Sealing material

Abstract

A sealing material of the present invention is a sealing material for sealing a metal material, including 70 mass % to 100 mass % of glass powder including alkali silicate glass and 0 mass % to 30 mass % of ceramic powder, and having a linear thermal expansion coefficient in a temperature range of from 30 C. to 380 C. of more than 10010.sup.7/ C. and 17010.sup.7/ C. or less.

Claims

1. A sealing material for sealing a metal material, comprising 70 mass % to 100 mass % of glass powder comprising alkali metal oxide silicate glass and 0 mass % to 30 mass % of ceramic powder, and having a linear thermal expansion coefficient in a temperature range of from 30 C. to 380 C. of more than 10010.sup.7/ C. and 17010.sup.7/ C. or less, wherein the glass powder comprises high-expansion glass powder, and wherein the high-expansion glass powder comprises as a glass composition, in terms of mol %, 55% to 75% of SiO.sub.2, 0% to 10% of B.sub.2O.sub.3, 1% to 12% of Al.sub.2O.sub.3, 17% to 28% of Li.sub.2O+Na.sub.2O+K.sub.2O, 10% to 23% of Na.sub.2O, 1% to 7% of CaO, and up to 9% of MgO+CaO+SrO+BaO.

2. The sealing material according to claim 1, wherein the glass powder comprises the high-expansion glass powder and low-expansion glass powder.

3. The sealing material according to claim 1, wherein the sealing material comprises 70 mass % to 99 mass % of the glass powder and 1 mass % to 30 mass % of the ceramic powder, and wherein the glass powder further comprises low-expansion glass powder, and the ceramic powder comprises high-expansion ceramic powder.

4. The sealing material according to claim 3, wherein the high-expansion ceramic powder comprises any one selected from the group consisting of cristobalite, tridymite, and calcium fluoride.

5. The sealing material according to claim 1, wherein the sealing material has a granular form.

6. The sealing material according to claim 1, wherein the sealing material comprises a sintered compact, wherein the sintered compact is formed by heating a green compact, and wherein the green compact is produced by tablet molding granules.

7. The sealing material according to claim 1, wherein the sealing material is used for sealing a hermetic terminal.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1A is a conceptual diagram for illustrating a hermetic terminal.

(2) FIG. 1B is a conceptual diagram for illustrating a state of a metal stem, a metal pin, and a sealing material before firing.

(3) FIG. 1C is a conceptual diagram for illustrating a state of the metal stem, the metal pin, and the sealing material after the firing.

DESCRIPTION OF EMBODIMENTS

(4) In a sealing material of the present invention, the content of glass powder is from 70 mass % to 100 mass %, preferably from 80 mass % to 100 mass %, more preferably from 90 mass % to 100 mass %, still more preferably from 95 mass % to 100 mass %, particularly preferably from more than 97 mass % to 100 mass %. In addition, the content of ceramic powder is from 0 mass % to 30 mass %, preferably from 0 mass % to 20 mass %, more preferably from 0 mass % to 10 mass %, still more preferably from 0 mass % to 5 mass %, particularly preferably from 0 mass % to less than 3 mass %. When the content of the glass powder is too small (when the content of the ceramic powder is too large), the amount of a melting accelerate component is reduced, and hence sufficient fluidity is not obtained in a sealing step, and hermetic reliability is liable to be reduced.

(5) The sealing material of the present invention has a linear thermal expansion coefficient in a temperature range of from 30 C. to 380 C. of more than 10010.sup.7/ C., preferably 10310.sup.7/ C. or more, more preferably 10610.sup.7/ C. or more, still more preferably 10810.sup.7/ C. or more. When the linear thermal expansion coefficient in a temperature range of from 30 C. to 380 C. is too low, in the case in which a metal pin comprising a highly conductive metal is sealed with the sealing material, the sealing material is liable to be subjected to a large tensile stress from the metal pin in the course of cooling to room temperature after the sealing step, and cracks are liable to occur in the sealing material. As a result, there is a risk in that hermetic leakage of a refrigerant occurs at the time of incorporation in a refrigerator and the like. Meanwhile, the sealing material of the present invention has a linear thermal expansion coefficient in a temperature range of from 30 C. to 380 C. of 17010.sup.7/ C. or less, preferably 15010.sup.7/ C. or less, more preferably 13010.sup.7/ C. or less, still more preferably 12010.sup.7/ C. or less. When the linear thermal expansion coefficient in a temperature range of from 30 C. to 380 C. is too high, it becomes difficult for the sealing material to be subjected to a compression stress from a metal stem after the sealing step, and the hermetic reliability of a hermetic terminal is liable to be reduced.

(6) In the sealing material of the present invention, it is preferred that the glass powder comprise at least high-expansion glass powder, and that the high-expansion glass powder comprise as a glass composition, in terms of mol %, 55% to 75% of SiO.sub.2, 0% to 10% of B.sub.2O.sub.3, 1% to 12% of Al.sub.2O.sub.3, 17% to 28% of Li.sub.2O+Na.sub.2O+K.sub.2O, and 0% to 15% of MgO+CaO+SrO+BaO. The reasons why the contents of the components of the high-expansion glass powder are limited as described above are described below. In the description of the contents of the components, the expression % means mol %.

(7) SiO.sub.2 is a main component for forming a glass skeleton, and the content of SiO.sub.2 is preferably from 55% to 75%, more preferably from 60% to 70%. When the content of SiO.sub.2 is too small, there is a risk in that the linear thermal expansion coefficient is increased improperly. In addition, water resistance and weather resistance are liable to be reduced. Meanwhile, when the content of SiO.sub.2 is too large, there is a risk in that the linear thermal expansion coefficient is reduced improperly. In addition, a bonding temperature is liable to be increased. When the water resistance and the weather resistance are reduced, glass has restriction in its handling in a granulation step, and further, there is a risk in that the long-term reliability of the hermetic terminal is reduced.

(8) B.sub.2O.sub.3 is a component which increases meltability and reduces the bonding temperature. The content of B.sub.2O is preferably from 0% to 10%, more preferably from 0% to 5%, still more preferably from 0% to 3%. When the content of B.sub.2O.sub.3 is too large, abnormal shrinkage is liable to occur in a temperature range around a glass transition point in the course of cooling to room temperature after the sealing step.

(9) Al.sub.2O.sub.3 is a component which increases the water resistance and the weather resistance. The content of Al.sub.2O.sub.3 is preferably from 1% to 12%, more preferably from 2% to 10%, still more preferably from 5% to 8%. When the content of Al.sub.2O.sub.3 is too small, the water resistance and the weather resistance are liable to be reduced. Meanwhile, when the content of Al.sub.2O.sub.3 is too large, there is a risk in that the linear thermal expansion coefficient is reduced improperly. In addition, the bonding temperature is liable to be increased.

(10) An alkali metal oxide (Li.sub.2O, Na.sub.2O, and K.sub.2O) is a component which increases the linear thermal expansion coefficient, and is also a component which reduces the bonding temperature, but is a component which reduces the water resistance and the weather resistance. The content of Li.sub.2O+Na.sub.2O+K.sub.2O is preferably from 17% to 28%, more preferably from 19% to 25%, still more preferably from more than 20% to 23%. The content of Li.sub.2O is preferably from 0% to 12%, more preferably from 0% to 8%, still more preferably from 0% to 5%. The content of Na.sub.2O is preferably from 10% to 23%, more preferably from 12% to 20%, still more preferably from 15% to 18%. The content of K.sub.2O is preferably from 1% to 12%, more preferably from 3% to 10%, still more preferably from 5% to 7%. When the content of the alkali metal oxide is too small, there is a risk in that the linear thermal expansion coefficient is reduced improperly. In addition, the bonding temperature is liable to be increased. Meanwhile, when the content of the alkali metal oxide is too large, the water resistance and the weather resistance are liable to be reduced.

(11) An alkaline earth metal oxide (MgO, CaO, SrO, and BaO) is a component which reduces the bonding temperature. The content of MgO+CaO+SrO+BaO is preferably from 0% to 15%, more preferably from 2% to 12%, still more preferably from 4% to 9%. The content of MgO is preferably from 0% to 7%, more preferably from 1% to 5%. The content of CaO is preferably from 0% to 7%, more preferably from 1% to 5%. The content of SrO is preferably from 0% to 5%, more preferably from 0% to 3%, still more preferably from 0% to 1%. The content of BaO is preferably from 0% to 5%, more preferably from 0% to 3%, still more preferably from 0% to 1%. When the content of the alkaline earth metal oxide is too small, the bonding temperature is liable to be increased. Meanwhile, when the content of the alkaline earth metal oxide is too large, the glass skeleton is liable to be unstable.

(12) Other than the above-mentioned components, for example, TiO.sub.2, ZrO.sub.2, F.sub.2, Cl.sub.2, La.sub.2O.sub.3, MnO.sub.2, Cr.sub.2O.sub.3, Fe.sub.2O.sub.3, Co.sub.2O.sub.3, and the like may be introduced at respective contents of from 0.1% to 5% unless the effects of the present invention are impaired improperly.

(13) In the sealing material of the present invention, the glass powder preferably comprises the high-expansion glass powder and low-expansion glass powder. In general, when the linear thermal expansion coefficient of the glass powder is to be increased, the content of the alkali metal oxide in a glass composition needs to be increased. In this case, however, the water resistance and the weather resistance of the glass powder are liable to be reduced. Therefore, the high-expansion glass powder tends to have low water resistance and low weather resistance, and the low-expansion glass powder tends to have high water resistance and high weather resistance. In view of the foregoing, the high-expansion glass powder and the low-expansion glass powder are mixed to be used as the glass powder, and thus the drawbacks of both the powders can be compensated for by each other. That is, the water resistance and the weather resistance can be increased while the linear thermal expansion coefficient is increased.

(14) Various alkali silicate glasses may be used as the low-expansion glass powder. Of those, low-expansion glass powder comprising as a glass composition, in terms of mol %, 65% to 82% of SiO.sub.2, 0% to 10% of B.sub.2O.sub.3, 0% to of Al.sub.2O.sub.3, 10% to 20% of Li.sub.2O+Na.sub.2O+K.sub.2O, and to 1% to 15% of MgO+CaO+SrO+BaO is preferred. With this, the water resistance and the weather resistance can be increased while the bonding temperature is reduced.

(15) Other than the above-mentioned case in which the sealing material of the present invention is formed only of the glass powder, it is also preferred that the sealing material of the present invention comprise 70 mass % to 99 mass % of the glass powder and 1 mass % to 30 mass % of the ceramic powder, the glass powder contain the low-expansion glass powder, and the ceramic powder contain high-expansion ceramic powder. When the low-expansion glass powder and the high-expansion ceramic powder are introduced in the sealing material, the water resistance and the weather resistance can be increased while the linear thermal expansion coefficient of the sealing material is increased. In this case, the content of the high-expansion ceramic powder is preferably from 1 mass % to 30 mass %, more preferably from 2 mass % to 15 mass %, still, more preferably from 3 mass % to 6 mass %. When the content of the high-expansion ceramic powder is too small, it becomes difficult to increase the linear thermal expansion coefficient of the sealing material. Meanwhile, when the content of the high-expansion ceramic powder is too large, the amount of the melting accelerate component is reduced, and hence bonding strength is reduced, and the hermetic reliability is liable to be reduced.

(16) Various ceramic powders may be used as the high-expansion ceramic powder, but from the viewpoint of compatibility with the alkali silicate glass, any one of cristobalite, tridymite, and calcium fluoride is preferred.

(17) The sealing material of the present invention preferably has a granular form. With this, a green compact having a predetermined shape, particularly a green compact having a through-hole for inserting a metal pin can be easily produced through tablet molding.

(18) The sealing material of the present invention preferably comprises a sintered compact. With this, when the sealing material having inserted therein a metal pin is housed in a metal stem, chipping of the sealing material can be suppressed.

EXAMPLES

(19) Now, the present invention is described by way of Examples. The following Examples are merely illustrative. The present invention is by no means limited to the following Examples.

(20) Sample Nos. 1 and 2 are shown in Table 1.

(21) TABLE-US-00001 TABLE 1 No. 1 No. 2 Glass SiO.sub.2 75 66 composition B.sub.2O.sub.3 0 0 (mol %) Al.sub.2O.sub.3 3 7 Li.sub.2O 0 1 Na.sub.2O 8 14 K.sub.2O 6 7 MgO 0 1 CaO 0 4 SrO 2 0 BaO 6 0 .sub.30-380 C. (10.sup.7/ C.) 97 118

(22) First, a glass batch obtained by blending glass raw materials so as to give the glass composition shown in Table 1 was loaded in a platinum crucible, and melted at 1,500 C. for 4 hours. At the time of the melting, the glass batch was stirred with a platinum stirrer to be homogenized. Next, the resultant molten glass was formed into a film shape with a double roller, pulverized with a ball mill, and then classified with a test sieve. Thus, Sample Nos. 1 and 2 each having an average particle diameter D.sub.50 of about 30 m were obtained, Sample Nos. 1 and 2 were each measured for a linear thermal expansion coefficient in a temperature range of from 30 C. to 380 C. The linear thermal expansion coefficients of Sample Nos. 1 and 2 are each an average value obtained through measurement using glass bulk processed into a predetermined shape as a measurement sample with a push-rod-type thermal expansion coefficient measurement apparatus (TMA).

Experiment 1

(23) A sealing material was obtained by mixing Sample No. 1 and Sample No. 2 at a mass ratio of 1:1, followed by granulation. The sealing material had a linear thermal expansion coefficient in a temperature range of from 30 C. to 380 C. of 11010.sup.7/ C. The linear thermal expansion coefficient of the sealing material is an average value obtained through measurement with TMA using, as a measurement sample, a sintered compact processed into a predetermined shape after having been sintered at a temperature higher than the softening point of the sealing material by 30 C. (the same applies to Experiment 2).

Experiment 2

(24) A sealing material, was obtained by mixing Sample No. 1 and cristobalite powder (average particle diameter D.sub.50: about 10 m) at a mass ratio of 96:4, followed by granulation. The sealing material had a linear thermal expansion coefficient in a temperature range of from 30 C. to 380 C. of 11010.sup.7/ C.

(25) The linear thermal expansion coefficients in a temperature range of from 30 C. to 380 C. of the sealing materials obtained in Experiments 1 and 2 are restricted within a predetermined range. Therefore, it is considered that cracks hardly occur in each of the sealing materials obtained in Experiments 1 and 2 when a metal pin comprising a highly conductive metal is sealed with the sealing material. As a result, it is considered that the current capacity and the hermetic reliability of a hermetic terminal can be increased through use of each of the sealing materials obtained in Experiments 1 and 2.

REFERENCE SIGNS LIST

(26) 1 hermetic terminal

(27) 11 metal stem

(28) 12 metal pin

(29) 13 sealing material