CN102190444A - Environmentally-friendly lead-free low-temperature glass powder used for barrier of PDP (plasma display panel), and preparation method thereof - Google Patents

Environmentally-friendly lead-free low-temperature glass powder used for barrier of PDP (plasma display panel), and preparation method thereof Download PDF

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CN102190444A
CN102190444A CN2010101253409A CN201010125340A CN102190444A CN 102190444 A CN102190444 A CN 102190444A CN 2010101253409 A CN2010101253409 A CN 2010101253409A CN 201010125340 A CN201010125340 A CN 201010125340A CN 102190444 A CN102190444 A CN 102190444A
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free low
environment
low temperature
friendly type
type lead
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李胜春
武荣丽
刘立起
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Abstract

The invention discloses an environmentally-friendly lead-free glass powder used for a barrier of a PDP (plasma display panel), and a preparation method thereof. The glass powder is composed of the following raw materials in percentage by weight: 30-50% Bi2O3, 5-30% of B2O3, 5-30% of MgO, 5-30% of V2O5, 1-10% of P2O5, 1-10% of K2O, 1-5% CaO, 1-5% of SiO2 and 1-5% of Al2O3, wherein the total percentage of Bi2O3, V2O5 and P2O5 is 45-75% by weight and the total percentage of CaO, SiO2 and Al2O3 is 3-12% by weight. The preparation method comprises the following processes: weighing, mixing raw materials, melting, tabletting, ball-milling and screening. The glass powder has the advantages of low softening temperature, no lead, high sealing airtightness and diverse colors.

Description

A kind of environment-friendly type lead-free low temperature PDP barrier glass powder and preparation method thereof
[technical field]
The present invention relates to the glass material field, specifically, is a kind of environment-friendly type lead-free low temperature PDP barrier glass powder and preparation method thereof.
[background technology]
Since the plasma display panel (PDP) sixties in 20th century (PDP) is come out, because its application prospects, cause the great attention of countries in the world government and group of enterprises, become the 21 century new growth engines, drawn and driven the research and development that large quantities of research units and group of enterprises are engaged in equipment, technology, technology and material.At present, main transnational company such as healthy and free from worry, Asahi Glass, electric nitre, Daejoo etc. all are considered as from now on the PDP display screen with the dominant direction of glass powder with PDP with lead-free glass powder.Because the PDP vital role of lead-free glass powder on the PDP display screen, so still drop into the new generation product of substantial contribution exploitation PDP, and visible trend of oriented other display applications expansions with lead-free glass powder in electronic material companies such as electric nitre, Daejoo.World's display screen developments shows, PDP with the development of lead-free glass powder to the service life of PDP display screen and the lifting of picture quality having very important effect.
The environmental issue that is caused by electronic product receives the concern of the public, related personnel and manufacturers day by day.The environmental protection legistration work at the electronics manufacture view has been strengthened in countries in the world.The U.S. has just issued plumbous tax law case as far back as in June, 1993.In November, 1998, EPA (USEPA) has released the strategy of control PBT pollutent.The toxic substance inventory (TRI) of EPA proposed new regulation in 1998, had increased some PBT in TRI, and had reduced the reporting standards of existing PBT among the TRI.In Japan, formulated and issued the law that electronic material and specialities reclaim, such as " the domestic electronic appliances absorption method " passed through in 1998, regulation must reclaim contained lead in the domestic electronic appliances.The many companies of Japan just are being devoted to substitute the material of hostile environment and the research of technology.European Parliament and EU Council and Japan have proposed simultaneously about the instruction of discarded electric/electronic device (WEEE) with about limit the instruction of using dangerous substance (RoHS) in electrical equipment, and the most finally in February, 2003 announced the instruction of removing plumbous use, come into force from July 1st, 2006.The many countries in Europe such as Holland, Switzerland, Sweden, Denmark, Norway etc., have also formulated the regulation of relevant recovery and regeneration electronic waste.China has formulated " electronics and IT products prevention and cure of pollution management method ", forbids or limits six kinds of objectionable impuritiess (lead, mercury, cadmium, sexavalent chrome, polymerization bromination biphenyl or polymerization bromination biphenyl) and produce or import in China.Because China's electronic industry is the producer roles such as main responsible OEM, ODM in global information electronics supply refining, during in the face of unleaded the requirement, China dealer bears pressure will be much larger than external industry.
Japanese kokai publication hei 9-218508 proposes the photosensitive glass material that a class can be used for making plasma display screen barrier, is characterized in that the barrier of making has high depth-width ratio, pattern working accuracy height.Wherein glass is bismuth-containing or plumbous low-melting glass, and the composition mass percent is SiO 2(3～60%), B 2O 3(5～40%), ZnO (2～40%), MgO (0～25%), Bi 2O 3Or PbO (5～50%), Al 2O 3(0～10%), glass Tg is 350～470 ℃, and the glass particle diameter is 0.1～10 μ m, and spheroidal particle accounts for more than 80%, and often sintering temperature is higher in use for this patent, can not satisfy as much as possible low sintering demand for development in the present use procedure.
The flat 6-144871 of SUMITOMO CHEMICAL cermet (strain) JP has proposed a class and has been applicable to the photosensitive pulp that the sensitization implantation is used, and glass powder composition mass percent is PbO (65%), B in the composition 2O 3(21%), SiO 2(11%), Al 2O 3(3%), 1200 ℃ of lower fusings, is ground into glass material.Add alumina powder in order to regulate the coefficient of expansion, when being characterized in exposing, in glass and the thick film layers a little less than the ultraviolet scattering, thereby to can be made into live width be below the 50 μ m, highly reaches the fine pattern barrier of 150 μ m, burns till under 520 ℃.The major defect of this glass material is leaded, can not satisfy the requirement of present unleaded development.
[summary of the invention]
The objective of the invention is to overcome the deficiency of existing barrier, provide a kind of environment-friendly type lead-free low temperature PDP barrier with glass powder and preparation method thereof, have that softening temperature is low, unleaded, the sealing-in resistance to air loss reaches the diversified characteristics of color well with glass powder with low melting point.
The objective of the invention is to be achieved through the following technical solutions:
A kind of environment-friendly type lead-free low temperature PDP barrier glass dust, raw materials by weight consists of: Bi 2O 3Be 30～50%, B 2O 3Be that 5～30%, MgO is 5～30%, V 2O 5Be 5～30%, P 2O 5Be 1～10%, K 2O is that 1～10%, CaO is 1～5%, SiO 2Be 1～5%, Al 2O 3Be 1～5%;
Described Bi 2O 3Be preferably 35～45%, the best is 44%;
Described B 2O 3Be preferably 15～25%, the best is 18%;
Described MgO is preferably 10～20%, and the best is 13%;
Described V 2O 5Be preferably 8～20%, the best is 12%;
Described P 2O 5Be preferably 3～8%, the best is 4%;
Described K 2O is preferably 3～8%, and the best is 4%;
Described CaO is preferably 2～4%, and the best is 3%;
Described SiO 2Be preferably 1～3%, the best is 1%;
Described Al 2O 3Be preferably 1～3%, the best is 1%;
Described Bi 2O 3, V 2O 5, P 2O 5Total percentage by weight be 45～75%;
Described CaO, SiO 2And Al 2O 3Total percentage by weight be 3～12%.
Another object of the present invention is to provide a kind of preparation method of above-mentioned a kind of environment-friendly type lead-free low temperature PDP barrier that be used to produce with glass powder.
A kind of environment-friendly type lead-free low temperature PDP barrier with the preparation method of glass powder, step is,
(1) weight percent according to each component takes by weighing each raw material;
(2) with the raw material thorough mixing that is taken by weighing;
(3) mixed compound is put into crucible, put into furnace temperature then and be 1200 ℃ electric furnace, insulation 40min;
(4) glass metal after will melting is poured tabletting machine into and is pressed into thin slice;
(5) foliated glass behind the compressing tablet is put into the ball mill ball milling;
(6) glass powder behind the ball milling is sieved, detects, packs.
Glass powder with low melting point of the present invention is applicable to the plasma display barrier wall glass powder with low melting point, but the purposes of glass powder with low melting point of the present invention is not limited thereto, and obtains having by adding different compositions and adjusting proportion relation between each component that to obtain the coefficient of expansion be 65～95 * 10 -7/ ℃, firing temperature is 530～670 ℃ a plasma display barrier wall glass powder with low melting point.
A kind of environment-friendly type lead-free low temperature of the present invention PDP barrier with the positively effect of glass powder and preparation method thereof is:
(1) the present invention is not leaded, satisfies the environmental requirement of WEEE, RoHS instruction, can be at the sintering after the silk screen printing that realizes article on plasma body display barrier wall material under the lower glass transition temperature of maintenance;
(2) applied widely, have the performance setting range of broad, simultaneously can also with the glass that conforms to the coefficient of expansion in this temperature, pottery, metal sealing, sealing property is good;
(3) add the difference of pigment, can realize the color variation behind the sintering, satisfy different clients' individual demand;
[embodiment]
In order to obtain lead-free low melting point glass powder for barrier, must replace lead oxides with having than low softening point and playing the component that reduces softening temperature.The invention provides the oxide compound that mainly contains bismuth, vanadium and phosphorus, 530～570 ℃ of sintering temperatures, thermal expansivity is 75～85 * 10 -7/ ℃ (300 ℃), and water tolerance and the good environment-friendly type lead-free glass powder of sealing strength.
Described raw material is chemical pure level raw material, works as Bi 2O 3Content during less than 30wt%, prepared frit-sintered temperature is higher, can not be used for plasma display barrier wall, works as Bi 2O 3Percentage by weight during greater than 50wt%, have the sintering temperature under the service condition of being suitable for, but Bi 2O 3Increasing of content increased the cost of raw material, simultaneously, and with Bi 2O 3Increasing of content, the coefficient of expansion of frit is greater than 85 * 10 -7/ ℃, can not satisfy plasma display barrier wall with the instructions for use of frit, cause not mating of both coefficients of expansion, so Bi 2O 3Content be preferably 35～45wt%.
B 2O 3Be the formation oxide of glass, can reduce the coefficient of expansion of glass, improve heat endurance, the chemical stability of glass, increase the refractive index of glass, improve the gloss of glass, improve the mechanical performance of glass.B 2O 3If content less than 5wt%, can not play the effect of flux, with the clarification of accelerating glass and the crystallizing power that reduces glass, if B 2O 3Content greater than 30wt%, because B 2O 3Often with the steam volatilization, the easy generation is rich in SiO on the surface of glass metal 2Crystallization material skin, so B 2O 3Content be preferably 15～25wt%.
If the content of MgO is less than 5wt%, then water tolerance descends.If surpass 30wt%, then can not obtain stable glassy state, the transition temperature of glass raises simultaneously, so the content of MgO is preferably 10～20wt%.V 2O 5Have the reduction glass softening point, make glass when fusing, have suitable flowability and the effect that increases thermal expansion coefficient of glass, V 2O 5If content less than 5wt%, the effect that then reduces temperature is inadequate or not obvious, if V 2O 5Content is greater than 30wt%, and then thermal coefficient of expansion increases greatly, so that descend with the sealing-in matching of glass plate, produces easily simultaneously a large amount of minute bubbles in the process of sealing-in, thereby unfavorable to the air-tightness after the sealing-in, in addition, has also increased greatly cost.So V 2O 5Content be preferably 8～20wt%.
P 2O 5Also has the effect that reduces glass softening point, P 2O 5If content less than 1wt%, the effect that then reduces temperature is inadequate or not obvious, if P 2O 5Content is greater than 10wt%, and then the chemical stability of glass is understood rapid reduction, has influence on the service life of plasma display barrier wall, so P 2O 5Content be preferably 3～8wt%.K 2The O component that is absolutely necessary is if content, then can not play the purpose that reduces glass transition temperature less than 1wt%, if K 2The content of O is greater than 10wt%, and then thermal coefficient of expansion changes, and resistance to water also descends, so K 2The content of O is preferably 3～8wt%.
CaO, SiO 2And Al 2O 3Can promote vitrifying, can also improve resistance to water, nitrogen content is too high, can cause the rising of glass transition temperature, so content is respectively 2～4wt%, 1～3wt% and 1～3wt%.
The embodiment of a kind of environment-friendly type lead-free low temperature of the present invention PDP barrier with glass powder and preparation method thereof below is provided.
Embodiment 1
One, the raw material composition is by weight percentage:
Bi 2O 3Be 44%, B 2O 3Be that 18%, MgO is 13%, V 2O 5Be 12%, P 2O 5Be 4%, K 2O is that 4%, CaO is 3%, SiO 2Be 1%, Al 2O 3Be 1%.
Two, preparation method:
(1) weight percent according to each component takes by weighing each raw material;
(2) with the raw material thorough mixing that is taken by weighing;
(3) mixed compound is put into crucible, put into furnace temperature then and be 1200 ℃ electric furnace, insulation 40min;
(4) glass metal after will melting is poured tabletting machine into and is pressed into thin slice;
(5) foliated glass behind the compressing tablet is put into the ball mill ball milling;
(6) glass powder behind the ball milling is sieved, detects, packs.
Three, test result:
The coefficient of expansion: 82 * 10 -7/ ℃ (300 ℃) sintering temperature: 535 ℃
Sintering time: 50min particle size range: 0.1～10 μ m
Volume specific resistance:＞10 12Ω cm water tolerance: good
Embodiment 2
One, the raw material composition is by weight percentage:
Bi 2O 3Be 34%, B 2O 3Be that 18%, MgO is 8%, V 2O 5Be 21%, P 2O 5Be 4%, K 2O is that 6%, CaO is 4%, SiO 2Be 2%, Al 2O 3Be 3%.
Two, preparation method: with embodiment one.
Three, test result:
The coefficient of expansion: 85 * 10 -7/ ℃ (300 ℃) sintering temperature: 540 ℃
Sintering time: 50min particle size range: 0.1～10 μ m
Volume specific resistance:＞10 12Ω cm water tolerance: good
Embodiment 3
One, the raw material composition is by weight percentage:
Bi 2O 3Be 39%, B 2O 3Be that 18%, MgO is 10%, V 2O 5Be 18%, P 2O 5Be 5%, K 2O is that 4%, CaO is 3%, SiO 2Be 2%, Al 2O 3Be 1%.
Two, preparation method: with embodiment one.
Three, test result:
The coefficient of expansion: 78 * 10 -7/ ℃ (300 ℃) sintering temperature: 550 ℃
Sintering time: 50min particle size range: 0.1～10 μ m
Volume specific resistance:＞10 12Ω cm water tolerance: good
Embodiment 4
One, the raw material composition is by weight percentage:
Bi 2O 3Be 42%, B 2O 3Be that 18%, MgO is 13%, V 2O 5Be 13%, P 2O 5Be 4%, K 2O is that 6%, CaO is 2%, SiO 2Be 1%, Al 2O 3Be 1%.
Two, preparation method: with embodiment one.
Three, test result:
The coefficient of expansion: 77 * 10 -7/ ℃ (300 ℃) sintering temperature: 565 ℃
Sintering time: 50min particle size range: 0.1～10 μ m
Volume specific resistance:＞10 12Ω cm water tolerance: good
It should be noted last that: above embodiment only is illustrative rather than definitive thereof technical scheme of the present invention, although the present invention is had been described in detail with reference to the foregoing description, those of ordinary skill in the art is to be understood that, still can make amendment or be equal to replacement the present invention, and not breaking away from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.

Claims (10)

1. an environment-friendly type lead-free low temperature PDP barrier glass dust is characterized in that raw materials by weight consists of, and raw materials by weight consists of: Bi 2O 3Be 30～50%, B 2O 3Be that 5～30%, MgO is 5～30%, V 2O 5Be 5～30%, P 2O 5Be 1～10%, K 2O is that 1～10%, CaO is 1～5%, SiO 2Be 1～5%, Al 2O 3Be 1～5%.
2. a kind of environment-friendly type lead-free low temperature PDP barrier glass dust according to claim 1 is characterized in that described Bi 2O 3Be 35～45%; Described B 2O 3Be 15～25%; Described MgO is 10～20%.
3. a kind of environment-friendly type lead-free low temperature PDP barrier glass dust according to claim 2 is characterized in that described Bi 2O 3Be 44%; Described B 2O 3Be 18%; Described MgO is 13%.
4. a kind of environment-friendly type lead-free low temperature PDP barrier glass dust according to claim 1 is characterized in that described V 2O 5Be 8～20%; Described P 2O 5Be 3～8%; Described K 2O is 3～8%.
5. a kind of environment-friendly type lead-free low temperature PDP barrier glass dust according to claim 4 is characterized in that described V 2O 5Be 12%; Described P 2O 5Be 4%; Described K 2O is 4%.
6. a kind of environment-friendly type lead-free low temperature PDP barrier glass powder according to claim 1 is characterized in that described CaO is 2～4%; Described SiO 2Be 1～3%; Described Al 2O 3Be 1～3%.
7. a kind of environment-friendly type lead-free low temperature PDP barrier glass powder according to claim 6 is characterized in that described CaO is 3%; Described SiO 2Be 1%; Described Al 2O 3Be 1%.
8. a kind of environment-friendly type lead-free low temperature PDP barrier glass dust according to claim 1 is characterized in that described Bi 2O 3, V 2O 5, P 2O 5Total percentage by weight be 45～75%.
9. a kind of environment-friendly type lead-free low temperature PDP barrier glass dust according to claim 8 is characterized in that described CaO, SiO 2And Al 2O 3Total percentage by weight be 3～12%.
10. a kind of environment-friendly type lead-free low temperature PDP barrier according to claim 1 is characterized in that with the preparation method of glass powder, comprises the steps:
(1) weight percent according to each component takes by weighing each raw material;
(2) with the raw material thorough mixing that is taken by weighing;
(3) mixed compound is put into crucible, put into furnace temperature then and be 1200 ℃ electric furnace, insulation 40min;
(4) glass metal after will melting is poured tabletting machine into and is pressed into thin slice;
(5) foliated glass behind the compressing tablet is put into the ball mill ball milling;
(6) glass powder behind the ball milling is sieved, detects, packs.
CN2010101253409A 2010-03-16 2010-03-16 Environmentally-friendly lead-free low-temperature glass powder used for barrier of PDP (plasma display panel), and preparation method thereof Pending CN102190444A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102875020A (en) * 2012-09-27 2013-01-16 广东风华高新科技股份有限公司 Lead-free glass material and preparation method thereof
CN114230187A (en) * 2022-01-19 2022-03-25 西安石油大学 Low-temperature lead-free electronic glass powder for photoelectric sealing

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102875020A (en) * 2012-09-27 2013-01-16 广东风华高新科技股份有限公司 Lead-free glass material and preparation method thereof
CN114230187A (en) * 2022-01-19 2022-03-25 西安石油大学 Low-temperature lead-free electronic glass powder for photoelectric sealing

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Application publication date: 20110921