JP2003252648A - Tin phosphate glass and composite material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass material which has the same characteristics as those of a conventional sealing material, a conventional insulating coating material, although not containing a lead component. <P>SOLUTION: The glass material consists of glass having the composition of, by mol%, SnO of 30-70%, P<SB>2</SB>O<SB>5</SB>of 20-45%, lanthanoid oxides of 0.1-25%, ZnO of 0-20%, MgO of 0-20%, Al<SB>2</SB>O<SB>3</SB>of 0-10%, SiO<SB>2</SB>of 0-15%, B<SB>2</SB>O<SB>3</SB>of 0-30%, and R<SB>2</SB>O (R is the total of Li, Na, K and/or Cs) of 0-20%. One kind or more selected from La<SB>2</SB>O<SB>3</SB>, CeO<SB>2</SB>, and Gd<SB>2</SB>O<SB>3</SB>are preferably used as lanthanoid oxides. Furthermore, the glass may be made a composite material by adding a powdery refractory filler to the glass. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a fluorescent display tube (VF).
D), a field emission display (FED), a plasma display (PDP), a cathode ray tube (CRT), and the like, and lead-free glass that can be used for sealing display tubes, and a composite material using the same.

[0002]

2. Description of the Related Art VFD, FED, PDP, CRT and other display tubes are sealed with a sealing temperature of 430 to 500 ° C. and a thermal expansion coefficient of 60 to 100 × 10 ⁻⁷ / ° C. A glass paste using a dressing material is used.

To seal the display tube, first, a glass paste is applied to the sealed portion of the object to be sealed, dried and then heated for debinding. After that, main baking is performed in a state of being in close contact with the other object to be sealed to complete the sealing. In addition, PDP, C
Since a display tube such as an RT is subjected to heat treatment for exhausting after sealing, it is necessary to select a material that does not deteriorate the airtightness due to the deterioration of the sealing material.

Further, in order to obtain a stronger bond, it is necessary to heat the glass powder to a temperature sufficient to wet the adhesive surface of the object to be sealed, but in some cases the process temperature must be kept as low as possible. Therefore, a material that can be sealed even at a low temperature is desired.

Under these circumstances, a composite material composed of a PbO-B ₂ O ₃ glass powder and a refractory filler powder, which can be sealed at a low temperature, has been mainly used as the sealing material of this type. .

[0006]

However, recently, it has been required to remove lead from glass from the viewpoint of environmental problems.

As lead-free glass, tin phosphate-based glass
Glass is JP-A-7-69672 and JP-A-9-2271.
No. 54 etc. have been proposed. However, this type of glass
Is P ₂O_FiveIn large amounts as the main glass-forming oxide
Therefore, the weather resistance of the powder fired product deteriorates and
Due to its high properties, it may deteriorate during storage of the powder, resulting in the specified characteristics.
There is a drawback that you cannot get it. Also, a large amount of SnO
In order to contain SnO, when SnO is heated in the binder removal step,
SnO₂And surface devitrification is likely to occur.
Phosphate gas
Lass-specific defects are likely to appear and are now widely used
PbO-B₂O₃The characteristics of glass-based glass have not yet been reached.

A glass obtained by adding In ₂ O ₃ to the composition of tin phosphate type glass for the purpose of improving hygroscopicity is disclosed in JP-A-200-200
No. 0-219536. However I
Since n ₂ O ₃ is a noble metal and is very expensive, even if it is a small amount, the price of the glass material increases significantly, which is not realistic. Further, even in the above proposal, the problem of devitrification on the surface has not been solved yet.

It is an object of the present invention to provide a glass material having the same characteristics as conventional sealing materials, insulating coating materials, etc., even without containing a lead component.

[0010]

As a result of various experiments, the present inventor has found that the above object can be achieved by introducing a predetermined amount of lanthanoid oxide into glass, and proposes the present invention. Is.

That is, the tin phosphate glass of the present invention comprises SnO 30 to 70% and P ₂ O ₅ 20 to 45 in terms of mol%.
%, Lanthanoid oxide 0.1 to 25%.

The composite material of the present invention is characterized by comprising the tin phosphate glass powder and the refractory filler powder.

[0013]

In the tin phosphate glass of the present invention, the reason why the glass composition range is limited as described above will be described below.

SnO is a component that lowers the melting point of glass. When SnO is less than 30%, the viscosity of glass becomes high and the firing temperature becomes too high, and when it exceeds 70%, it does not vitrify. If the SnO component is large, devitrification tends to occur during firing, so the content is preferably 60% or less. Further, when it is 40% or more, the fluidity is excellent and a high airtightness can be obtained, which is preferable.

P ₂ O ₅ is a glass-forming oxide. P ₂ O ₅
Is less than 20%, the stability of the glass is insufficient. If it is in the range of 20 to 45%, the glass will have sufficient stability, but if it exceeds 45%, the moisture resistance will be poor. Further, when P ₂ O ₅ is 25% or more, the glass is more stabilized, but when it exceeds 35%, the weather resistance of the fired product tends to be slightly deteriorated, so that it is preferably 25 to 35%.

The lanthanoid oxide is a network modifying oxide and is an essential component in the present invention. By including the lanthanoid oxide in the glass component in a total amount of 0.1% or more, the following effects 1) to 3) can be obtained.

1) It is effective in reducing the hygroscopicity when the glass is crushed and then stored in the powder state. If the amount of lanthanoid oxide is low, it may absorb moisture during storage and the desired characteristics may not be obtained during use.

2) It is possible to improve the weather resistance after firing (for example, main firing for sealing). When the amount of the lanthanoid oxide is small, powdery substances are likely to emerge on the glass surface or exudate around the fired body when stored in a hot and humid state after firing.

3) calcination (eg heat for debinding)
Devitrification does not occur during processing). Also under severe conditions after firing
Reheated (for example, in the PDP manufacturing process, after sealing
10 to 20 hours at 350 ° C to 450 ° C for evacuation
That is, heat treatment with a relatively high temperature and long heating time is performed.
Even if the case), the glass does not deteriorate. Lanta
If the amount of the oxides is low, devitrification will occur during firing, and
It may not be possible to seal the seal. Also undergoes severe reheating
If it is peeled, devitrification may occur and the quality may deteriorate, and air tightness may not be maintained
There is. The cause of devitrification is SnO which is a glass component.
Is SnO during firing ₂Due to the change to and precipitation.

On the other hand, when the content of the lanthanoid oxide exceeds 25%, the viscosity of the melt during melting is increased and the fluidity during firing is impaired. Considering the balance between the storage stability of the powder for a long period of time, the weather resistance after firing, and the fluidity, the total content of the lanthanoid oxide is 2 to 15%, particularly 4 to 1%.
It is preferably 5%.

As the lanthanoid oxide, it is preferable to use one or more selected from La ₂ O ₃ , CeO ₂ and Gd ₂ O ₃ which do not cause glass coloring.

La ₂ O ₃ is a component having a great effect of improving the humidity resistance and the weather resistance. However, since it tends to increase the viscosity when melted, it is better not to use a large amount. When La ₂ O ₃ is used alone as the lanthanoid oxide, its content is 0.1 to 10%, particularly 1 to 5%, and further 3 to 5%.
Is preferred.

Although CeO ₂ has a smaller effect of improving moisture resistance and weather resistance than La ₂ O ₃ , it has a smaller tendency to increase the viscosity during melting than that of La ₂ O ₃ , so a relatively large amount of CeO ₂ should be contained. You can It is also relatively inexpensive among the lanthanoid-based raw materials. When CeO ₂ is used alone, its content is 0.1 to 15%, especially 5 to 10%, and further 5 to
It is preferably 8%. In order to obtain a sufficient effect, it is desirable to contain 5% or more.

Gd ₂ O ₃ is effective in improving the moisture resistance and the weather resistance similarly to La ₂ O ₃ . Further, the tendency to increase the viscosity during melting is smaller than that of La ₂ O ₃ . However, it is better not to use a large amount because it increases the devitrification tendency at the time of sealing after debinding. When Gd ₂ O ₃ is used alone, its content is 0.1-10%, especially 1-5%, and further 3-5%.
Is preferred.

As described above, when the lanthanoid oxide is used alone, there are large restrictions on the composition design of glass,
It may be difficult to obtain sufficient effect. On the other hand, when two or more kinds of lanthanoid oxides are used in combination, the degree of freedom in composition design is expanded and desired characteristics can be easily obtained.

In the following, La ₂ O ₃ , CeO ₂ and Gd ₂ O _{3 are} added.
A suitable composition range when these are used in combination is shown.

When combining La ₂ O ₃ and CeO ₂ ,
The content of each component is La ₂ O ₃ 0.1 to 10%, CeO ₂
0.1 to 15%, especially La ₂ O ₃ 1 to 8%, CeO ₂
1-10%, more _{La 2 O 3 1~5%, CeO} 2
It is preferably 3 to 10%.

When combining CeO ₂ and Gd ₂ O ₃ ,
The content of each component is CeO ₂ 0.1 to 15%, Gd ₂ O ₃
0.1-10%, especially CeO ₂ 1-10%, Gd ₂ O
_{3 to} 8%, further CeO ₂ 3 to 10%, Gd ₂ O ₃
It is preferably 1 to 5%.

When combining La ₂ O ₃ and Gd ₂ O ₃ ,
The content of each component is La ₂ O ₃ 0.1 to 10%, Gd ₂ O ₃
0.1% to 10%, in particular _{La 2 O 3 1~8%, Gd} 2 O 3
1 to 8%, further La ₂ O ₃ 1 to 5% Gd ₂ O ₃ 1
-5% is preferable.

When these three types are used, the content of each component is La ₂ O ₃ 0.1-5%, CeO ₂ 0.1
-10%, Gd ₂ O ₃ 0.1-5%, especially La ₂ O _{3
0.5~5%, CeO 2 1~10%,} Gd 2 O 3 0.
1 to 5%, further La ₂ O ₃ 0.5 to 3%, CeO ₂
It is preferably 1 to 5% and Gd ₂ O ₃ 0.1 to 3%.

In addition to the lanthanoid oxide, it is more effective to use other rare earth elements such as Y ₂ O ₃ . The addition amount of rare earths other than lanthanoid oxide is preferably 0 to 5%.

In addition to the above-mentioned components, the tin phosphate glass of the present invention contains ZnO 0-20% and MgO 0-20.
%, Al ₂ O ₃ 0-10%, SiO ₂ 0-15%, B
₂ O ₃ 0 to 30%, R ₂ O (R is the total of Li, Na, K and / or Cs) It is preferable to have a composition of 0 to 20%. The reason for limiting the above range will be described below.

ZnO is an intermediate oxide. ZnO is not an essential component, but since it has a large effect of stabilizing the glass, it is desirable to contain 4% or more. But ZnO
If it exceeds 20%, devitrification tends to occur on the glass surface during firing. Further, when there is a heat treatment step for a long time (for example, 1 hour or more) after firing, devitrification is likely to occur, so it is necessary to consider so that the glass becomes more stable. In such a case, the content of ZnO is 5 to 15%.
Is desirable.

MgO is a network modifying oxide and has the effect of stabilizing the glass. When MgO exceeds 20%, devitrification is likely to occur on the glass surface during firing. The content of MgO is preferably 0 to 5%.

Al ₂ O ₃ is an intermediate oxide. Although Al ₂ O ₃ is not an essential component, it has the effect of stabilizing the glass and the effect of lowering the coefficient of thermal expansion, so it is desirable to contain it. However, if it exceeds 10%, the softening temperature rises and the fluidity during firing is impaired. When considering the stability of glass, coefficient of thermal expansion and fluidity,
The range of 5% is more preferable.

SiO ₂ is a glass-forming oxide. Si
O ₂ has an effect of suppressing devitrification in sealing after debinding, and thus it is desirable to contain O ₂ . If it exceeds 15%, the softening temperature rises and the fluidity during firing remarkably deteriorates. When considering fluidity as a low melting point material,
The SiO ₂ content is preferably 0 to 10%.

B ₂ O ₃ is a glass-forming oxide. B ₂ O ₃
Has the effect of reducing scum generated by glass separation during melting. It also has the effect of stabilizing the glass. However, if it is more than 30%, the viscosity of the glass becomes too high, the fluidity at the time of firing remarkably deteriorates, and the airtightness of the sealed portion is impaired. A preferred range of B ₂ O ₃ is 0 to 25%. Since B ₂ O ₃ has a strong tendency to increase the viscosity of glass, very high fluidity is required, and B ₂ O ₃ should not be contained if the softening point needs to be significantly lowered.

R ₂ O (R is Li, Na, K, Cs) is not an essential component, but since at least one of the R ₂ O components is added to the composition, it has a strong adhesive force with the adherend. Become. However, if the total amount exceeds 20%, devitrification tends to occur during firing. When considering surface devitrification and fluidity, R ₂
It is desirable that the total amount of O is 10% or less. Also R ₂ O
Among the components, Li ₂ O has the highest ability to improve the adhesive force with the substrate.

The glass of the present invention may further contain various components in addition to the above components. For example WO
₃ , MoO ₃ , Nb ₂ O ₅ , TiO ₂ , ZrO ₂ , CuO, M
A glass stabilizing component such as nO or R′O (R ′ is Mg, Ca, Sr, or Ba) can be contained in a total amount of 35% or less. The content of these stabilizing components is 35%.
The reason for limiting the content to the following is that if the content exceeds 35%, the glass becomes unstable and devitrification easily occurs during molding. In order to obtain a more stable glass, it is preferably 25% or less. In addition, In ₂ O ₃ or the like may be contained in order to improve weather resistance and moisture resistance.

The content of the stabilizing component and the reason for limiting the content will be described below.

The contents of WO ₃ and MoO ₃ are both 0 to 2
It is preferably 0%, particularly preferably 0 to 10%. If the content of each of these components exceeds 20%, the viscosity of the glass tends to increase.

The contents of Nb ₂ O ₅ , TiO ₂ and ZrO ₂ are all 0 to 15%, preferably 0 to 10%. If each of these components exceeds 15%, the devitrification tendency of the glass tends to increase.

The contents of CuO and MnO are both 0 to 1
0%, especially 0 to 5% each is preferred. If the content of each of these components exceeds 10%, the glass tends to become unstable.

The total content of R'O is preferably 0 to 15%, more preferably 0 to 5%. If R'O exceeds 15%, the glass tends to be unstable.

In ₂ O ₃ can be used for the purpose of obtaining a high degree of weather resistance and moisture resistance when cost is taken into consideration. The content of In ₂ O ₃ is preferably 0 to 5%.

In the case of VFD, FED, CRT, PDP, and other display tube applications, halogens such as F and Cl adversely affect electronic discharge and the like, which may cause problems such as reduction in display brightness. Therefore, when the glass of the present invention is used for display tubes, it is desirable that the glass does not contain halogen.

The glass having the above composition is 270 to 3
It has a glass transition point of 80 ° C and exhibits good fluidity in the temperature range of about 400 to 600 ° C. Further, it has a coefficient of thermal expansion of about 90 to 150 × 10 ⁻⁷ / ° C. at 30 to 250 ° C.

The tin phosphate glass of the present invention having such characteristics can be used alone as a sealing material for a material having a suitable thermal expansion coefficient.

On the other hand, a material whose thermal expansion coefficient does not match, for example, alumina (70 × 10 ⁻⁷ / ° C.), high strain point glass (85
× 10 ^-7 / ℃), soda plate glass (90 × 10 ^-7 / ℃)
In the case of sealing and the like, a refractory filler powder may be added to form a composite material. It is important to design the thermal expansion coefficient of the composite material to be lower by about 10 to 30 × 10 ⁻⁷ / ° C. than that of the material to be sealed. This is to prevent the sealing material from breaking due to tensile stress applied to the sealing material after sealing. In the case of sealing VFD, FED, PDP, and CRT, the thermal expansion coefficient is adjusted to be about 60 to 100 × 10 ⁻⁷ / ° C. In addition to adjusting the coefficient of thermal expansion, a refractory filler powder can be added to improve mechanical strength, for example.

When the refractory filler powder is mixed,
The mixing amount is preferably 50 to 100% by volume of glass powder and 0 to 50% by volume of filler powder. This is because if the content of the filler powder is more than 50% by volume, the ratio of the glass powder becomes relatively low and it becomes difficult to obtain the required fluidity.

Various materials can be used as the refractory filler powder, for example, cordierite, zircon, tin oxide,
Examples thereof include niobium oxide, zirconium phosphate, willemite, mullite, and the like. Further, NbZr (PO ₄ ) ceramic powder containing 2% by weight of MgO contains phosphoric acid in its component, and therefore is well suited to the tin phosphate glass of the present invention.

In the case of CRT sealing application, it is desirable to crystallize the sealing material in order to improve the strength. To crystallize, crystalline fine powder may be added separately from the refractory filler powder. Zirconia is typically used as the fine powder, but is not particularly limited as long as it is a fine powder that promotes crystallization. The addition ratio of the crystalline fine powder is preferably 0.1 to 1.0 wt% with respect to the total powder weight.

In order to produce the tin phosphate glass of the present invention and the composite material using the same, the raw materials are first prepared so as to have the above composition, and melted to be vitrified. Within the glass composition range of the present invention, there is no problem even if melting in air is carried out, but it is necessary to take care so that SnO is not oxidized to SnO ₂ during melting. Therefore or melted in N _2, etc. to N ₂ bubbled through the melt, it is preferable to perform the melt in a non-oxidizing atmosphere. At the laboratory level, it is desirable to cover the crucible with a lid to melt it.

Thereafter, the molten glass is molded, crushed and classified.

In this way, tin phosphate glass powder can be obtained. Further, a refractory filler powder may be added and mixed if necessary to obtain a composite material.

Next, the composite material of the present invention was applied to VFD and FE.
An example of use as a sealing material for a display tube of D, PDP, CRT, etc. will be shown.

First, a sealing material is applied to the sealing surface of an object to be sealed and dried. In applying, the sealing material may be made into a paste and a dispenser may be used.

Next, if necessary, heating for debinding is performed, and then main firing is performed while contacting with the other object to be sealed. In the main baking, the objects to be sealed can be sealed together by baking the glass under conditions sufficient to wet the adhesive surface of the objects to be sealed. VFD, FED,
Typical sealing temperature for PDP and CRT is 430-5
It is 00 ° C. Also, the holding time at the maximum temperature for sealing is usually about 10 minutes for VFD, FED, and PDP, and CR
At T, about 30 minutes is appropriate.

When the tin phosphate glass or the composite material of the present invention is made into a paste, it is kneaded with a vehicle using ethyl cellulose as a resin and terpineol as a solvent, or a vehicle using nitrocellulose as a resin and isoamyl acetate as a solvent. Good. It is preferable to use a vehicle using nitrocellulose as a resin and isoamyl acetate as a solvent because the devitrification property after firing is small.

Further, higher alcohol may be used in place of terpineol or isoamyl acetate. Exemplary higher _{alcohols, C n H 2n + 1 OH} (n = 8~
Although it is possible to use isoaicosyl alcohol from isohexyl alcohol represented by 20), considering viscosity, one having a molecular weight of isodecyl alcohol (n = 10) or more is preferable when mixed with powder. It is easy to make the viscosity suitable. Further, in consideration of easiness of incineration during firing, those having a molecular weight of isohexadecyl alcohol (n = 16) or less are preferable. Therefore, when higher alcohols are used, isododecyl alcohol and isotridecyl alcohol are preferable. Isotridecyl alcohol is most suitable from the total balance.

Although the tin phosphate glass and the composite material using the same have been described as the sealing material for the display tube, the present invention is not limited to this and is applicable to, for example, the sealing of an IC package or a lamp. Sealing material used, PD
It is applicable to various applications such as insulating coating materials used for P and FEDs, partition wall forming materials for PDPs, and the like.

Below, examples of use as an insulating coating material such as VFD and PDP will be shown.

First, an insulating coating material is prepared by adding refractory filler powder to glass as needed so that the substrate to be coated has a coefficient of thermal expansion. The soda plate glass (about 90 × 10 ⁻⁷ / ° C.) is mainly used in VFD, and the high strain point glass (about 85 × 10 ⁻⁷ / ° C.) is mainly used in PDP, so that the thermal expansion coefficient is 60 to 80 × 10 ^{−. It} may be adjusted to about ⁷ / ° C.

Next, on the surface of the substrate on which electric wiring and the like are provided,
The insulation coating material is applied by screen printing. When applying, the material may be used in the form of paste like the sealing material.

Thereafter, the glass can be coated by baking under conditions sufficient for the glass to wet the surface of the object to be sealed. The heat treatment condition of the insulation coating material is generally higher than that of the sealing material, and the temperature is 500 ° C.
It is about 580 ° C.

[0066]

EXAMPLES The present invention will be described in detail below based on examples. (Example 1) Tables 1 and 2 show L as a lanthanoid oxide.
glass powder sample of the present invention using a ₂ O ₃ (Sample a~
g), and the glass powders of Comparative Examples (Samples I to III), respectively.

[0067]

[Table 1]

[0068]

[Table 2]

Each glass powder was prepared as follows.
First, prepare the raw materials so that they have the composition shown in the table, and
It was melted at 00 to 900 ° C. for 1 to 2 hours.

At the time of melting, the melting crucible was covered with a lid so that tin monoxide was not easily oxidized. Further, stannous pyrophosphate and zinc metaphosphate were used as the phosphorus raw material used,
Orthophosphoric acid (orthophosphoric acid), which is a liquid raw material, is not used,
All solid raw materials were used. This is for the following reason.
In other words, if the liquid raw material is directly melted, there is a problem of spillage, and in order to avoid this, it has to be dried once. On the other hand, the solid raw material has an advantage that it is not necessary to change the conventional manufacturing process.

Next, the molten glass was passed between water-cooled rollers to form a thin plate, which was crushed by a ball mill and then opened 10
After passing through a 5 μm sieve, tin phosphate glass powder having an average particle size of about 10 μm was obtained.

The glass transition point, the coefficient of thermal expansion and the moisture resistance of the obtained glass powder sample were evaluated. as a result,
Glass transition point is 271-333 ° C, thermal expansion coefficient is 11
It was 0.1 to 120.7 × 10 ⁻⁷ / ° C. In addition, the samples a to g which are examples were good in moisture resistance. On the other hand, Comparative Examples Samples I to III were inferior in moisture resistance.

The glass transition point is a differential thermal analysis (DTA).
Thus, the coefficient of thermal expansion was determined by a push rod type thermal expansion measuring device.

The moisture resistance was evaluated as follows. First, glass powder having a weight corresponding to the true specific gravity of glass was pressed into a button shape having an outer diameter of 20 mm with a mold to obtain a button-shaped glass powder molded body. Next, this molded body is subjected to a temperature of 70 ° C. and a humidity of 95
After being stored in a constant temperature and high humidity tank for 24 hours, it was fired under the conditions shown in the table. The flow state at this time was evaluated by visual observation. In addition, for each sample, the same molded body was fired without being placed in a constant temperature and humidity chamber, and this was used as a comparison target as an ordinary fired product. As a result of the observation, when the fluidized state is the same as that of the ordinary fired product, it is judged that the button shape is distorted and the fluidized state is slightly inferior to the normally fired product.
○ No foaming, × lava-like foaming
And

Next, glass powder samples a to g and I to III
Was mixed with the filler powder at a ratio shown in Tables 3 to 5 to obtain a composite material sample. Sample No. 1 to 11 are examples of the present invention, and sample No. 12-14 has shown the comparative example, respectively.

Sample No. 1 to 3 and 12 to 14 are V
The FD is sealed and the two soda glass plates (thermal expansion member
Number 90 x 10^-7/ ° C) for sealing. Sample N
o. Nos. 4 to 10 are for PDP sealing, and two high strain point
Lath plate (coefficient of thermal expansion 85 × 10 ^-7/ ° C) seal each other
It is a material. Sample No. 11 is a CRT sealing wear,
CRT panel and funnel (coefficient of thermal expansion 100 x 1 each
0^-7/ ° C) for sealing.

The filler powder contains 2% by weight of MgO.
Added NbZr (PO ₄ ) ₃ ceramic powder (NZ
P), cordierite, niobium oxide, and tin dioxide were used. In addition, sample No. For No. 11, zirconia was further added as a crystalline fine powder.

The samples thus prepared were subjected to various evaluations. The evaluation results are shown in Tables 3-5.

[0079]

[Table 3]

[0080]

[Table 4]

[0081]

[Table 5]

As is apparent from the table, No. 1 which is an embodiment of the present invention. Each of the samples 1 to 11 had a thermal expansion coefficient of 65.5 to 76.1 × 10 ⁻⁷ / ° C. at 30 to 250 ° C. 21.5 to 23.5 mm under the firing conditions shown in the table
And had a good fluidity. Further, each sample was excellent in weather resistance and resealing property.

On the other hand, Sample No. which is a comparative example. 12
Nos. 14 to 14 were inferior in weather resistance and resealing property.

The flow diameter was evaluated by the following flow button test. First, a powder having a weight corresponding to the true specific gravity of the composite material was pressed into a button shape having an outer diameter of 20 mm with a mold to obtain a button-shaped composite powder compact. Next, this molded body was placed on a glass substrate, then heated in air to the firing temperature shown in the table at a rate of 10 ° C./min and held for 10 minutes. Then, the diameter of the button was measured. This flow button diameter is preferably 20 mm or more when used as a sealing material. As the glass substrate, soda glass was used as the VFD material, high strain point glass was used as the PDP material, and CRT panel glass was used as the CRT material.

The weather resistance of the fired body was evaluated by visually observing the surface state of the sample after the flow button test after storing it in a constant temperature and high humidity chamber at a temperature of 70 ° C. and a humidity of 95% for 168 hours. As a result of the observation, the flow button surface maintains the gloss and the surface state does not change at all ◎, the flow button surface has no gloss but does not ooze out ○, the surface has a bleeding component It was set to x.

The resealing property was evaluated as follows. First, the button-shaped composite powder compact was placed on the substrate and held at a temperature 30 ° C. higher than the firing temperature shown in the table for the time shown in the table. Then, another substrate was placed, both were fixed with a clip, and it was evaluated again whether or not they were adhered by firing under the conditions shown in the table. As a result, the flow button was completely reflowed by firing and the flow buttons were completely crushed, and the substrates were bonded to each other ◎, a part of the flow button was crushed and slightly bonded to Δ, the shape of the flow button was not changed, and Those that did not adhere were marked with x. In this evaluation, it can be judged that the adhered ones do not cause devitrification during the heat treatment during debinding.
The substrate used was made of the same material as the material to be sealed of each sample.

The residual strain is 5 m after the flow button after the test.
It is cut into m widths, and the magnitude of tensile stress of the glass substrate is measured by a polarimeter (strain gauge). From the viewpoint of the strength of the composite material and the substrate, it is ideal that tensile stress is applied to the substrate side.

N used as a refractory filler powder
The bZr (PO ₄ ) ₃ ceramic powder was mixed with niobium pentoxide, low α-ray zirconia, ammonium dihydrogen phosphate and magnesia, baked at 1450 ° C. for 16 hours, crushed, and passed through a sieve with an opening of 45 μm. A powder having an average particle diameter of 5 μm was used.

The cordierite powder was prepared as follows. First, the stoichiometric composition (2MgO · 2Al ₂ O ₃ ·
Glass having 5SiO ₂ ) is crushed to form an aperture 105
It was passed through a μm sieve. This glass powder is then
It heated at 0 degreeC for 10 hours, and produced the crystallized material. afterwards,
The crystallized product was crushed and passed through a sieve having an opening of 45 μm to obtain cordierite powder.

For the niobium oxide powder and the tin oxide powder, the raw material powder was heated at 1400 ° C. for 10 hours to produce a crystallized product. After that, the crystallized product is crushed to form an opening 45.
After passing through a μm sieve, the desired powder was obtained. (Example 2) Tables 6 to 9 show glass powder samples (Samples h to w) of the present invention containing CeO ₂ and Gd ₂ O ₃ .

[0091]

[Table 6]

[0092]

[Table 7]

[0093]

[Table 8]

[0094]

[Table 9]

Each glass powder was prepared in the same manner as in Example 1.

The obtained glass powder sample was evaluated in the same manner as in Example 1, and as a result, the glass transition point was found to be 273 to.
323 ° C., thermal expansion coefficient 102.1 to 118.5 × 10
^{It was −7} / ° C., and all samples had good moisture resistance.

Next, glass powder samples h to w were mixed with filler powders to obtain composite material samples (Nos. 15 to 30).
Sample No. 15, 16, 20, 21, and 28 are VF
For sealing D, the sample No. 17-19, 22-2
Sample Nos. 3, 25 to 27, 29 and 30 were used for sealing PDP. 24 was produced as a CRT sealing member.

The samples thus prepared were subjected to various evaluations in the same manner as in Example 1. The evaluation results are shown in Tables 10-1.
3 shows.

[0099]

[Table 10]

[0100]

[Table 11]

[0101]

[Table 12]

[0102]

[Table 13]

As is apparent from the table, No. 15-30
Each sample has a thermal expansion coefficient of 6 at 30 to 250 ° C.
It was 7.1 to 76.0 × 10 ^-7 / ° C. In addition, it shows a flow diameter of 22.5 to 24.5 mm under the firing conditions shown in the table,
It had good flowability. Further, each sample was excellent in weather resistance and resealing property.

[0104]

As described above, the tin phosphate glass of the present invention has a glass transition point of 270 to 380 ° C. and exhibits good fluidity by heat treatment at 500 ° C. or lower. Furthermore, there are no drawbacks peculiar to phosphate glass. Therefore, it is possible to produce a lead-free sealing material and an insulating coating material having the same performance as that of the conventional product. In addition to these uses, P
It can be used for various purposes such as a partition wall forming material for DP.

Further, the composite material of the present invention can be sealed at a low temperature, and can seal a display tube such as a fluorescent display tube (VFD), a field emission display (FED), a plasma display (PDP) or a cathode ray tube (CRT). It is suitable as a dressing material. Further, an insulating coating material for a substrate on which electric wiring such as FED and PDP is formed, a partition wall forming material for PDP, I
It can also be used as a sealing material for C packages and lamps. Further, other than the above, it can be applied as a substitute for a material containing lead-containing glass used in various electronic parts.

Continued front page    F term (reference) 4G062 AA09 BB09 CC08 DA01 DA02                       DA03 DA04 DB01 DB02 DB03                       DC01 DC02 DC03 DC04 DD04                       DD05 DE01 DE02 DE03 DE04                       DF01 EA01 EA02 EA03 EA04                       EB01 EB02 EB03 EB04 EC01                       EC02 EC03 EC04 ED01 ED02                       ED03 ED04 EE01 EF01 EG01                       FA01 FB01 FC01 FD01 FE05                       FE06 FF01 FG01 FH01 FJ01                       FK01 FK02 FK03 FK04 FL01                       FL02 FL03 FL04 GA01 GB01                       GC01 GD01 GE01 HH01 HH03                       HH05 HH07 HH09 HH11 HH13                       HH15 HH17 HH20 JJ01 JJ03                       JJ05 JJ07 JJ10 KK01 KK02                       KK03 KK04 KK05 KK06 KK07                       KK08 KK10 MM08 MM13 NN32                       NN33 PP01

Claims (14)

[Claims] 1. SnO 30 to 70% in terms of mol%, P
₂ O ₅ 20-45%, lanthanoid oxide 0.1-2
Tin phosphate glass characterized by having a composition of 5%. 2. The lanthanoid oxide is La ₂ O ₃ , Ce.
The tin phosphate glass according to claim 1, which is selected from O ₂ and Gd ₂ O ₃ . 3. SnO 30-70%, P in mol% display
_{2 O 5 20~45%, La 2} O 3 0.1~10% of claim 1 or 2 of tin phosphate glass and having a composition. 4. SnO 30 to 70% in terms of mol%, P
₂ O ₅ 20-45%, CeO ₂ 0.1-15% has a composition, The tin-phosphate type | system | group glass of Claim 1 or 2 characterized by the above-mentioned. 5. SnO 30 to 70% in terms of mol%, P
_{2. The} tin phosphate glass according to claim 1, which has a composition of 20 to 45% ₂ O _{5 and} 0.1 to 10% Gd ₂ O ₃ . 6. The tin phosphate glass according to claim 1 or 2, wherein two or more kinds of components are used as the lanthanoid oxide. 7. SnO 30 to 70% in terms of mol%, P
₂ O ₅ 20-45%, La ₂ O ₃ 0.1-10%, Ce
The tin phosphate glass according to claim 1, 2 or 6, which has a composition of O ₂ 0.1 to 15%. 8. SnO 30 to 70% in terms of mol%, P
₂ O ₅ 20-45%, CeO ₂ 0.1-15%, Gd ₂
O ₃ 0.1 to 10% of claims 1, 2 or 6 tin phosphate glass in and having a composition. 9. SnO 30-70%, P in mol% display
₂ O ₅ 20-45%, La ₂ O ₃ 0.1-10%, Gd
_The tin phosphate glass according to claim 1, 2 or 6 having a composition of 0.1 to 10% of ₂ O ₃ . 10. SnO 30 to 70% in mol% display,
_{P 2 O 5 20~45%, La} 2 O 3 0.1~5%, Ce
The tin phosphate glass according to claim 1, 2 or 7, which has a composition of O ₂ 0.1 to 10% and Gd ₂ O ₃ 0.1 to 5%. 11. ZnO 0-20%, MgO
0-20%, Al ₂ O ₃ 0-10%, SiO ₂ 0-1
5%, B ₂ O ₃ 0 to 30%, R ₂ O (R is Li, Na,
K, Cs) The composition has a composition of 0 to 20%, and the tin phosphate glass according to any one of claims 1 to 10. 12. A composite material comprising the tin phosphate glass powder according to claim 1 and a refractory filler powder. 13. Tin phosphate glass powder 50 to 100
13. The composite material according to claim 12, wherein the composite material comprises volume% and refractory filler powder 0 to 50 volume%. 14. A sealing material comprising the composite material according to claim 12 or 13.