Tin phosphate-based glass-containing crystallizable composition
Abstract
[Task] Provided is a tin-phosphate glass-containing crystalline composition that crystallizes stably during firing and has a high crystallinity.
Solution.0.01 to 30% by weight of one or more metaphosphate compound powders selected from the group consisting of tin phosphate glass powder 70 to 99.99% by weight, magnesium metaphosphate, calcium metaphosphate, strontium metaphosphate, barium metaphosphate and aluminum metaphosphate. % Containing tin phosphate glass-containing crystalline composition.

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5 claims: 3 independent, 2 dependent
- 1【特許請求の範囲】 【請求項1】リン酸スズ系ガラス粉末を70~99.99重量%、メタリン酸マグネシウム、メタリン酸カルシウム、メタリン酸ストロンチウム、メタリン酸バリウムおよびメタリン酸アルミニウムからなる群から選ばれた1種以上のメタリン酸化合物粉末を0.01~30重量%含有するリン酸スズ系ガラス含有結晶性組成物。
- 2【請求項2】ZnOの含有量が0~25モル%であるリン酸スズ系ガラス粉末を40~99重量%、ZnOの含有量が26~70モル%であるリン酸亜鉛系ガラス粉末を1~60重量%含有するリン酸スズ系ガラス含有結晶性組成物。
- 3【請求項3】リン酸スズ系ガラス粉末を95~99.99重量%、鉄粉末を0.01~5重量%含有するリン酸スズ系ガラス含有結晶性組成物。
- 4【請求項4】前記リン酸スズ系ガラス粉末の組成が実質的にモル%表示で、 P 2 O 5 25~38%、 SnOに換算したスズ酸化物 43~75%、 ZnO 0~25%、 SiO 2 0~5%、 Al 2 O 3 0~5%、 B 2 O 3 0~10%、 MoO 3 0~5%、 In 2 O 3 0~5%、 WO 3 0~5%、 MgO+CaO+SrO 0~15%、 である請求項1、2または3に記載のリン酸スズ系ガラス含有結晶性組成物。
- 5【請求項5】セラミックスフィラーを1~40重量%含有する請求項1、2、3または4に記載のリン酸スズ系ガラス含有結晶性組成物。
Independent claims5
79 paragraphs in 1 section, as filed
Description: TECHNICAL FIELD [Detailed description of the invention]
【0001】
[Technical field to which the invention belongs]
The present invention relates to a tin phosphate glass-containing crystalline composition suitable for sealing, coating, forming PDP (plasma display panel) ribs, and particularly suitable for sealing and wearing a cathode ray tube panel and a funnel.
【0002】
[Conventional technology]
A lead-free material is required as a sealing material for cathode ray tube panels and funnels. A typical example of such a material is tin phosphate glass. For example, Japanese Patent Application Laid-Open No. 6-183775 states SnO-ZnO-P in which the molar ratio of SnO: ZnO is in the range of 1: 1 to 5: 1.<sub>2</sub>O<sub>5</sub>System glass is disclosed.
【0003】
[Problems to be Solved by the Invention]
Tin phosphate glass powder containing 30 to 70 mol% of SnO has a low softening point and is a material having excellent properties for sealing or coating. However, the crystallization of glass that occurs during firing is unstable, the surface layer of glass crystallizes faster than the inside, and uncrystallized glass may seep out from the inside, causing a problem.
【0004】
SnO-ZnO-P disclosed in JP-A-6-183775<sub>2</sub>O<sub>5</sub>The system glass aims at stable crystallization of the glass by containing a large amount of ZnO, but a higher crystallization rate is required. An object of the present invention is to solve the above problems and to provide a tin phosphate glass-containing crystalline composition which crystallizes stably at the time of firing and has a high crystallinity.
【0005】
[Means for solving problems]
The present invention is one or more metaphosphate compound powders selected from the group consisting of 70 to 99.99% by weight of tin phosphate glass powder, magnesium metaphosphate, calcium metaphosphate, strontium metaphosphate, barium metaphosphate and aluminum metaphosphate. A tin phosphate-based glass-containing crystalline composition containing 0.01 to 30% by weight of the above (1st invention).
【0006】
Further, the present invention comprises 40 to 99% by weight of tin phosphate glass powder having a ZnO content of 0 to 25 mol%, and zinc oxide glass powder having a ZnO content of 26 to 70 mol%. Provided is a zinc phosphate-based glass-containing crystalline composition containing 1 to 60% by weight (second invention).
【0007】
Further, the present invention provides a tin phosphate glass-containing crystalline composition containing 95 to 99.99% by weight of tin phosphate glass powder and 0.01 to 5% by weight of iron powder (third invention).
【0008】
The present inventor has found that the crystallization rate can be increased by precipitating crystal A, which will be described later, at the time of firing, and came to the present invention.
【0009】
BEST MODE FOR CARRYING OUT THE INVENTION
The tin phosphate glass in the present invention is P.<sub>2</sub>O<sub>5</sub>It is a glass containing 25 mol% or more of tin oxide (hereinafter, simply referred to as SnO) converted to SnO and 30 mol% or more. P<sub>2</sub>O<sub>5</sub>If it is less than 25 mol%, vitrification becomes difficult. It is preferably 28 mol% or more. If SnO is less than 20 mol%, the softening point becomes too high. It is preferably 40 mol% or more.
【0010】
The tin phosphate glass-containing crystalline composition of the present invention (hereinafter, simply referred to as the crystalline composition of the present invention) contains a tin phosphate glass powder and a crystallization accelerator. The crystallization accelerator referred to here has an action of promoting the precipitation of "crystal A" when the crystalline composition of the present invention is fired at 350 to 550 ° C. "Crystal A" is a diffraction pattern by powder X-ray diffraction using CuKα rays, which has the strongest diffraction peak at a lattice spacing d of 3.41 angstroms, d of 3.84 angstroms, 3.70 angstroms, 3.25 angstroms, and 3.11 angstroms. It is a crystal having a small diffraction peak at each location, and is considered to be an angstrom pyrophosphate crystal or a similar tin phosphate crystal.
【0011】
When the composition containing the tin phosphate glass powder containing ZnO is fired, "crystal B" may be precipitated. "Crystal B" is a crystal whose diffraction pattern by powder X-ray diffraction method using CuKα rays has strong diffraction peaks at lattice intervals d of 3.86 angstroms, 2.99 angstroms, and 2.53 angstroms, respectively, and zinc. It is considered to be a crystal containing.
【0012】
The crystalline composition of the present invention stably precipitates crystals during firing. Here, "stable precipitation of crystals" means that crystallization during firing proceeds in substantially the same manner both on the surface layer and inside. As a result, there is no possibility that a large amount of uncrystallized glass will seep out from the inside and cause a problem. Further, the crystalline composition of the present invention has a higher crystallization rate and a higher strength after firing than a composition in which crystals A are not precipitated and crystals B are precipitated during firing.
【0013】
In the crystalline composition of the first invention of the present invention, as a crystallization accelerator, one or more metalins selected from the group consisting of magnesium metaphosphate, calcium metaphosphate, strontium metaphosphate, barium metaphosphate and aluminum metaphosphate. Contains 0.01 to 30% by weight of acid compound powder. If it is less than 0.01% by weight, the effect is small. It is preferably 3% by weight or more, more preferably 6% by weight or more. If it exceeds 30% by weight, the fluidity during firing becomes too small. It is preferably 20% by weight or less, more preferably 10% by weight or less.
【0014】
In the crystalline composition of the second invention of the present invention, the ZnO content of the tin phosphate glass powder is 0 to 25 mol%, and the ZnO content of the crystallization accelerator is 26 to 70 mol%. Contains 1 to 60% by weight of zinc phosphate glass powder. If it is less than 1% by weight, the effect is small. It is preferably 10% by weight or more, more preferably 20% by weight or more, and particularly preferably 30% by weight or more. If it exceeds 60% by weight, the fluidity during firing becomes too small. It is preferably 50% by weight or less, more preferably 40% by weight or less.
【0015】
The zinc phosphate glass is P.<sub>2</sub>O<sub>5</sub>25 to 50 mol%, ZnO 35 to 70 mol%, and SnO 0 to 25 mol%, respectively. In addition to the above components, SiO is used to increase the stability of the glass or suppress the precipitation of crystal B.<sub>2</sub>, Al<sub>2</sub>O<sub>3</sub>, B<sub>2</sub>O<sub>3</sub>, In<sub>2</sub>O<sub>3</sub>, WO<sub>3</sub>, TiO<sub>2</sub>, CuO, MoO<sub>3</sub>, MgO, CaO, SrO, BaO and the like may be contained up to 10 mol% in total.
【0016】
The crystalline composition of the third invention of the present invention contains 0.01 to 5% by weight of iron powder as a crystallization accelerator. If it is less than 0.01% by weight, the effect is small. It is preferably 0.5% by weight or more, more preferably 0.8% by weight or more. If it exceeds 5% by weight, it foams during firing. It is preferably 3% by weight or less, more preferably 2% by weight or less.
【0017】
The crystalline composition of the present invention contains tin phosphate glass powder and the above crystallization accelerator as essential components, but other components may be added in an amount depending on the application as long as the object of the present invention is not impaired. It may be contained up to 50% by weight. For example, a ceramic filler may be included to adjust the coefficient of thermal expansion. The average linear expansion coefficient of the ceramic filler from room temperature to 300 ° C is 70 × 10.<sup>-7</sup>It is preferably less than / ° C, and examples thereof include silica, β-eucryptite, β-spojumen, cordierite, and zircon. The preferred content range of the ceramic filler is 1-40% by weight. When used for forming PDP ribs, a white pigment such as titanium oxide or alumina may be contained.
【0018】
The preferred composition of tin phosphate glass in the present invention is substantially in mol%. P<sub>2</sub>O<sub>5</sub> 25 ~ 38%, SnO 43 ~ 75%, ZnO 0 ~ 25%, SiO<sub>2</sub> 0 ~ 5%, Al<sub>2</sub>O<sub>3</sub> 0 ~ 5%, B<sub>2</sub>O<sub>3</sub> 0 ~ 10%, MoO<sub>3</sub> 0 ~ 5%, In<sub>2</sub>O<sub>3</sub> 0 ~ 5%, WO<sub>3</sub> 0 ~ 5%, MgO + CaO + SrO 0 ~ 15%, Is. Hereinafter, the reason for limiting the composition will be described by simply expressing mol% as%.
【0019】
P<sub>2</sub>O<sub>5</sub>If the content of is less than 25%, vitrification becomes difficult. It is preferably 28% or more, more preferably 29% or more. Water resistance decreases above 38%. It is preferably 36% or less, more preferably 34% or less.
【0020】
If the SnO content is less than 43%, the softening point will be too high. It is preferably 45% or more, more preferably 50% or more, and particularly preferably 60% or more. If it exceeds 75%, vitrification becomes difficult. It is preferably 73% or less, more preferably 70% or less, and particularly preferably 65% or less.
【0021】
ZnO is not required, but may be contained up to 25% to stabilize the glass. If it exceeds 25%, the softening point may become too high. It is more preferably 15% or less, and particularly preferably 7% or less. Further, it is more preferable to contain 3% or more.
【0022】
When ZnO is contained, the SnO content is preferably 3 times or more the ZnO content in order to prevent zinc pyrophosphate crystals from precipitating during firing. More preferably, it is 5 times or more. Zinc pyrophosphate crystals have a negative coefficient of thermal expansion in the temperature range from room temperature to about 100 ° C, and if these crystals precipitate during firing, expansion matching may become difficult.
【0023】
SiO to stabilize the glass<sub>2</sub>Up to 5%, Al<sub>2</sub>O<sub>3</sub>Up to 5%, B<sub>2</sub>O<sub></sub><sub>3</sub>Up to 10%, MoO<sub>3</sub>Up to 5%, In<sub>2</sub>O<sub>3</sub>Up to 5%, WO<sub>3</sub>May be contained up to 5%, and MgO, CaO, and SrO may be contained up to 15% in total.
【0024】
The tin phosphate glass in the present invention is substantially composed of the above components, but other components may be contained in a total amount of up to 5 mol% as long as the object of the present invention is not impaired. For example, Fe to color glass<sub>2</sub>O<sub>3</sub>Etc. may be contained, and TiO<sub>2</sub>, CuO, AgO<sub>2</sub>, BaO and the like may be contained.
【0025】
The softening point of the tin phosphate glass in the present invention is preferably 450 ° C. or less. Above 450 ° C, the fluidity during firing may become too small.
【0026】
The firing temperature of the crystalline composition of the present invention is preferably 400 to 550 ° C. The crystalline composition of the present invention contains resin components such as ethyl cellulose and nitrocellulose, α-terpineol, isoamyl acetate, ethylene glycol monoethyl ether, diethylene glycol din-butyl ether, butyl carbitol acetate, and ethylene glycol monophenyl ether. You may use it by kneading it with a vehicle containing a solvent such as, and making it into a paste.
【0027】
The crystalline composition of the present invention is used for sealing, coating, PDP rib formation, and the like. It is particularly suitable for sealing CRT panels and funnels.
【0028】
[Example]
Table P<sub>2</sub>O<sub>5</sub>~ ZrO<sub>2</sub>The raw materials are mixed so as to have the composition described in mol% in the column of, put in a quartz crucible, melted at 1200 ° C for 30 minutes, and the obtained glass is poured into a stainless steel roller to form flakes, and then alumina. It was pulverized for 100 minutes with a ball mill to obtain a tin phosphate glass powder. In addition, the composition described in mol% is P.<sub>2</sub>O<sub>5</sub>The raw materials were prepared so as to have 30%, SnO: 20%, and ZnO: 50%, and a zinc phosphate-based glass powder was obtained in the same manner as in the case of the tin phosphate-based glass powder. The softening points of the tin phosphate glass powder and the zinc phosphate glass powder were measured by a differential thermal analyzer (DTA). The softening point of the zinc phosphate glass powder was 471 ° C. The softening point (unit: ° C) of tin phosphate glass powder is shown in the table.
【0029】
Next, tin phosphate glass powder, calcium metaphosphate powder (manufactured by Lhasa Industry Co., Ltd.), aluminum metaphosphate powder (manufactured by Lhasa Industry Co., Ltd.), zinc phosphate glass powder, iron powder, cordierite powder (Asahi Glass Co., Ltd.) (Manufactured by the company) was mixed at the ratio described in% by weight in the table to obtain a tin phosphate glass-containing composition. Regarding the obtained tin phosphate glass-containing composition, the flow button diameter (unit: mm) and the coefficient of thermal expansion (unit: × 10)<sup>-7</sup>/ ° C), precipitated crystals, and critical exhaust heating rate (unit: ° C / min) were measured by the following methods. Examples 1 to 4 are examples, and examples 5 to 6 are comparative examples.
【0030】
Flow button diameter: A molded product obtained by pressure-molding 3.8 g of sample powder into a cylinder with a diameter of 12.7 mm was fired on a glass plate at 440 ° C for 35 minutes to allow the molded product to flow. Measure the diameter of the button. This flow button diameter is an index of fluidity at the time of sealing, and is preferably 16 mm or more.
【0031】
Coefficient of thermal expansion: Approximately 5 g of sample powder is pressure-molded into a rod of appropriate size, fired in the same way as when measuring the flow button diameter, and then polished into a cylinder with a diameter of 5 mm and a length of 15 to 20 mm. Get a sample. This sample was heated using a thermal expansion measuring device (Diratomometer 5000 manufactured by Mac Science Co., Ltd.) at a heating rate of 10 ° C / min to measure the elongation, and average linear expansion of 50 to 250 ° C. The coefficient was calculated. The coefficient of thermal expansion is 60 × 10<sup>-7</sup>~105×10<sup>-7</sup>It is preferably / ° C.
【0032】
Precipitated crystals: The flow button was pulverized to prepare a sample, and the types of crystals present in this sample were examined by powder X-ray diffraction using CuKα rays. Crystal A has the strongest diffraction peak at a lattice spacing d of 3.41 angstroms and small diffraction peaks at d at 3.84 angstroms, 3.70 angstroms, 3.25 angstroms, and 3.11 angstroms. Crystal B has strong diffraction peaks at d of 3.86 angstroms, 2.99 angstroms, and 2.53 angstroms, respectively. The cordierite detected in Examples 1, 5 and 6 is due to the cordierite powder in the tin phosphate glass composition, and is considered not to be a precipitated crystal.
【0033】
Limit exhaust heating rate: A glass bulb with a panel and funnel for a 29-inch CRT sealed at 440 ° C, 10<sup>-6</sup>While exhausting to Torr, the temperature was raised to 320 ° C at various heating rates, and the temperature rising rate at the limit of breaking the glass bulb was obtained. It is preferably 15 ° C / min or higher.
【0034】
[table 1]
<img file="JP2000327369A_D0001.tif" />【0035】
[Table 2]
<img file="JP2000327369A_D0002.tif" />【0036】
[Effect of the invention]
According to the present invention, tin-phosphate glass-containing crystals that undergo stable crystallization when fired at 400 to 550 ° C and are applicable to lead-free sealing, coating, PDP rib formation, etc. A sex composition is obtained. In particular, when applied to the sealing of cathode ray tube panels and funnels, high sealing strength can be obtained.
2 sheets
Sheet 1 Sheet 2
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| US7704903B2 | Cited by | United States of America | Applicant |
| DE102004011520A1 | Cited by | Germany | Search report |
| US8080490B2 | Cited by | United States of America | Applicant |
| US7709027B2 | Cited by | United States of America | Applicant |
| US8461069B2 | Cited by | United States of America | Applicant |
| EP1580172A2 | Cited by | European Patent Office (EPO) | Applicant |
2 priority claims, no other members on record
Priority claims2
| Document | Office | Kind | Date |
|---|---|---|---|
| 14202899 | Japan | A | |
| JP19990142028 | – | – | – |
Numbers
- Publication
- 2000-327369
- Publication, DOCDB
- 2000327369
- Publication, EPODOC
- JP2000327369
- Application
- 11142028
- Application, DOCDB
- 14202899
- Application, EPODOC
- JP19990142028
Titles2
- Japanese
- リン酸スズ系ガラス含有結晶性組成物
- English
- INDUSTRIAL APPLICABILITY [Title of Invention] A crystalline composition containing tin phosphate glass.
Classification
- IPC, 9
- H01J29 86
- C03C8 08
- C03C8 18
- C03C8 22
- C03C8 24
- C03C10 00
- H01J11 22
- H01J11 34
- H01J11 36