KR20100081777A - Preparation of soda lime silicate glass batches for plate, bottle and tableware containing cullet of tft-lcd substrate glass - Google Patents

Abstract

PURPOSE: A soda lime silicate batch composition for a plate glass, a bottle, and tableware is provided to improve a manufacturing process and physiochemical properties of the plate glass, the bottle, and the tableware even when a raw material is replaced for cullet of TFT-LCD. CONSTITUTION: A soda lime silicate batch composition for a plate glass, a bottle, and tableware includes 30-39 parts by weight of soda ash(sodium carbonate), 24-34 parts by weight of limestone, 1-25 parts by weight of dolomite, 0-25 parts by weight of feldspar, 0.5-1.5 parts by weight of sodium sulfate, and 3-24 parts by weight of cullet of TFT-LCD based on 100.0 parts by weight of silica, quartz, or their mixture.

Description

Soda-lime silicate-based glass, bottle and tableware badge compositions based on cullet of thin-film transistor liquid crystal display glass substrates for glass, bottle and tableware containing cullet of TFT-LCD substrate glass

The present invention is to recycle the cullet generated in the commercial production process of the thin film transistor liquid crystal display (TFT-LCD) glass substrate as a raw material of soda lime silicate-based glass, bottles and tableware (aka flint glass), plate glass, bottle and It relates to a badge composition for maintaining or improving the manufacturing process and physicochemical properties of the dish glass.

A cullet is defined as defective glass, shattered glass, glass shavings or crushed products of glass products. Such cullet inevitably occurs in the manufacturing and processing of glass or glass products, but in general, cullet in the glass industry Is considered a material that can be recycled as a raw material and is very important to manage.

In particular, since TFT-LCD substrate glass plays a role of protecting display core parts and transmitting images, even small defects do not occur. Therefore, manufacturing process or quality control is very strict compared with general window glass or tableware glass. Therefore, in the manufacturing and processing process of the substrate glass, dissolution, appearance defects and dimensional defects, etc., should be regarded as a defective product and disposed of, and a large amount of cullet is generated in this process. However, in order to ensure the continuous quality of the substrate glass as the display component, once the defective substrate glass is culletized, it is not recycled again in the manufacturing process of the TFT-LCD substrate glass, and these cullet is discarded as it is by landfilling. The amount is considerable.

Substrate glass for TFT-LCD does not contain alkali at all, and SiO ₂ , Al ₂ O ₃ , Alkaline (MgO + CaO + SrO + BaO) and B ₂ O ₃ are the main components. Highly homogeneous glass because it is well mixed throughout. Thus, the TFT-LCD cullet can be part of the raw material, i.e., the badge composition, needed to produce soda-lime silicate-based glass by controlling the appropriate amount.

Therefore, there is a growing interest in recycling such TFT-LCD cullet, and there is a need to continuously discover and apply a method and field that can be recycled without discarding the cullet.

As a related art related to the recycling of TFT-LCD cullet, Korean Patent Laid-Open Publication No. 1998-034394 discloses a method for regenerating a glass substrate of a TFT substrate for TFT-LCD (Thin Film Transistor Liquid Crystal Display). The technique relates to a method of regenerating substrate glass by removing a film from a glass substrate caused by an error in a TFT-LCD manufacturing process, and is characterized by removing various films formed on the glass substrate by a chemical method. Therefore, the above prior art seeks a recyclable field of the TFT-LCD cullet, and is merely related to a processing method for regeneration of the TFT-LCD substrate glass, not a direction in which it can be put to practical use.

In addition, the Republic of Korea Patent Publication No. 10-2006-0025097 discloses a "recovery method of the LCD cullet," the above technique is a trim glass with a vinyl protective film generated by the edge cutting after the glass is formed into a plate form The present invention relates to a process technology for mechanically crushing to remove vinyl and adjust particle size.

On the other hand, but are, this was purified to the slag generated in the steel mill technology proposed by the badge composition as the glass-producing materials Patent Patent 0,154,589 No. Republic of Korea, has been disclosed respectively in Patent 0,168,482 call, the above description of the wave glass is SiO ₂ and CaO It is characterized by using glass-like refined slag, which is a major component and contains relatively high iron, as a raw material for the production of colored glass, and by controlling the amount of refined slag constituting colored glass badges, Claims are made for a badge composition for colored slag-containing colored glass raw materials that can control the color and improve the meltability and clarity of the badge.

In view of the patented significance of the slag recycling technology described above, the TFT-LCD cullet is incorporated into a badge composition for producing glass or glassware as in the present invention, from which the glass having low manufacturing cost and high quality Alternatively, a method of manufacturing glass products and a badge composition for the same may also be considered as a technology having great significance since it is able to actively foster the recycling field of TFT-LCD cullet which is currently discarded in bulk without finding a recycling method.

The present invention has been made to solve the problems described above, the present invention is a part of the raw material for the production of soda lime silicate-based glass, bottles and tableware silica or silica, limestone, dolomite and feldspar as TFT-LCD cullet It is an object of the present invention to provide a glass badge composition which, despite the substitution, can at least not compromise or further enhance the physicochemical properties of the panes, bottles and tableware.

In addition, the present invention, despite the use of TFT-LCD cullet, can maintain the existing glass manufacturing process and process parameters as possible, economical without the need to introduce a new process according to a new composition or to expand a new line It is another object to provide a glass badge composition.

In addition, another object of the present invention is to provide a glass badge composition that can directly reduce the TFT-LCD cullet discarded as it is, raw material costs and lower the manufacturing cost.

The present invention, in order to achieve the above object, in the soda lime silicate-based glass, bottle and dish glass badge composition, when the silica composition, silica or a mixture of silica and silica in the badge composition to 100 parts by weight, TFT-LCD wave Provided is a soda-lime silicate-based plate glass, a bottle and a dish glass badge composition using cullet of a thin film transistor liquid crystal display glass substrate including 3 to 24 parts by weight of glass.

The badge composition is 30 parts by weight to 39 parts by weight of soda ash, 24 to 34 parts by weight of limestone, and dolomite when the weight of parts other than the TFT-LCD cullet is 100 parts by weight of the silica sand, silica or a mixture of silica and silica. ~ 25 parts by weight, feldspar 0 to 25 parts by weight, 0.5 to 1.5 parts by weight of manganese, it is preferable to comprise 3 to 24 parts by weight of the TFT-LCD cullet.

The TFT-LCD cullet is SiO ₂ 58 ~ 64 parts by weight, Al ₂ O ₃ 15 ~ 18 parts by weight, B ₂ O ₃ 7 ~ 11 parts by weight, MgO 0 ~ 4 parts by weight, CaO 3 ~ 8 parts by weight, SrO 0.5 to 8 parts by weight, BaO 0 to 3 parts by weight, SnO ₂ parts by weight 0 to 0.5 parts by weight, ZnO 0 to 0.5 parts by weight, Sb ₂ O ₃ 0 to 0.5 parts by weight, As ₂ O ₃ 0 It is preferable that it is comprised in the range of -0.8 weight part.

As described above, the present invention, while partially replacing the raw material for the production of soda-lime silicate-based glass, bottles and tableware with TFT-LCD cullet, but not impairing or further improving the manufacturing process and physicochemical properties of the glass By lowering the manufacturing cost of the glass, there is an effect to greatly reduce the environmental burden caused by the disposal or landfill of the TFT-LCD cullet.

That is, some or all of the silica sand, limestone and soda feldspar are replaced by TFT-LCD cullet in a badge composition in which the weight portion of the TFT-LCD cullet is increased in a limited range, thereby significantly reducing the manufacturing cost of the glass and at low temperatures. It has the positive effects such as dissolution and clarification, excellent glass forming ability without devitrification, and improvement of thermal shock and chemical durability.

Hereinafter, the present invention will be described in more detail based on the preferred embodiments.

In the badge composition for soda-lime silicate-based glass, bottles and tableware glass, 30 to 39 parts by weight of soda ash, 24 to 34 parts by weight of limestone, dolomite 0 to about 100 parts by weight of silica sand or quartz or a mixture of silica and silica 25 parts by weight, feldspar 0 to 25 parts by weight, manganese 0.5 to 1.5 parts by weight, TFT-LCD cullet 3 to 24 parts by weight, the glass is prepared by melting the badge composition as a chemical component, SiO ₂ 71 ~ 75 parts by weight, Al ₂ O ₃ 1.5 ~ 3 parts by weight, B ₂ O ₃ 0.1 ~ 1.5 parts by weight, Na ₂ O + K ₂ O 12 ~ 14 parts by weight, MgO + CaO + SrO + BaO 10 ~ 13 parts by weight , SrO 0.1 to 1 parts by weight, ZnO 0 to 0.1 parts by weight, SnO ₂ 0 to 0.2 parts by weight, Sb ₂ O ₃ 0 to 0.1 parts by weight, As ₂ O ₃ 0 to 0.1 parts by weight.

The TFT-LCD wave glass used is of SiO _2, Al ₂ O _3, alkaline earth (MgO + CaO + SrO + BaO), and B ₂ O ₃ is because the main component of the silica sand or silica, the feedstock of SiO ₂ CaO supplying the raw material and limestone and dolomite, Al ₂ O ₃ supplied sufficient to be a raw material of a raw material that can be partially or replace all of the feldspar, as well as TFT-LCD Cullet is required for visible light and the transmittance the amount of iron is extremely low, As a raw material for flat glass, bottles and tableware. In particular, since most of the raw materials that make up the badge are crystalline solids, considerable energy is required during melting into the liquid.However, since TFT-LCD cullet is already liquid structured glass, energy savings can be achieved by replacing the crystalline raw materials. You can expect the effect.

Badge melting temperature of plate glass, bottle and dish glass is 1450 ~ 1550 ℃, and the melt is formed into a plate or container in the temperature range corresponding to the viscosity of about 10 ⁴ ~ 10 ^7.6 poise through the clarification process of removing bubbles. do. In particular, the liquidus temperature should be lower than the operating temperature corresponding to 10 ⁴ poise to prevent devitrification of local crystals. In addition, each glass has a variety of physicochemical properties that must be provided as a commodity.

Therefore, in order to maximize the effect of TFT-LCD cullet, which is used as an alternative raw material, TFT-LCD occupies in the badge composition so that the physicochemical properties are maintained or improved within the range of maintaining the manufacturing process of plate glass, bottle, and dish glass as much as possible. It is very important to select an appropriate amount of cullet, and the content range of cullet based on these quantitative characteristics is of critical significance.

More specifically, if the TFT-LCD cullet is less than 3 parts by weight, the effect as a substitute raw material is insignificant, and the advantage of lowering the manufacturing cost of the glass disappears. If it exceeds 24 parts by weight, the physical and chemical properties of the glass are not only changed. Its properties change and lose its value as panes, bottles and tableware.

Accordingly, in the present invention, various badge compositions in which TFT-LCD cullet and other raw materials are mixed in consideration of the composition of soda-lime silicate-based glass, bottles, and tableware glass are prepared, and the characteristics of the glass prepared after melting are investigated. And a badge composition for maintaining or improving the manufacturing process and physicochemical properties of the dish glass.

The TFT-LCD cullet used in the present invention is a cullet generated in the manufacturing and processing process of the substrate glass for TFT-LCD, and has a composition as shown in Table 1 below.

ingredient Parts by weight SiO ₂ 58 to 64 Al ₂ O ₃ 15 to 18 B ₂ O ₃ 7 to 11 MgO 0 to 4 CaO 3 to 8 SrO 0.5 to 8 BaO 0 to 3 SnO ₂ 0 to 0.5 ZnO 0 to 0.5 Sb ₂ O ₃ 0 to 0.5 As ₂ O ₃ 0 to 0.8

On the other hand, the role and advantages of each main component replaced by the application of the TFT-LCD cullet is as follows.

SiO ₂ is an essential oxide involved in glass formation and is a component that stabilizes the network structure of glass. Substituting TFT-LCD cullet with a portion of crystalline silica or silica sand, which is a feedstock of SiO ₂ , improves the meltability of the badge, thus reducing the energy input during the manufacture of glass or glass products.

In addition, Al ₂ O ₃ is a component added to suppress the devitrification of the glass and to enhance chemical durability.If part or all of the crystalline soda feldspar, which is a feedstock of Al ₂ O ₃ , is replaced with a TFT-LCD cullet, Meltability is enhanced, resulting in energy savings and significant cost savings.

In addition, B ₂ O ₃ together with SiO ₂ is an oxide involved in glass formation, which promotes the melting of the badge, reduces the coefficient of thermal expansion of the glass, increases the softening point and enhances chemical durability. When TFT-LCD cullet is used as a raw material for flat glass, bottles and tableware, some B ₂ O ₃ components are accompanied, so that the chemical durability of the glass can contribute to the improvement.

In addition, MgO, CaO, SrO and BaO has the effect of lowering the viscosity of the glass at high temperatures and increasing the viscosity of the glass at low temperatures while promoting the melting of the badge. If part of the crystalline dolomite or limestone, the feedstock of MgO and CaO, is replaced by TFT-LCD cullet, the meltability of the badge can be improved, and the additional SrO and BaO added together are extremely small. Has little effect on

The badge composition according to the present invention includes a TFT-LCD cullet that supplies such components, thereby maintaining or improving the overall properties of the panes, bottles and dishware. In this case, the general characteristics are the clarification temperature corresponding to 100 poise related to the production of plate glass, bottle and tableware glass below 1460 ℃, the working temperature corresponding to 10,000 poise below 1035 ℃ and the liquid temperature below 1020 ℃. The difference between the working temperature and the liquidus temperature is 25 ° C or higher, the viscosity value in the liquidus temperature is 15,000 poises or more, the coefficient of thermal expansion of 91 × 10 ^-7 / ° C or less in terms of glass products, which is a measure of chemical durability against water. Alkali dissolution degree means less than 0.25mg / g.

[Example]

Based on the badge composition ratio of [Table 2], prepare a batch composition by mixing each raw material so that the weight of the total badge is 500g, using a 700cc platinum crucible and melting for 3 hours at 1550 ℃ using a platinum stirrer The molten glass was homogenized and then molded into a plate shape. The glass was completely cooled by maintaining the temperature at 550 ° C. for 2 hours and lowering the temperature to 350 ° C. by 5 ° C. per minute.

For each badge, high temperature viscosity, liquidus temperature, softening point, thermal expansion, and alkali dissolution rate were measured for each prepared glass, and the results are shown in the lower part of [Table 2]. In [Table 2], the badge meltability (℃) means the temperature at which the crystal phase disappears after maintaining each badge for 4 hours in the temperature range of 900 ~ 1300 ℃, T _m means a temperature corresponding to 100 poise, T _w means the temperature corresponding to 10,000 poise at which molding starts. In addition, T _liq means the liquidus temperature at which devitrification occurs, and the viscosity value (at T _liq ) at the liquidus temperature was calculated using logη = A + B / (TT _o ), which is a temperature-dependent expression of viscosity. Where η is the viscosity, A, B and T _o are constants and T is the temperature (° C.). ΔT denotes the difference between the molding temperature and the liquidus temperature (T _w -T _liq ), and α denotes the coefficient of thermal expansion between 25 and 500 ° C., respectively.

Raw materials and properties Example Comparative Example Parts by weight One 2 3 4 One 2 Quartz sand 100 100 100 100 100 100 Soda ash 30.8 31 31.5 31.5 34 34 Limestone 29.5 27.6 27.1 27 30 29 Sodastone 13 2.8 0 0 20 22 sulphate of soda 0.9 0.9 0.9 0.9 0.8 0.9 TFT-LCD cullet 4.5 13.4 15.9 16.3 0 0 characteristic







Badge Melt (℃) 1100 1070 1050 1030 1100 1100 T _m (℃) 1455 1450 1442 1441 1455 1457 T _w (℃) 1029 1028 1025 1024 1028 1031 T _liq (℃) 978 980 996 998 980 977 η at T _liq (poise) 24520 24512 15934 16325 25108 25601 △ T (℃) 51 48 29 26 48 54 Softening point (℃) 726 726 728 730 721 724 α (x10 ^-7 / ° C) 90.2 90.6 87.4 85.6 89.9 89.7 Alkaline Dissolution Rate (mg / g) 0.20 0.20 0.17 0.13 0.23 0.23

Comparative Example of Table 2 shows a commercial badge composition of a bottle or a dish glass, Examples 1 to 4 is a badge composition containing 4.5 to 16.3 parts by weight of TFT-LCD cullet with respect to 100 parts by weight of silica sand. . According to the embodiment, as the weight part of the TFT-LCD cullet is increased, the weight part of limestone and soda ash is changed very little, and the weight part of feldspar is gradually reduced, so that Examples 3 and 4 become economical badge compositions without any feldspar.

Looking at the characteristics of the glass corresponding to each of the badge composition appearing at the bottom of the [Table 2] while comparing the Examples and Comparative Examples as follows.

1. In the case of the Example, since the temperature at which the crystal phase disappears completely from the badge is at most 70 ° C. lower than that of the comparative example, the meltability of the badge is improved as the weight part of the TFT-LCD cullet increases.

2. In the case of Example, economic dissolution and clarification of the badge composition is possible because the clarification temperature (T _m ) corresponding to 100 poise and the working temperature (T _w ) corresponding to 10,000 poise are generally lower than those of the comparative example. .

3. The liquidus temperature (T _liq ) of the Example is up to 21 ° C. higher than the comparative example, but the difference between the working temperature and the liquidus temperature (ΔT) of each composition is 25 ° C. or higher and the viscosity value (η at T _liq ) at the liquidus temperature. Since it is more than 15,000 poise, it shows the outstanding glass forming ability which excludes devitrification.

4. The softening point of the embodiment fluctuates only within the range of 6 ° C., and the coefficient of thermal expansion (α) tends to decrease, so that the thermal shock of the glass is enhanced.

5. Alkaline elution that may occur in the process of using bottles and tableware decreases the chemical durability of glass made from badge compositions containing TFT-LCD cullet, since the examples are reduced rather than the comparative examples. It is shown.

When the components of the glass prepared from the badge composition shown in Examples and Comparative Examples of Table 2 are expressed in parts by weight, that is, the composition is as shown in Table 3 below. When comparing the commercial composition shown in the comparative example of [Table 3] and the composition of the example using the TFT-LCD cullet as a raw material, the amount of Al ₂ O ₃ and Na ₂ O in the embodiment according to the present invention slightly increased or Decreases, and further components of B ₂ O ₃ , SrO, SnO ₂ appear, but as shown in the properties of [Table 2] the original glass properties are not deteriorated as well as the original glass properties are at least maintained or more. Further improvement can be seen.

Example Comparative Example ingredient One 2 3 4 One 2 Furtherance
(weight %) SiO ₂
Al ₂ O ₃
B ₂ O ₃ 74.2
1.9
0.31 74.2
1.9
0.54 73.4
2.4
0.9 73.5
2.5
1.1 73.5
2.1
0 74.3
1.8
0 Na ₂ O
K ₂ O 12.6
0.32 12.7
0.07 12.3
0 12.1
0.01 13.1
0.28 12.8
0.24 MgO
CaO
SrO
BaO 0.12
10.6
0.14
0 0.13
10.6
0.2
0 0.13
10.5
0.3
0 0.13
10.3
0.4
0 0.18
10.6
0
0 0.12
10.8
0
0 SnO ₂ 0.01 0.01 0.02 0.03 0 0

While specific embodiments of the present invention have been described as described above, it is obvious that the present invention may be modified and practiced by those skilled in the art. Such modified embodiments should not be individually understood from the technical spirit or viewpoint of the present invention, and these modified embodiments should be included within the claims of the present invention.

Claims (3)

Soda-lime silicate-based glass, bottles and tableware glass composition, Soda using as a raw material a glass of a thin film transistor liquid crystal display glass substrate, characterized in that it comprises 3 to 24 parts by weight of a TFT-LCD cullet when 100 parts by weight of silica sand, silica or a mixture of silica and silica in the badge composition is used. Lime silicate-based glass, bottle and dish glass badge compositions. The method of claim 1, The badge composition is 30 parts by weight to 39 parts by weight of soda ash, 24 to 34 parts by weight of limestone, and dolomite when the weight of parts other than the TFT-LCD cullet is 100 parts by weight of the silica sand, silica or a mixture of silica and silica. ~ 25 parts by weight, feldspar 0 to 25 parts by weight, 0.5 to 1.5 parts by weight of manganese, soda lime silicate-based plate glass, bottle and tableware badge composition comprising a 3 to 24 parts by weight TFT-LCD cullet. The method according to claim 1 or 2, TFT-LCD cullet is SiO ₂ 58 ~ 64 parts by weight, Al ₂ O ₃ 15 ~ 18 parts by weight, B ₂ O ₃ 7 ~ 11 parts by weight, MgO 0 ~ 4 parts by weight, CaO 3 ~ 8 weight Parts by weight, SrO 0.5 to 8 parts by weight, BaO 0 to 3 parts by weight, SnO ₂ parts by weight 0 to 0.5 parts by weight, ZnO 0 to 0.5 parts by weight, Sb ₂ O ₃ 0 to 0.5 parts by weight, As ₂ O ₃ 0 to A soda lime silicate-based plate glass, a bottle and a dish glass badge composition which is made of cullet of a thin film transistor liquid crystal display glass substrate, the composition being 0.8 parts by weight.