate as described above. This substrate had a small degree of warpage and excellent flatness because the original base plate was manufactured by the float method.

Using the magnetic disk substrate manufactured as described above, a magnetic disk medium was manufactured. The production of the medium was performed by a sputtering method. First, a substrate that has been precisely cleaned is coated with Cr as a base layer and Co-C as a recording layer.
r-Ta and C as a protective layer were each formed by a sputtering method. Further, a lubricating layer was formed to obtain a magnetic disk medium. The medium thus obtained was mounted on a sealed magnetic disk drive and continuously operated. In this case, the temperature inside the drive increased due to the heat generated from the motor and the friction with the air on the disk surface. Did not occur.

[0058]

As described above, according to the glass composition for chemically strengthened glass of the present invention, it is easy to produce a high quality glass base plate, and furthermore, the chemically strengthened glass article having good water resistance after chemical strengthening treatment. Is obtained.

Further, since the glass phase for chemical strengthening of the present invention has a liquidus temperature lower than the working temperature and is excellent in solubility and moldability, it can be manufactured by a float method. Therefore, a high quality glass plate having high flatness, which is a feature of the float method, can be easily obtained.

Further, since the expansion coefficient can be matched with that of a metal fixing jig, application to an information recording medium substrate or the like is possible.

Claims (7)

[Claims] 1. A expressed in terms of _{weight%, SiO 2 58~66%, Al} 2 O 3 13~19%, Li 2 O 3~ 4.5%, Na 2 O 6~13%, K 2 O 0~ _{5%, R 2 O 10~18%} , ( provided _{that, R 2 O = Li 2 O} + Na 2 O + K 2 O) MgO 0~ 3.5%, CaO 1~ 7%, SrO 0~ 2%, BaO 0~ 2 %, RO 2 to 10%, (RO = MgO + CaO + SrO + BaO) TiO ₂ 0 to 2%, CeO ₂ 0 to 2%, Fe ₂ O ₃ 0 to 2%, MnO 0 to 1%, (However, TiO ₂ + CeO ₂ + Fe ₂ O ₃ + MnO = 0.
(01-3%). 2. The glass composition for chemical strengthening according to claim 1, wherein the average linear thermal expansion in a temperature range of 50 to 350 ° C. is 80 × 10 ⁻⁷ / K or more. 3. The glass composition for chemical strengthening according to claim 1, wherein 60 to 66% of SiO ₂ , 15 to 18% of Al ₂ O ₃ , and 3 to 4.5% of Li ₂ O are expressed by weight%. _{, Na 2 O 7.5~12.5%, K} 2 O 0~ 2%, ( provided _{that, Li 2 O + Na 2 O} + K 2 O = 11~17%) MgO 0.5~ 3%, CaO 2.5~ 6%, SrO 0 to 2%, BaO 0 to 2%, (however, MgO + CaO + SrO + BaO = 3 to 9
_{%) TiO 2 0~ 2%,} CeO 2 0~ 2%, Fe 2 O 3 0~ 2%, MnO 0~ 1%, ( provided _{that, TiO 2 + CeO 2 + Fe} 2 O 3 + MnO = 0.
01 to 3%). 4. The glass composition for chemical strengthening according to claim 3, wherein the average linear thermal expansion in a temperature range of 50 to 350 ° C. is 84 × 10 ⁻⁷ / K or more. 5. The glass composition for chemical strengthening according to claim 1, wherein the glass composition has a melting temperature (a temperature having a viscosity of 10 ² poise) of 1550 ° C. or less and an operating temperature of 10 ⁴ poise. (A temperature having viscosity) is 1100 ° C. or lower and the liquidus temperature is lower than or equal to the working temperature. 6. The chemically strengthened glass article according to claim 5, wherein the at 1540 ° C. or less (temperature with 10 ² poise viscosity) the melting temperature of the glass composition has a working temperature (10 ⁴ poise viscosity Temperature) is 1055 ° C. or lower and the liquidus temperature is lower than or equal to the working temperature. 7. A glass composition for chemical strengthening according to claim 1, wherein Li ions and / or Na ions near the surface are replaced by monovalent metal ions having an ionic radius larger than that of Li ions. A chemically strengthened glass article having a compressive stress in the vicinity of the surface.