KR101902014B1 - Preparation of long fiber glass batches containing OLED cullet - Google Patents

Abstract

The present invention relates to a borosilicate-based long-fiber glass batch composition which uses crushed glass generated in a commercial production process of non-alkali alumina borosilicate-based substrate glass materials to be used on organic light emitting diode (OLED) display devices. More specifically, the borosilicate-based long-fiber glass batch composition includes 16-100 parts by weight of the non-alkali alumina borosilicate-based crushed glass of OLEDs for 100 parts by weight of limestone. The non-alkali alumina borosilicate-based crushed glass waste generated in the OLED glass manufacturing process can be recycled and reduced. Compared to the natural raw materials used in a conventional long-fiber glass manufacturing process, high-quality glass raw materials can be supplied at a low cost while lowering the process temperature in melting and molding operations and lowering the manufacturing cost of the glass batch composition.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a long fiber glass badge composition containing an organic light emitting diode (OLED) wave glass,

The present invention recovers wafers generated in the commercial production process of alkali-free alumina borosilicate substrate glass used for organic light emitting diode (OLED) displays as a raw material of borosilicate-based long-fiber glass, Lt; RTI ID = 0.0 > chemical properties. ≪ / RTI >

Alkali-alumina borosilicate-based OLED glass in organic light-emitting diode (OLED) display panel, which is a new display method replacing thin-film transistor liquid crystal display (TFT-LCD), protects the key components of organic light- Therefore, it receives very strict quality control.

Therefore, if a defect occurs in the manufacturing process of the organic light emitting diode display glass, it is regarded as a defective product and crushed, and a large amount of cullet is generated. However, in order to ensure continuous quality as a display glass, wave glass produced from serious defects or contamination is not recycled into the glass manufacturing process, and these wave glasses are discarded by landfill or the like.

Such an organic light emitting diode display glass is designed to be suitable for an organic light emitting diode display panel manufacturing process which is higher than a manufacturing process temperature of a conventional thin film transistor liquid crystal display panel. The organic light emitting diode display glass is composed of SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ And alkaline earth oxides (MgO, CaO, etc.) are the main components and these components are well mixed through the melting process.

On the other hand, a long fiber glass to be applied to a composite material in the form of a woven or non-woven fabric is a borosilicate glass containing substantially no alkali oxide and composed of SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ and CaO The organic light emitting diode display wave glass can be a part of the raw material necessary to manufacture the long fiber glass, that is, a member of the badge composition, by appropriate amount of adjustment, since it matches the main components of the organic light emitting diode display glass.

As a conventional technique for recycling the alkali-free alumina borosilicate type display wave glass in accordance with the present invention, Korean Patent No. 10-0917269 discloses "a borosilicate-based long glass fiber made from wave glass of a thin film transistor liquid crystal display glass substrate The present invention relates to a method for recycling a wave glass produced in a substrate glass manufacturing process for a thin film transistor liquid crystal display, and more particularly, to an organic light emitting diode display wave glass having a different composition as a raw material for a long fiber glass It is irrelevant to the application.

As a conventional technique relating to the recycling of alkali-free alumina borosilicate type display wave glass, Korean Registered Patent No. 10-0929869 discloses "a soda lime silicate based single fiber glass raw material composition using a wave glass of a thin film transistor liquid crystal display glass substrate as a raw material "Which discloses an economical badge composition that uses a thin film transistor liquid crystal display wave glass as a feedstock for constructional insulation short fiber glass, and is characterized in that the organic light emitting diode display wave glass is applied to a long fiber glass It is irrelevant.

As a conventional technique related to the recycling of alkali-free alumina borosilicate type display wave glass, Korean Patent Registration No. 10-0990875 entitled " Low Iron Plate Glass Badge Composition for Solar Cells Using Non-Alkali Alumina Borosilicate Type Display Wave Glass as a Material " The above technology features an economical badge composition using a non-alkali alumina borosilicate thin film transistor liquid crystal display wave glass containing a small amount of iron as a raw material for low iron plate glass for soda lime silicate solar cells. However, this is also different from applying organic light emitting diode display wave glass to long fiber glass.

As a conventional technique related to recycling of alkali-free alumina borosilicate-based display waste glass, Korean Patent No. 10-1489349 entitled " Badge composition of cutting glass fiber for borosilicate nonwoven fabric using waste glass as display raw material " The above technology relates to a method for recycling waste glass generated in a thin film transistor liquid crystal display panel process as a raw material for non-woven cutting glass fiber. The organic light emitting diode display wave glass having a different composition is used as a raw material .

As a conventional technique related to the recycling of alkali-free alumina borosilicate-based display waste glass, Korean Registered Patent No. 10-1541081 discloses a soda-lime borosilicate based sound absorbing thermal insulating glass bead composition made from waste glass. The above technology features an economical badge composition that uses a mixture of waste glass generated from a thin film transistor liquid crystal display panel process as a raw material of a sound insulating glass, and waste glass generated from the window pane of a building or automobile. However, this is also irrelevant to the application of organic light emitting diode display wave glass to long fiber glass.

Alkali alumina borosilicate thin film transistor liquid crystal display for the production of the above-mentioned fiber glass, low iron plate glass for solar cell and sound absorbing insulation glass In view of the patent significance of the recycling technology using the composition of glass or waste glass, , A badger composition that incorporates a non-alkali alumina borosilicate based organic light emitting diode display wave glass into a badge composition for producing a long fiber glass and maintains the low cost and the characteristics of the long fiber as it is, It is a technology that has great significance because it can actively nurture the field of recycling of LED display wave glass.

DISCLOSURE OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a method for replacing limestone, pyrophyllite, borosilicate and borax, which are raw materials for producing borosilicate- And it is an object of the present invention to provide a glass bead composition which does not deteriorate the properties while maintaining the manufacturing process of the fiber glass.

In addition, the present invention relates to a method for producing a glass-ceramics, which comprises mixing limestone or talc as a raw material of CaO, pyrophyllite as a raw material of SiO ₂ , dolomite as a raw material of B ₂ O ₃ , and pyrophyllite as a raw material of Al ₂ O ₃ , , It is possible to reduce the cost of raw materials significantly, and in particular, to reduce energy costs and carbon emissions by reducing the temperature of the entire glass manufacturing process owing to a decrease in the viscosity of the molten glass, It is another object to provide a glass badge composition.

In addition, although the present invention uses an organic light emitting diode display wave glass, it is necessary to introduce a new process according to a new composition or to add a new line because the existing long fiber glass manufacturing process and process variables can be maintained as much as possible Another object of the present invention is to provide an economical long-fiber glass badge composition which is economical.

In order to achieve the above-mentioned object, the present invention provides a borosilicate-based long-fiber glass bead composition comprising 16 to 100 parts by weight of an alkali-free alumina borosilicate based organic light emitting diode wave glass per 100 parts by weight of limestone in the above- Based on the glass transition temperature of the organic borosilicate glass substrate.

The present invention relates to a method for preparing a glass composition for a glass substrate, comprising the steps of: preparing a glass composition comprising a glass composition, By weight and 1.2 to 1.8 parts by weight, respectively.

Industrial Applicability As described above, the present invention can be achieved by partially replacing the raw material for producing borosilicate-based long-fiber glass with wave glass of an alkali-free alumina borosilicate-based display glass used for an organic light-emitting diode display, By providing a badge composition that does not compromise the properties of the long fibers, the manufacturing cost of the long fiber glass is reduced, and the environmental burden caused by disposal or landfill of the organic light emitting diode display wave glass is significantly mitigated.

That is, in the batch composition in which the organic light-emitting diode display wave glass is increased in a limited range, a part of limestone, pyrophyllite, dolomite and the like is replaced with an alkali-free alumina borosilicate type organic light emitting diode display wave glass, Reduction can have a positive effect.

In particular, the supply of the B ₂ O _3, because the feed of borax of Na ₂ O containing a B ₂ O ₃ is treated is difficult as water and the reaction was so strong hygroscopic material to the atmosphere high in price compared to hoebung seokyina soda ash The raw materials are diverted to the glass with the alumina borosilicate-based organic light-emitting diode display waveguide and the non-alkali alumina, simplifying the management of the raw material of the long fiber glass and lowering the price further. That is, the present invention has a distinctive feature in that borax is completely excluded as a feedstock for B ₂ O ₃ .

In addition, since all the raw materials constituting the long fiber glass badge are crystalline solid, a considerable energy is required in the melting process to the liquid, but since the organic light emitting diode display wave glass already has the liquid structure, The amount of energy saved can be expected to be reduced, thereby contributing to the reduction of carbon emissions.

In addition, Korean Patent No. 10-0917269 and Ki-Dong Kim, Jong-Hee Hwang's (Recycling of TFT-LCD cullet as a raw material for fiber glasses. Glass Technol .: European Journal of Glass Science & Compared with the conventional thin-film transistor liquid crystal display (TFT-LCD) wave glass proposed in U.S.A., 2011, 181-184, the organic light-emitting diode display wave glass has lower energy consumption and carbon It is anticipated that the effect will greatly contribute to the emission reduction.

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

The present invention relates to a borosilicate-based long-fiber glass bead composition comprising 150 to 220 parts by weight of pyrophyllite, 35 to 49 parts by weight of pyroxene, 0 to 0.4 parts by weight of soda ash, 1.2 to 1.8 parts by weight of manganese, And 16 to 100 parts by weight of a diode display wave glass.

The long fiber glass has a badge melting temperature of 1500 ° C or higher, and the molten glass is formed into long fibers at a temperature corresponding to a viscosity of about 1000 poise through a process of removing air bubbles. Therefore, in order to maximize the effect of the organic light-emitting diode display wave glass used as a substitute raw material, in order to maintain or improve the characteristics of the long fiber within the range of maintaining the production process of the long fiber glass as much as possible, It is very important to select an appropriate range of silicate-based organic light-emitting diode display wave glass, and the range of wave glass content based on such quantitative characteristics has its critical significance.

More specifically, when less than 16 parts by weight of glass-free alumina-borate-based organic light-emitting diode display glass is used per 100 parts by weight of limestone, the total amount of B ₂ O ₃ If the content of the glass is less than 5% by weight, the economical effect of replacing the expensive raw feldspar or the borax raw material is insufficient. If the amount exceeds 100 parts by weight, the flowability of the glass is unstable due to the decrease in the homogeneity of the whole glass melt. The productivity is decreased due to difficulties in melting, bubble removal and molding process.

Accordingly, the inventors of the present invention prepared a variety of badge compositions in which organic light emitting diode display wave glass and other raw materials were mixed in consideration of the composition of commercial borosilicate based long glass fiber glass, investigated the characteristics of glass produced after melting, And characteristics of the badge composition.

The alkali-free alumina borosilicate-based wave glass used in the present invention is a wave glass generated in a process of manufacturing and processing a substrate glass used for an organic light emitting diode display. Specific composition is shown in Table 1 below, and a conventional thin film transistor liquid crystal display Compared to glass, the organic light emitting diode display wave glass differs in that the Al ₂ O ₃ weight ratio is 2 to 7 higher and the B ₂ O ₃ weight ratio is 1 to 9 lower. This difference in composition is due to the high manufacturing process temperature of the organic light emitting diode display panel.

ingredient Thin film transistor liquid crystal display glass
(Parts by weight) Organic Light Emitting Diode Display Glass
(Parts by weight) SiO ₂ 58 to 64 58 to 64 Al ₂ O ₃ 15-17 17 ~ 22 B ₂ O ₃ 9-11 2 to 8 MgO 0 to 4 0-5 CaO 3 to 8 3 to 10 SrO 0 to 8 0 to 8 BaO 0 to 3 0 to 8 SnO ₂ 0 to 0.5 0 to 0.5

The borosilicate-based badge composition according to the present invention includes organic light-emitting diode display wave glass that supplies the above-mentioned components, thereby maintaining various properties of the long-fiber glass. In this case, the characteristics are referred to as Wallenberger, FT, Smrcek, A. (The liquidus temperature: its critical role in glass manufacturing, Int. J. Appl. Glass Sci., 1, 2010, 151-163) A molding temperature corresponding to 100 poise is 1450 DEG C or less, a molding temperature corresponding to 1000 poise is 1250 DEG C or less, and a difference between the molding temperature and the liquid temperature is 55 DEG C or more.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

 [Example]

Each raw material was weighed and mixed so that the weight of the total badge was 400 g based on the badge composition ratio shown in the following [Table 2], melted at 1550 ° C for 3 hours using a 600cc platinum crucible, and melted glass was melted using a platinum stirrer Homogenized, molded into a plate, maintained in an electric furnace at a temperature of 700 DEG C for 1 hour, and then slowly cooled to room temperature to prepare glass.

The composition of the glass prepared in the middle of [Table 2] is shown for each of the badge compositions, and the result of measurement of the high temperature properties of the glass at the bottom of [Table 2] is shown. In the high-temperature properties, T _m means the temperature corresponding to 100 poise, T _w means the molding temperature corresponding to 1000 poise, T _liq means the liquid temperature which is the highest temperature at which crystallization occurs, refers to - (T _liq T _w) to the difference between the liquid phase temperature.

Raw materials, composition and high temperature viscosity Example Comparative example division One 2 3 4 5 6 7 Raw material (chemical formula)
And the weight portion Limestone (CaCO ₃₎ 100 100 100 100 100 100 100 100 Pyroxene
(Al ₂ O ₃ 4SiO ₂ H ₂ O) 220 207 155 129 102 49 0 232 Gypsum
_{(2CaO3B 2 O 3 5H 2 O} ) 49 47 37 32 27 17 7 46 Soda ash (Na ₂ CO ₃ ) 0 0 0.38 0.62 0.87 1.38 1.83 0 (Na ₂ SO ₄ ) 1.26 1.35 1.71 1.89 2.07 2.43 2.78 1.17 Organic Light Emitting Diode Wave Glass 16 32 97 130 162 230 298 0 ingredient SiO ₂
Al ₂ O ₃
B ₂ O ₃
CaO
Na ₂ O
MgO
SrO
BaO
SnO ₂ 52.3
14.2
6.6
22.1
0.70
2.0
0.02
0.24
0.01 52.2
14.2
6.6
22.1
0.68
1.99
0.04
0.48
0.03 51.6
14.3
6.4
21.8
0.66
2.11
0.11
1.43
0.07 51.3
14.3
6.4
21.7
0.65
2.15
0.15
1.89
0.09 51.0
14.4
6.4
21.6
0.65
2.2
0.19
2.36
0.12 50.5
14.4
6.3
21.4
0.64
2.27
0.26
3.27
0.17 50.3
14.6
6.2
20.8
0.63
2.35
0.33
4.1
0.21 52.5
14.2
6.6
22.9
0.7
2.0
0
0
0 High temperature property T _m (° C) 1410 1408 1386 1376 1367 1352 1338 1418 T _w (° C) 1220 1221 1211 1200 1192 1180 1177 1219 T _liq () 1110 1117 1130 1149 1158 1161 1210 1097 ΔT (T _w - T _liq ) 110 104 81 51 34 19 -33 122

The comparative examples in Table 2 show the commercial badge compositions and composition of long fiberglass, and in Examples 1 to 7 of Table 2, non-alkali alumina borosilicate based organic light emitting diode display wave glass 16 to 298 parts by weight, and the composition and high-temperature properties of the glass produced using the present badge composition.

According to the embodiment of Table 2, the weight portion of pyrophyllite and perovskite decreases with the increase of the weight of non-alkali alumina borosilicate based organic light emitting diode display wave glass, and in Example 2, 10% of the B ₂ O ₃ content is reduced 29% of the B ₂ O ₃ content in Example 3, even 87% of the B ₂ O ₃ content in Example 7, is provided by the non-alkali alumina borosilicate based organic light emitting diode wave glass .

Further, according to the composition of the examples, the content of the component SiO ₂ that stabilizes the glass network structure of the glass of the comparative example is decreased while the weight of the non-alkali alumina borosilicate based organic light emitting diode wave glass is increased and the component due to a composition change that BaO is increased [Table 2] High temperature viscosity is an embodiment when the 100 poise melting and fining temperature (T _m) and a working temperature corresponding to 1000 poises of the glass that appears at the bottom of the ( T _w ) are lowered by about 80 ° C and 42 ° C, respectively, than the comparative example, and the energy cost for melting and bubbling and molding process will be greatly reduced. The decrease in melting and working temperature due to the increase in weight of the organic light-emitting diode wave glass is considerably less than the result of increase in the weight of the conventional thin film transistor liquid crystal display (TFT-LCD) wave shown in Korean Patent No. 10-0917269 Respectively.

On the other hand, the increase of the alkali-free alumina borosilicate type organic light-emitting diode wave glass causes the increase of the liquid temperature which is the highest temperature at which the crystallization occurs, and the difference between the molding temperature and the liquid temperature, That is, since ΔT is continuously decreased, ΔT decreases to less than 55 ° C. from Example 4, and thus Example 7 shows -33 ° C., so that the liquidus temperature becomes higher than the molding temperature. This decrease in DELTA T will cause local crystallization in the fiber forming process, resulting in a decrease in productivity. Nonetheless, the application of the alkali-free alumina borosilicate-based organic light emitting diode wave glass as a constituent of the badge is very positive for the manufacturing process of the long fiber glass up to Example 3 where the safe range in the molding process, Respectively.

While specific embodiments of the invention have been described above, it will be obvious that the same may be varied in many ways by those skilled in the art. Such modified embodiments should not be understood individually from the technical idea or viewpoint of the present invention, and these modified embodiments should be included in the claims of the present invention.

Claims (2)

In the borosilicate-based long-fiber glass badge composition,
Alkali metal alumina borosilicate based organic light emitting diode wave glass is contained in an amount of 16 to 100 parts by weight based on 100 parts by weight of limestone in the badge composition,
The organic light emitting diode wave glass contains 17 to 22 parts by weight of Al ₂ O ₃ and 2 to 8 parts by weight of B ₂ O ₃ to reduce the melting temperature corresponding to 100 parts by weight of the composition containing no organic light emitting diode waveguide glass Lt; / RTI &
The present invention relates to a method for preparing a glass composition for a glass substrate, comprising the steps of: preparing a glass composition comprising a glass composition, By weight and 1.2 to 1.8 parts by weight, respectively,
A B ₂ O ₃ component is supplied from the organic light emitting diode wave glass and the raw material management is simplified without using borax which is strong in hygroscopicity as a raw material of B ₂ O _{3 and} is difficult to handle. A borosilicate based long glass fiber glass badge composition based on glass.
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