KR100851522B1 - Pb-FREE BARRIER RIB GLASS COMPOSITION USING ETCHING METHOD FOR PLASMA DISPLAY PANEL - Google Patents

Abstract

The present invention relates to a lead-free bulkhead glass composition that can be applied to a high-definition etching partition wall forming method of a plasma display panel, comprising: A) 10 to 50 wt% of ZnO, 5 to 30 wt% of BaO, and 10 to 50 wt% of B ₂ O _3. , P ₂ O ₅ 1-20% by weight, 0-20% by weight of at least one oxide selected from the group consisting of Na ₂ O, Li ₂ O and K ₂ O, or B) 1-20% by weight of Li ₂ O, B ₂ O ₃ 10-50 wt%, P ₂ O ₅ 1-20 wt%, ZnO 10-50 wt%, C) 0-30 wt% BaO, 0-10 wt% CaO, 0-10 wt% MgO, 0-10 wt% SrO, 0-10 wt% Al ₂ O ₃ and SiO ₂ 0 It consists of at least one oxide selected from the group consisting of ˜10% by weight.

The lead-free barrier glass composition for forming a high-definition etch barrier rib of the present invention is environmentally friendly because it does not contain lead oxide harmful to the environment, and has a lower dielectric constant than conventional Pb-based glass compositions, thereby reducing power consumption of the plasma display panel. In addition, it is possible to manufacture fixed-size bulkheads that have limitations due to single layer etching.

PDP, Lead Free Glass, Etching Method, Etching, Upper Bulkhead, Lower Bulkhead

Description

Pb-FREE BARRIER RIB GLASS COMPOSITION USING ETCHING METHOD FOR PLASMA DISPLAY PANEL}

The present invention relates to a lead-free bulkhead glass composition for a plasma display panel (PDP) high-definition etched bulkhead method, and more particularly, to a double-layered bulkhead that solves the limitation of high-definition formation of a single-layer bulkhead. It is a lead-free glass composition suitable for the high-definition partition wall formation method using the difference in the etching rate between the lower partition wall and the lower partition wall. In addition, the glass frit for low-temperature firing is more secure and more reliable than the difference in etching rate due to the change of filler of the upper and lower barrier ribs.

The PDP is a display device using a plasma phenomenon, and discharge occurs when at least one potential difference is applied between two spatially separated contacts in a non-vacuum gas atmosphere. This is called a gas discharge phenomenon.

A plasma display element is a flat panel display element which applied such gas discharge phenomenon to image display. PDP, which is generally used at present, is a reflective AC drive PDP. In the case of a back substrate structure, a phosphor layer is formed in discharge cells partitioned by partition walls.

The PDP, like other flat panel display devices such as fluorescent display tubes (VFDs) and field emission displays (FEDs), has a rear panel and a front substrate (referred to as first and second substrates for convenience) at an arbitrary distance. Substantially arranged in parallel to form the appearance, the substrates are bonded by a bonding material disposed along the circumference therebetween to form a discharge cell in a vacuum state.

Sandblasting method and etching method are mainly used to form the partition on the first substrate of the PDP. Among them, there is a disadvantage that high resolution is difficult when the partition is formed by the etching method. In addition to the low thermal expansion rate, the partition wall is divided into two layers to form a partition wall, and thus, a distinct etching rate difference between the upper and lower partition walls is required.

However, conventionally, since the etching rate is controlled by changing the filler level of the upper and lower layers, there is a problem in terms of precision and reliability, so it is necessary to proceed with the development of glass to control the etching rate of the mother glass itself.

The present invention is to solve the above problems, an object of the present invention is environmentally friendly, does not contain lead oxide, and is divided into an upper partition and a lower partition by a method for producing a high-definition partition by the etching barrier rib forming method. The etching rate difference between the partition walls is used, and the etching rate of the mother glass itself is controlled to ensure the accuracy and reliability of the etching rate.

The present invention provides a lead-free bulkhead glass composition for PDP consisting of the following A) and C), or B) and C) in order to achieve the above object.

That is, the present invention is A) ZnO 10-50% by weight, BaO 5-30% by weight, B ₂ O ₃ 10-50% by weight, P ₂ O ₅ 1-20 wt%, 0-20 wt% of at least one oxide selected from the group consisting of Na ₂ O, Li ₂ O and K ₂ O,

C) 0-30% by weight of BaO, 0-10% by weight of CaO, 0-10% by weight of MgO, 0-10% by weight of SrO, 0-10% by weight of Al ₂ O _{3 and} 0-10% by weight of SiO ₂ It is a lead-free partition glass composition for PDP which consists of at least 1 sort (s) of oxide.

In addition, the present invention is B) Li ₂ O 1-20 wt%, B ₂ O ₃ 10-50 wt%, P ₂ O ₅ 1-20 wt%, ZnO 10-50 wt%, C) 0-30 wt% BaO, 0-10 wt% CaO, 0-10 wt% MgO, 0-10 wt% SrO, 0-10 wt% Al ₂ O ₃ and SiO ₂ 0 A lead-free bulkhead glass composition for PDP consisting of at least one oxide selected from the group consisting of ˜10% by weight.

In addition, the present invention provides a lead-free bulkhead glass composition for PDP consisting of the following A ') and C'), or B ') and C').

That is, the present invention is A ') ZnO, BaO and B ₂ O ₃ and C') ZnO, P ₂ O ₅ , SiO ₂ , Bi ₂ O _{3 ,} V ₂ O _{5 ,} Na ₂ O, Li ₂ O, K ₂ At least one oxide selected from the group consisting of O, CaO, MgO, BaO, MoO ₃ , Al ₂ O _{3 ,} As ₂ O ₃ , Sb ₂ O ₃ , CuO, Cr ₂ O ₃ , CoO, NiO and TiO ₂ A lead-free partition glass composition for PDP.

In addition, the present invention is B ') Li ₂ O, B ₂ O ₃ , P ₂ O ₅ and C') ZnO, P ₂ O ₅ , SiO ₂ , Bi ₂ O _{3 ,} V ₂ O _{5 ,} Na ₂ O, Li ₂ 1 selected from the group consisting of O, K ₂ O, CaO, MgO, BaO, MoO ₃ , Al ₂ O _{3 ,} As ₂ O ₃ , Sb ₂ O ₃ , CuO, Cr ₂ O ₃ , CoO, NiO and TiO ₂ It is a lead-free partition glass composition for PDP consisting of more than one type of oxide.

Here, the lead-free glass composition for PDP etching partition walls of the present invention is a composition for forming a partition wall for partitioning the discharge cells of the second substrate, and does not contain lead oxide, and upper and lower partition walls can be used without distinction. The upper partition is composed of ZnO, BaO and B ₂ O ₃ , the lower partition is composed mainly of Li ₂ O, B ₂ O ₃ , P ₂ O ₅ , that is, the upper partition is composed of A) and C), Particular preference is given to compositions consisting of B) and C).

The upper lead-free glass composition comprises first ZnO, BaO, B ₂ O ₃ , ZnO, P ₂ O ₅ , SiO ₂ , Bi ₂ O _{3 ,} V ₂ O _{5 ,} Na ₂ O, Li ₂ O, K ₂ O At least one oxide selected from the group consisting of CaO, MgO, SrO, MoO ₃ , Al ₂ O _{3 ,} As ₂ O ₃ , Sb ₂ O ₃ , CuO, Cr ₂ O ₃ , CoO, NiO and TiO ₂ It is preferable to include.

In addition, the upper lead-free glass composition includes a second ZnO, BaO, B ₂ O ₃ and P ₂ O ₅ , ZnO, P ₂ O ₅ , SiO ₂ , Bi ₂ O _{3 ,} V ₂ O _{5 ,} Na ₂ O , Li ₂ O, K ₂ O, CaO, MgO, SrO, MoO ₃ , Al ₂ O _{3 ,} As ₂ O ₃ , Sb ₂ O ₃ , CuO, Cr ₂ O ₃ , CoO, NiO and TiO ₂ More preferably, it further comprises at least one oxide selected.

The lower lead-free glass composition firstly comprises Li ₂ O, B ₂ O ₃ , P ₂ O ₅ , ZnO, P ₂ O ₅ , SiO ₂ , Bi ₂ O _{3 ,} V ₂ O _{5 ,} Na ₂ O, Li _{2 1 selected from the group} consisting of O, K ₂ O, CaO, MgO, SrO, MoO ₃ , Al ₂ O _{3 ,} As ₂ O ₃ , Sb ₂ O ₃ , CuO, Cr ₂ O ₃ , CoO, NiO and TiO ₂ It is preferable to further contain an oxide of a species or more.

In addition, the lower lead-free glass composition includes a second Li ₂ O, B ₂ O ₃ , P ₂ O ₅ and ZnO, SiO ₂ , Bi ₂ O _{3 ,} V ₂ O _{5 ,} Na ₂ O, Li ₂ O, K _At least one oxide selected from the group consisting of ₂ O, CaO, MgO, SrO, MoO ₃ , Al ₂ O _{3 ,} As ₂ O ₃ , Sb ₂ O ₃ , CuO, Cr ₂ O ₃ , CoO, NiO and TiO ₂ It is more preferable to further include.

The glass compositions are used as raw materials for melting the glass, and since metal ions and oxygen are present in the final glass frit in an amorphous structure, the same molar ratio of metal carbides, nitrides and compounds as metal oxides may be used.

Each of the components according to the content, the glass transition temperature (Tg), softening temperature (Ts), thermal expansion coefficient (TEC), etching rate, density, dielectric constant, gelation of the lead-free glass composition for PDP bulkhead of the present invention And color. Looking at the effect of each of the components on the lead-free glass composition as follows.

In the lead-free glass composition for the etching barrier Li ₂ O is a yellowish glass formula, which controls the firing temperature by lowering the glass transition temperature (Tg) of the lead-free glass composition, increases the dielectric constant, increases the coefficient of thermal expansion (TEC) and the etching rate. . Therefore, when the sum of the oxides is less than 1% by weight relative to the total weight of the lead-free glass composition, the glass transition temperature may be increased and thus may not be fired. When the amount of the oxide is added more than 20% by weight, the glass transition temperature may be drastically lowered. May be generated and the coefficient of thermal expansion may be increased to hinder the morphological stability of the partition wall, so it is preferably included in an amount of 1 to 20% by weight, more preferably 5 to 15% by weight.

B ₂ O ₃ is a light-forming glass forming agent that increases the glass transition temperature (Tg) of the lead-free glass composition, lowers the coefficient of thermal expansion (TEC), stabilizes the glass, and increases the gelation frequency. Therefore, when the content of the B ₂ O ₃ is less than 10% by weight relative to the total weight of the lead-free glass composition, glass is not formed. When the content of the B ₂ O ₃ exceeds 50% by weight, the Tg is excessively increased and powder phase occurs. It is preferably included in 50 to 50% by weight, more preferably included in 20 to 30% by weight.

P ₂ O ₅ is a light-forming glass forming agent that has a slightly higher glass transition temperature (Tg) and etching rate of the lead-free glass composition, lowers the dielectric constant, slightly reduces the coefficient of thermal expansion (TEC) and gelation frequency. And excessive crystallization causes crystallization. Therefore, when the content of the P ₂ O ₅ exceeds 20% by weight relative to the total weight of the lead-free glass composition, powder phase or crystallization may occur, so it is preferable to include 1 to 20% by weight, and 5 to 15% by weight. More preferably included in%.

ZnO, as a glass formula, lowers the glass transition temperature (Tg), dielectric constant, coefficient of thermal expansion (TEC) and gelation frequency of the lead-free glass composition, while functioning to improve the etching rate. Therefore, when the ZnO content is less than 10% by weight relative to the total weight of the lead-free glass composition, the effect of improving the etching rate is insignificant; It may be included in 10 to 50% by weight, and more preferably included in 20 to 50% by weight.

Al ₂ O ₃ is a white glass stabilizer, which increases the glass transition temperature (Tg) of the lead-free glass composition, decreases the crystallinity of the glass, and lowers the coefficient of thermal expansion (TEC), etching rate, and gelation frequency. Therefore, when the content of Al ₂ O ₃ exceeds 10% by weight relative to the total weight of the lead-free glass composition, since the firing temperature may increase and the etching rate may decrease rapidly, the Al ₂ O ₃ content may be included in an amount of 0 to 10% by weight. More preferably included in an amount of 5% by weight.

SiO ₂ is a light-forming glass forming agent that increases the glass transition temperature (Tg) of the lead-free glass composition, dramatically lowers the coefficient of thermal expansion (TEC) and etching rate, and lowers the gelation frequency. Therefore, when the content of SiO ₂ exceeds 10% by weight based on the total weight of the lead-free glass composition, the Tg is excessively increased and the etching rate may be sharply lowered, so that the content of 0 to 10% by weight is included. It is preferred and more preferably contained in 0 to 5% by weight.

Further, in the second ZnO, SrO, B ₂ O ₃ , P ₂ O ₅ , Na ₂ O, Li ₂ O and K ₂ O at least one oxide glass composition selected from the group consisting of,

ZnO, as a glass formula, lowers the glass transition temperature (Tg), dielectric constant, coefficient of thermal expansion (TEC) and gelation frequency of the lead-free glass composition, while functioning to improve the etching rate. Therefore, when the ZnO content is less than 20% by weight with respect to the total weight of the lead-free glass composition, the effect of improving the etching rate is insignificant. When the content of the ZnO exceeds 50% by weight, the etching rate is improved, but the dielectric constant is lowered to function as a partition wall. There is a risk of loss and may be unmelted when melting, so it is preferably included in 20 to 50% by weight, more preferably contained in 30 to 40% by weight.

SrO has a dark color and functions to slightly increase the glass transition temperature and etching rate of the lead-free glass composition, and to increase the coefficient of thermal expansion and dielectric constant. The content of SrO is preferably included in 10 to 30% by weight or less, more preferably in 20 to 30% by weight based on the total weight of the lead-free glass composition.

B ₂ O ₃ is a light-forming glass forming agent that increases the glass transition temperature (Tg) of the lead-free glass composition, lowers the coefficient of thermal expansion (TEC), and increases the etching rate and gelation frequency. Therefore, when the content of the B ₂ O ₃ is less than 10% by weight relative to the total weight of the lead-free glass composition, the effect of improving the etching rate is insignificant, and when it exceeds 40% by weight, the Tg is excessively increased. It is preferably included in 40% by weight, more preferably included in 20 to 30% by weight.

P ₂ O ₅ is a light-forming glass forming agent that has a slightly higher glass transition temperature (Tg) and etching rate of the lead-free glass composition, lowers the dielectric constant, slightly reduces the coefficient of thermal expansion (TEC) and gelation frequency. Do it. Therefore, when the content of the P ₂ O ₅ exceeds 20% by weight relative to the total weight of the lead-free glass composition, the dielectric constant may be lowered, so it is preferable to include 0 to 20% by weight, and preferably 10 to 20% by weight. More preferably included

Na ₂ O, Li ₂ O, and K ₂ O are all yellow-colored glass formulas, which can control the firing temperature by increasing the glass transition temperature (Tg) of the lead-free glass composition, increase the dielectric constant, and improve the coefficient of thermal expansion (TEC). ) And increase the etching rate. Therefore, when any one selected from Na ₂ O, Li ₂ O, or K ₂ O, or the sum of two or more oxides exceeds 10 wt% based on the total weight of the lead-free glass composition, the glass transition temperature may be rapidly lowered. In addition, since the coefficient of thermal expansion may increase to inhibit the shape stability of the partition, it is preferably included in 5 to 10% by weight.

CuO, NiO, Cr ₂ O ₃ , As ₂ O ₃ , Sb ₂ O ₃ and CoO are used as additives in the glass and control the coordination number, stability and mobility in the lead-free glass composition. Therefore, the total content of the at least one component is preferably included in an amount of 0-1% by weight or less with respect to the total weight of the lead-free glass composition, and when it is 1% by weight or more, excessive coloring and glass stability may be reduced.

BaO is a dark colored glass formulating agent, which lowers the glass transition temperature (Tg) of the lead-free glass composition, and increases the etching rate, dielectric constant, coefficient of thermal expansion (TEC) and gelation frequency. Therefore, when the BaO content is less than 10% by weight based on the total weight of the lead-free glass composition, the effect of improving the etching rate is insignificant, and when the content of the BaO is more than 50% by weight, the coefficient of thermal expansion is increased to inhibit the shape stability of the PDP partition wall. Since it may be, it is preferably included in 10 to 50% by weight, more preferably included in 10 to 25% by weight.

Al ₂ O ₃ is a glass stabilizer that exhibits white color, and functions to increase the glass transition temperature (Tg) and dielectric constant of the lead-free glass composition, and to lower the coefficient of thermal expansion (TEC), etching rate, and gelation frequency. However, when the content of Al ₂ O ₃ exceeds 10% by weight based on the total weight of the lead-free glass composition, since the etching rate may be sharply reduced, it is more preferably included in an amount of 0 to 10% by weight.

In addition, the upper partition glass composition for PDP etching barrier of the present invention comprises a) 20 to 40% by weight of ZnO, 10 to 30% by weight of BaO, 20 to 40% by weight of B ₂ O ₃ , b) i) P ₂ 10 to 20 wt% O ₅ , 0 to 20 wt% SiO _2, 0 to 20 wt% Bi ₂ O ₃ and V ₂ O ₅ At least one first oxide selected from the group consisting of 0-30% by weight, ii) 5-15% by weight of at least one oxide selected from the group consisting of Na ₂ O, Li ₂ O and K ₂ O, iii ) 0-10% by weight of at least one oxide selected from the group consisting of As ₂ O ₃ , Sb ₂ O ₃ , CuO, Cr ₂ O ₃ , CoO and NiO, 0-10% by weight of Al ₂ O ₃ and TiO ₂ It is preferable to further include at least one oxide selected from the group consisting of at least one third oxide selected from the group consisting of 0 to 10% by weight.

In addition, the top barrier-free glass composition for PDP etching barrier of the present invention is a) 20 to 40% by weight of ZnO, 10 to 30% by weight of BaO, 20 to 40% by weight of B ₂ O ₃ , 10 to 20 weight of P ₂ O ₅ B) i) 0-20 wt% SiO ₂ , 0-20 wt% Bi ₂ O ₃ and V ₂ O ₅ At least one first oxide selected from the group consisting of 0-30% by weight, ii) 5-15% by weight of at least one oxide selected from the group consisting of Na ₂ O, Li ₂ O and K ₂ O, iii ) 0-10% by weight of at least one oxide selected from the group consisting of As ₂ O ₃ , Sb ₂ O ₃ , CuO, Cr ₂ O ₃ , CoO and NiO, 0-10% by weight of Al ₂ O ₃ and TiO ₂ More preferably, at least one oxide selected from the group consisting of at least one third oxide selected from the group consisting of 0 to 10% by weight is further included.

In addition, the lower barrier-free lead-free glass composition for PDP etching barrier of the present invention is a) Li ₂ O 5-15% by weight, B ₂ O ₃ 20-40% by weight, P ₂ O ₅ 5 to 15 wt% and b) i) ZnO At least one first oxide selected from the group consisting of 20-50% by weight, SiO ₂ 0-10% by weight, Al ₂ O ₃ 0-10% by weight, ii) Na ₂ O, Li ₂ O and K ₂ O 5-15% by weight of at least one second oxide selected from the group consisting of iii) at least one selected from the group consisting of As ₂ O ₃ , Sb ₂ O ₃ , CuO, Cr ₂ O ₃ , CoO and NiO At least one oxide selected from the group consisting of at least one third oxide selected from the group consisting of 0-10% by weight of oxides, 0-10% by weight of Al ₂ O ₃ , and 0-10% by weight of TiO ₂ . It is preferable to further include.

In addition, the lower barrier-free lead-free glass composition for PDP etching barrier of the present invention is a) Li ₂ O 5-15% by weight, B ₂ O ₃ 20-40% by weight, P ₂ O ₅ 5-15 wt%, ZnO 20-50 wt%, b) i) at least one first oxide selected from the group consisting of 0-10 wt% SiO _2, 0-10 wt% Al ₂ O ₃ , ii) 5-15% by weight of at least one second oxide selected from the group consisting of Na ₂ O, Li ₂ O and K ₂ O, iii) As ₂ O ₃ , Sb ₂ O ₃ , CuO, Cr ₂ O ₃ At least one oxide selected from the group consisting of 0-10 wt%, Al ₂ O ₃ 0-10 wt% and TiO ₂ 0-10 wt%, at least one oxide selected from the group consisting of CoO and NiO More preferably, at least one oxide selected from the group consisting of oxides is further included.

Therefore, as the most preferred example of the lead-free glass composition for the upper and lower partitions of the PDP etching barrier of the present invention, the upper partition is first ZnO 20 ~ 40% by weight, BaO 10 ~ 30% by weight, B ₂ O ₃ 20 ~ 40% by weight, P ₂ O ₅ A composition comprising 10-20% by weight, 5-15% by weight of Li ₂ O and 1-10% by weight of SiO 2, or comprising As ₂ O ₃ , Sb ₂ O ₃ , CuO, Cr ₂ O ₃ , CoO and NiO The composition comprising 0 to 10% by weight of at least one oxide selected from the group Also the lower partition is Li ₂ O 5-15% by weight, B ₂ O ₃ 20-40% by weight, P ₂ O ₅ 5-15 wt%, ZnO It is preferred to have a composition comprising 20 to 50% by weight, 0 to 5% by weight of SiO _{2 and} 0 to 5% by weight of Al ₂ O ₃ .

Here, it is preferable that the lead-free glass composition has a coefficient of thermal expansion of 70 to 90 × 10 ⁻⁷ / ° C. and a difference in etching rate between the upper and lower partition walls is 20% or more.

In addition, when the etching rate difference between the upper bulkhead and the lower partition is 20-50%, the thickness ratio is 1: 2, when the etching rate difference is 50-300%, the thickness ratio is 1: 1, and the etching rate difference is 300 or more It is preferable to apply the thickness ratio at 2: 1.

In addition, the lead-free glass composition preferably has a glass softening temperature of 450 to 510 ℃ and excludes alkaline earth metal oxide.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 (Upper partition and lower partition composition for PDP etching partition)

For the upper bulkhead using a ball mill or zero gravity mixer (equipment), 35 kg ZnO, 15 kg BaO, 30 kg B ₂ O ₃ and P ₂ O ₅ 10 kg, Li ₂ O 9 kg and Al ₂ O 3 6 kg, in the second case, Li ₂ O 10 kg, B ₂ O ₃ 35 kg, P ₂ O ₅ 10 kg, ZnO 40 kg, 3 kg of SiO ₂ , 3.5 kg of Al ₂ O ₃ were mixed and the mixture was melted in a furnace at a temperature of 1200-1350 ° C. The molten mixture was quenched by a method using twin rolls in a dry manner, coarsely pulverized with a disk mill, and finely pulverized with a dry mill to prepare a lead-free glass composition for PDP partition walls.

The glass softening temperature of the prepared lead-free glass composition is 480-505 ℃, the coefficient of thermal expansion is 70-85x10 ^-7 / ^o C, the average particle diameter is 3㎛. The glass softening temperature was measured using a thermal analyzer (TMA, SHIMADZU, TMA-50, Japan), the thermal expansion coefficient was measured using a thermal analyzer (TMA, TMA, SHIMADZU, TMA-50, Japan), the average particle diameter Was measured using a particle size analyzer (Mastersizer 2000, Malvern, UK).

  Example 2 (Etching Characteristics of Pb-Etched Bulkhead Upper and Lower Bulkhead Lead-Free Glass Compositions)

70-80 parts by weight of the lead-free glass composition prepared according to Example 1, 1-5 parts by weight of prepared ethylcellulose, 1-5 parts by weight of butylcarbitol acetate (BCA) and 18-30 parts by weight of terpineol After adding three roll milling, defoaming to prepare a lead-free glass composition paste, and coating the lead-free glass composition paste to a thickness of 300-400㎛ on the first substrate on which the address electrode and the dielectric layer are formed and dried. The dried lead-free glass composition paste was baked at a temperature of 540-560 ° C. to form a partition layer, and then a dry film resist was applied, exposed and developed to form a pattern. The barrier layer on which the dry film resist pattern was formed was etched for 1 minute with a 1% by weight solution of nitric acid, and then washed to measure the etching rate. The etching rate measured in the etching process is an average of 10 ㎛ / min in the upper partition and 12um and 15um / min on the lower partition.

Example 3 (Etching factor according to the upper and lower thickness ratio of upper and lower partition lead-free glass composition for PDP etching partition)

In addition, the lead-free glass composition for the upper and lower partition bulkheads prepared according to Example 2 was used to have a thickness ratio of the upper partition (etching rate of 10um) and the lower partition (etching rate of 12um and 15um) of 1: 1 and 1: 2, respectively, for the production of high-definition partitions. , 2: 1 after coating and baking and pattern formation to form a partition wall. As a result of etching, the difference between upper and lower etching rate is 20% in the upper partition (etching rate 10um) and lower partition (etching rate 12um), so the etching factor is less than 0.5 at 1: 1, 1: 2, and 2: 1 thickness ratios. It was difficult to manufacture the fixed bulkhead, and the upper and lower etch rates were 15% for the upper bulkhead (etching rate 10um) and the lower bulkhead (15um etching rate). In both thickness ratios, the fixed factor bulkhead can be manufactured with an etching factor of more than 0.5

 In particular, when the upper and lower etch rate difference is 50%, the upper and lower layer thickness ratio of 1: 2 shows the best etching factor, and the upper and lower etch rate is increased and the upper and lower thickness ratio is 1: 2. In application, it is possible to manufacture high-definition bulkheads.

Therefore, the upper and lower lead-free glass compositions for etching barriers obtained in the present invention have a difference in etching rate between the upper and lower barrier ribs of 50% or more to improve the lower barrier ribs, and the thickness ratio is fixed when applying the lower layer portion 1: 2 to the upper layer portion. It was confirmed that three bulkheads could be manufactured.

As described above, the upper and lower layer lead-free glass compositions for PDP etching partition walls of the present invention are environmentally friendly because they do not contain lead oxide harmful to the environment. When the etching rate is improved by more than 50% and the thickness ratio is applied to the lower layer at 1: 2 compared to the upper layer, there is an advantage that a high-precision bulkhead can be manufactured by the etching method.

Claims (5)

In the lead-free glass composition for plasma display panel etching partition wall, A lead-free glass composition for a plasma display panel etching barrier, characterized in that consisting of the following A) + C) as the upper partition of the etching barrier, B) + C) as the lower partition. A) 10-50 wt% ZnO, 5-30 wt% BaO, 10-50 wt% B ₂ O ₃ , 1-20 wt% P ₂ O ₅ , and Na ₂ O, Li ₂ O and K ₂ O 1-20 wt% of at least one oxide selected from the group, B) 1-20 wt% Li ₂ O, 10-50 wt% B ₂ O ₃ , 1-20 wt% P ₂ O ₅ and ZnO 10-50 wt%, C) 1-30% by weight of BaO, 1-10% by weight of CaO, 1-10% by weight of MgO, 1-10% by weight of SrO, 1-10% by weight of Al ₂ O _{3 and} 1-10% by weight of SiO ₂ At least one oxide being. delete The method of claim 1, The lead-free glass composition is a lead-free glass composition for a plasma display panel etching barrier, characterized in that the difference in etching rate between the upper partition and the lower partition 20-50% and the thickness ratio 1: 2 between the upper partition and the lower partition. The method of claim 1, The lead-free glass composition is a lead-free glass composition for a plasma display panel etching barrier, characterized in that the difference in etching rate between the upper partition and the lower partition is 50-300% and the thickness ratio of the upper partition and the lower partition 1: 1. The method of claim 1, The lead-free glass composition is a lead-free glass composition for a plasma display panel etching barrier, characterized in that the difference in etching rate between the upper partition and the lower partition is 300% or more and is applied in a thickness ratio of 2: 1 between the upper and lower partitions.