JP6118483B2 - Metal bonding parts and metal bonding materials - Google Patents

Description

  The present invention relates to a metal joint component, and more particularly to a technique for joining a pair of metal members in an insulating state while ensuring airtightness and water resistance using glass.

Some in-vehicle electronic device components need to be joined in an insulated state without gas leakage. Conventionally, although such a joining location is joined with glass, in order to approximate the thermal expansion coefficient (about 5 to 9 × 10 ⁻⁶ / K) of glass used for general purposes, it is expensive such as Kovar metal. Metals were sometimes used. In recent years, aluminum and copper are considered to be applied to such metals in order to reduce costs, improve performance, reduce weight, and the like. Aluminum and copper have large thermal expansion coefficients of about 23 to 25 × 10 ⁻⁶ / K and about 16 to 18 × 10 ⁻⁶ / K, respectively, and have similar or slightly lower thermal expansion coefficients to reduce stress. It is desirable to select a bonding material (see Non-Patent Document 1). Further, aluminum has a low melting point (about 660 ° C.), and copper is easily oxidized and deteriorated at 600 ° C. or higher. Moreover, not only insulation but also water resistance in a high temperature environment of about 70 to 90 ° C. may be required for joining metal members used for in-vehicle electronic components and the like.

  Conventionally, there are few reports on glass for joining metal parts for vehicles, but lead glass, bismuth borate glass (see Patent Document 1), zinc phosphate glass, etc. from the viewpoint of low-temperature bonding, insulation and water resistance. Can be considered.

JP 2008-254974 A JP 2008-308393 A

Ceramics 46 (2011) No11 "Sealing with glass frit and linear expansion coefficient" Satoshi Fujimine AIST Press Release: Development of lead-free industrial glass with improved water resistance and discoloration resistance (November 21, 2006)

However, lead-based materials are highly affected by environmental pollution, as in the RoHS directive, and are currently difficult to use. Although bismuth borate glass has high water resistance, it generally has a thermal expansion coefficient of around 10 × 10 ⁻⁶ / K, which is lower than that of aluminum or copper. In addition, zinc phosphate-based glass may not have sufficient water resistance for in-vehicle use (see Patent Document 2). In order to lower the softening temperature of the glass and increase the thermal expansion coefficient, there is an addition of an alkali component, but in many cases, this results in poor water resistance (see Non-Patent Document 2). It is conceivable to add leucite crystal [leucite: KAlSi ₂ O ₆ ] as another method for increasing the thermal expansion coefficient of glass, but the softening point is also increased, which is necessary for joining aluminum and copper. Joining at 550 ° C. or lower is difficult. Although bonding with resin is also conceivable, it may be possible if it has only a sealing function, but there is a problem that when high voltage is applied, it becomes conductive and breaks down.

  The present invention has been made in the background of the above circumstances, and its purpose is to be 550 ° C. or lower while ensuring a predetermined insulating property, airtightness, and water resistance while being easy to the environment and less affected by the difference in thermal expansion. It is to be able to join metal members such as aluminum and copper at a low temperature.

In order to achieve such an object, the first invention is a metal joint part in which a pair of metal members made of aluminum or copper are joined in an insulated state while ensuring airtightness and water resistance, and (a) Leucite A glass containing crystals, and (b) a pair of glass members interposed between the glass member and the pair of metal members, respectively. A mixture of thermosetting resin and ceramic powder, and (c) the pair of metal members are integrally joined to each other with the glass sandwiched through the pair of mixtures , and ( d) The glass is characterized in that the content of the leucite crystal is in the range of 10 to 70 wt% .
Aluminum may be an aluminum alloy, and copper may be a copper alloy. Moreover, wt% means weight%.

The second aspect, in the first shot bright metal bonding component, the thermosetting resin of the pair of the mixture, a phenol resin, an epoxy resin, one or selected from among urea resin, melamine resin, and alkyd resin It consists of more than seeds.

According to a third invention, in the metal joined part of the first invention or the second invention, at least one of the pair of metal members is aluminum , and the glass does not contain a Si component. Features.

A fourth invention is characterized in that, in the metal joined part of any of the first to third inventions, the glass has a thermal expansion coefficient in the range of 12 to 26 × 10 ⁻⁶ / K.

According to a fifth aspect of the present invention, in the metal joined component according to any one of the first to fourth aspects, the content of the ceramic powder in the mixture is in a range of 30 to 90 wt%.

The sixth invention, in any one of the metal bonding component of the first invention to the fifth invention, the matrix of the glass, 23～30Mol% of Z nO, 13~18mol% of B ₂ O _3, a Bi ₂ O ₃ It is characterized by being bismuth borate glass that is contained in an amount of 40 to 53 mol% and R ₂ O (R is an alkali component) is added as an optional component within a range of 23 mol% or less .

A seventh invention is a metal bonding material for bonding a pair of metal members made of aluminum or copper in an insulated state while ensuring airtightness and water resistance, and includes (a) a leucite crystal. A mixture of glass and (b) a pair of thermosetting resin and ceramic powder, which are interposed between the glass and the pair of metal members, respectively, and integrally fix the glass and the pair of metal members respectively. And (c) the glass is characterized in that the content of the leucite crystal is in the range of 10 to 70 wt% .

In such a metal bonded component, a pair of metal members are integrally bonded with a glass sandwiched between a pair of thermosetting resin and ceramic powder, and the glass contains leucite crystals. Therefore, the coefficient of thermal expansion becomes high, the influence of stress due to the difference in thermal expansion with the metal member is suppressed, and the mixture of the thermosetting resin and the ceramic powder is interposed, so that the temperature is 550 ° C. or lower. Metal members can be appropriately bonded, and excellent bonding strength, adhesion, and airtightness can be obtained. Since the difference in thermal expansion between glass and metal members is small, even in environments where the temperature is greatly increased or decreased, such as in electronic components mounted on vehicles, cracking, peeling, gas leaks, etc. are suppressed and excellent thermal durability Sex is obtained. Thermosetting resins have a relatively high coefficient of thermal expansion, but when ceramic powder is mixed, the coefficient of thermal expansion of the mixture decreases and the difference in thermal expansion from aluminum and copper decreases, which is even higher. Bonding strength, adhesion, airtightness, and thermal durability can be obtained. On the other hand, as a glass material, for example, bismuth borate glass can be adopted as in the sixth invention, and it is not necessary to use lead-based glass that causes environmental pollution, and it has excellent insulation and water resistance. Can be secured. Since insulation is ensured by glass, there is no possibility that the insulation is impaired even when a high voltage is applied. Thereby, even metal members, such as aluminum and copper, which need to be bonded at a relatively low temperature, can be appropriately bonded while ensuring excellent insulation, water resistance, and airtightness.
Further, since the glass contains leucite crystals in the range of 10 to 70 wt%, the thermal expansion coefficient of the glass can be about 12 to 26 × 10 ⁻⁶ / K, and the thermal expansion of aluminum The coefficient of thermal expansion (approximately 23 to 25 × 10 ⁻⁶ / K) and the coefficient of thermal expansion of copper ( approximately 16 to 18 × 10 ⁻⁶ / K) are slightly lower, and the difference in thermal expansion from those metal members Therefore, it is possible to appropriately suppress the effects of stress and the like, and to ensure excellent bonding strength, adhesion, airtightness, and thermal durability. If the content of the leucite crystal is lower than 10 wt%, the thermal expansion coefficient is low, and the effect of suppressing the influence of the difference in thermal expansion may not be obtained properly, whereas if it exceeds 70 wt%, the thermal expansion coefficient is high. In some cases, the bonding strength, adhesion, and airtightness may be impaired due to a difference in thermal expansion.

In the third invention, when at least one of the pair of metal members is aluminum and the glass containing no Si component is used in the matrix, the bonding strength can be appropriately ensured. That is, when glass contains Si component, the Si component reacts with aluminum and foams, and joint strength may be inhibited. A mixture of a thermosetting resin and ceramic powder exists between the glass and the metal member, but may react and foam due to contamination (contamination such as contamination).

In the fourth invention, since the thermal expansion coefficient of the glass is in the range of 12 to 26 × 10 ⁻⁶ / K, the thermal expansion coefficient of aluminum (about 23 to 25 × 10 ⁻⁶ / K) or the thermal expansion coefficient of copper. (About 16-18 × 10 ⁻⁶ / K), which is the same or slightly lower value, and can appropriately suppress the influence of stress and the like due to the difference in thermal expansion with those metal members, and the thermosetting resin and ceramic powder Combined with the presence of the mixture, it is possible to ensure excellent bonding strength, adhesion, airtightness, and thermal durability.

Since the mixture of the fifth invention has a ceramic powder content in the range of 30 to 90 wt%, the thermal expansion coefficient of the mixture should be appropriately reduced while ensuring low temperature bonding performance with a thermosetting resin. It is possible to reduce the difference in thermal expansion from aluminum and copper metal members, and to appropriately improve the bonding strength, adhesion, airtightness, and thermal durability. When the content of the ceramic powder is less than 30 wt%, the effect of reducing the thermal expansion coefficient and improving the bonding strength, thermal durability, and the like may not be sufficiently obtained. On the other hand, when the content exceeds 90 wt% In some cases, the bonding performance at a low temperature by the thermosetting resin may be hindered.

The sixth invention is a case where the glass matrix is bismuth borate glass, and the addition of leucite crystals can make the thermal expansion coefficient about 12 to 26 × 10 ⁻⁶ / K, and the difference in thermal expansion from the metal member. In addition, it is possible to appropriately suppress the influence of the above and to ensure excellent insulation and water resistance.

The seventh invention relates to a metal bonding material for bonding a pair of metal members made of aluminum or copper while ensuring airtightness and water resistance in an insulated state, and glass containing leucite crystals, The glass has a pair of thermosetting resin and ceramic powder interposed between the glass and the pair of metal members, respectively , and the glass contains leucite crystals in a range of 10 to 70 wt%. because you are, the same effect as substantially first invention is obtained.

It is a perspective view which shows an example of the metal joining component of this invention. It is sectional drawing explaining the structure of the junction part of the metal joining component of FIG. 1, and is an expanded sectional view of the II-II arrow part in FIG.

Since the metal bonding part and the metal bonding material of the present invention have excellent electrical insulation, air tightness, and water resistance, they are suitable for bonding metal members made of aluminum or copper used in electronic parts mounted on vehicles. However, it can be used for joining other on-vehicle components or other metal members made of aluminum or copper . In the present invention, a mixture in which ceramic powder is mixed with a thermosetting resin is used. Therefore, a difference in thermal expansion from aluminum or copper is reduced, and high thermal durability can be obtained. For example, a heat cycle temperature width ΔT Can be used under severe conditions of about 200 ° C.

The shape of the glass used as the metal bonding material is appropriately determined according to the bonding mode of the metal members to be bonded, and various forms such as a flat plate shape, a ring shape, and a cylindrical shape are possible, and the metal member is bonded. A pair of mixtures is provided in a state where they are electrically insulated from each other on two surfaces (a flat surface, an end surface, an inner peripheral surface, an outer peripheral surface, etc.). As the glass matrix, bismuth borate glass is preferably used as in the sixth invention, but other glass such as alkali glass that can increase the thermal expansion coefficient with leucite crystal can also be adopted. The composition of the bismuth borate glass of the sixth invention is an example, and bismuth borate glass deviating from the composition range can be used depending on the use conditions and the like.

  The pair of metal members to be joined may be the same material or different materials. The kind of the thermosetting resin of the mixture interposed between the metal member and the glass is appropriately determined. When the material of the pair of metal members is different, a different kind of thermosetting resin is used. Also good. When the materials of the pair of metal members are different, a common thermosetting resin can be used.

The type and content (mixing ratio) of the ceramic powder are also appropriately determined according to the material of the metal member and the type of thermosetting resin, but are common regardless of the material of the metal member and the type of thermosetting resin. The ceramic powder may be employed, or the ceramic powder may be mixed with a certain content. The ceramic powder content is desirably in the range of 30 to 90 wt%, for example, but even if it is less than 30 wt%, the effect of reducing the thermal expansion coefficient of the mixture containing the thermosetting resin is obtained. As the ceramic powder, oxide ceramics such as Al ₂ O ₃ (alumina), YSZ (yttria stabilized zirconia), MgO (magnesia), ZnO (zinc oxide) are preferably used. The lower the thermal expansion coefficient of the ceramic powder, the greater the effect of lowering the thermal expansion coefficient. Therefore, the content can be set according to the thermal expansion coefficient. For example, the thermal expansion coefficient of ZnO is about 8-9 × 10 ⁻⁶ / K, the thermal expansion coefficient of YSZ is about 10-11 × 10 ⁻⁶ / K, and the thermal expansion coefficient of MgO is 22-24 × 10 ^−6. The content may be reduced in the order of MgO, YSZ, and ZnO.

In the third invention, when at least one of the pair of metal members is aluminum, glass containing no Si component is used in the matrix. However, when both of the pair of metal members are other than aluminum, glass containing the Si component is used. Can also be used. The glass containing Si component contains, for example, SiO ₂ , specifically, K ₂ O: 15 wt%, SiO ₂ : 60 wt%, CaO: 15 wt%, MgO: 10 wt% glass, or B ₂ O ₃ : 50 wt%. %, SiO ₂ : 30 wt%, Bi ₂ O ₃ : 15 wt%, Ba ₂ O ₃ : 5 wt%, etc. When the present inventors conducted an aluminum joining test, SiO ₂ and aluminum reacted. Foamed and could not be joined.

In the 4th invention, the thermal expansion coefficient of the glass containing a leucite crystal is in the range of 12-26 * 10 < ^-6 > / K, and it is used suitably for joining of the metal member of aluminum or copper. In the present invention , the glass contains leucite crystals in the range of 10 to 70 wt%, and the thermal expansion coefficient of the glass is about 12 to 26 × 10 ⁻⁶ / K, so that the metal member of aluminum or copper is used. Ru preferably used in bonding.

  As for the airtightness of the metal bonded part, for example, when the metal bonded part has a bottomed cylindrical shape in which a metal plate is bonded to one end of a cylindrical metal tube, the metal bonded part is held in water and is, for example, about 0.2 MPa. It is desirable that pressure air is supplied into the cylinder and has airtightness to such an extent that bubbles are not generated from the joint portion to the outside. As for insulation, for example, it is desirable that the insulation be maintained so that the insulation state is maintained even when a voltage of about 2.6 kV is applied between the pair of metal members. Regarding the difference in thermal expansion, for example, even if a temperature change (heat cycle) of −40 to + 130 ° C. is repeated a predetermined number of times, cracks and peeling do not occur, and the above-mentioned airtightness is maintained for the bottomed cylindrical part. It is desirable to have a degree of thermal durability. In the present invention, an excellent thermal durability is obtained because a mixture in which ceramic powder is mixed with a thermosetting resin is used. Depending on the use environment, the heat cycle temperature width ΔT is 200 ° C. such as −40 to + 160 ° C. It can also be configured to meet the severe thermal durability of the degree. As for water resistance, it is desirable that the glass has a water resistance of 1% or less after the glass is immersed in warm water at 80 ° C. for 24 hours, for example, for in-vehicle electronic parts that require high temperature water resistance. It is also preferably used for joining metal members used. Regarding the bonding strength, for example, it is desirable that a tensile strength of 60 MPa or more is obtained by a tensile test using a tensile tester.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
A metal joining component 10 shown in FIG. 1 is obtained by integrally joining a metal plate 16 so as to hermetically close one end of a cylindrical metal tube 14 using a metal joining material 12 (hereinafter simply referred to as a joining material 12). Therefore, it is used for in-vehicle electronic components exposed to a high temperature atmosphere of about 70 to 90 ° C. The metal tube 14 and the metal plate 16 correspond to a pair of metal members, which are each made of conductive aluminum or copper, insulated from each other by the bonding material 12, and having a predetermined airtightness and water resistance. It is integrally joined in a secured state.

  FIG. 2 is an enlarged cross-sectional view taken along the line II-II in FIG. 1. The bonding material 12 has a ring shape corresponding to the metal tube 14, and the first mixture 22 and the second mixture are formed on both end surfaces of the glass 20. It is comprised by the 3 layer structure in which the 2 mixture 24 was provided. While the inner diameter of the bonding material 12 is smaller than the inner diameter of the metal tube 14, the outer diameter of the bonding material 12 is larger than the outer diameter of the metal tube 14 and protrudes to the inside and the outside of the metal tube 14. The glass 20 contains leucite crystals, and both ends of the glass 20 are provided with a first mixture 22 and a second mixture 24 in which ceramic powder is mixed with a thermosetting resin, and the metal tube 14 and The metal plate 16 is integrally fixed to both end faces of the glass 20 via the first mixture 22 and the second mixture 24, respectively. That is, the metal tube 14 and the metal plate 16, which are a pair of metal members, are in a state in which the glass 20 is sandwiched between the pair of first mixture 22 and second mixture 24 in which ceramic powder is mixed with thermosetting resin. They are joined together. Since such a bonding material 12 has the first mixture 22 and the second mixture 24 containing thermosetting resins on both sides of the glass 20, the metal tube 14 and the metal plate 16 are bonded at a low temperature of 550 ° C. or less. They can be joined together in an insulated state.

The glass 20 is, 0~23mol% of R ₂ O (R is an alkali component) in the present embodiment, ZnO and 23~30mol%, B ₂ O ₃ to 13~18mol%, Bi ₂ O ₃ to 40～53Mol% A bismuth borate glass containing no Si component such as SiO ₂ is used as a matrix, and a leucite crystal is contained within a range of 10 to 70 wt%. With the addition of this leucite crystal, the thermal expansion coefficient of the glass 20 is such that the thermal expansion coefficient of aluminum (23-25 × 10 ⁻⁶ / K) or the thermal expansion coefficient of copper (16-18 × 10 ⁻⁶ / K). It is in the range of 12 to 26 × 10 ⁻⁶ / K which is the same or slightly lower. The water resistance of the glass 20 is slightly lower than that of the bismuth borate glass to which no leucite crystal is added, but still high water resistance is ensured. In particular, when the content of the leucite crystal is about 60 wt% or less, high high temperature water resistance with a weight reduction rate of 1% or less after being immersed in warm water at 80 ° C. for 24 hours can be obtained. The content of the leucite crystal is appropriately determined within a range of 10 to 70 wt% in consideration of the glass composition and the like so that a predetermined water resistance can be obtained according to the use environment of the metal bonded part 10 or the like. A first mixture 22 and a second mixture 24 each containing a thermosetting resin are integrally fixed to both end faces of the ring-shaped glass 20, but the inner peripheral surface and the outer peripheral surface are exposed. Water resistance is required.

On the other hand, the thermosetting resin constituting the first mixture 22 and the second mixture 24 is one or more selected from phenol resin, epoxy resin, urea resin, melamine resin, and alkyd resin. Composed. The ceramic powder mixed with these thermosetting resins is Al ₂ O ₃ , YSZ, MgO, ZnO, etc., and the content thereof is the material of the metal tube 14, the metal plate 16, and the thermosetting resin. It is determined appropriately according to the type and the like, for example, within a range of 30 to 90 wt%. The first mixture 22 and the second mixture 24 may be different from each other in the types and mixing ratios of the thermosetting resin and ceramic powder, but are the same mixture in which the types and mixing ratios of the thermosetting resin and ceramic powder are equal to each other. It may be.

  In such a metal joined part 10 of the present embodiment, the metal tube 14 and the metal plate 16 made of aluminum or copper are made of glass through the first mixture 22 and the second mixture 24 in which thermosetting resin and ceramic powder are mixed. Since the glass 20 contains leucite crystals, the glass 20 has a relatively high thermal expansion coefficient. As a result, the difference in thermal expansion between the metal tube 14 or the metal plate 16 and the glass 20 is reduced to suppress the influence of stress or the like, and the first mixture 22 and the second mixture 24 containing the thermosetting resin. Therefore, the metal tube 14 and the metal plate 16 can be appropriately bonded at a low temperature of 550 ° C. or lower, and excellent bonding strength, adhesion, and airtightness can be obtained. Since the difference in thermal expansion between the glass 20, the metal tube 14, and the metal plate 16 is small, generation of cracks, peeling, gas leaks, and the like are suppressed even in a use environment where the temperature greatly increases and decreases like an electronic component mounted on a vehicle. Excellent thermal durability. In addition, although the thermosetting resin has a relatively high thermal expansion coefficient, it is decreased by mixing ceramic powder having a low thermal expansion coefficient, and the first mixture 22 and the second mixture 24, the metal tube 14, the metal plate 16, and the like. Therefore, higher bonding strength, adhesion, airtightness, and thermal durability can be obtained. On the other hand, since bismuth borate glass is used as the matrix of the glass 20, there is no fear of causing environmental pollution unlike lead-based glass, and excellent insulation and water resistance can be obtained. Since insulation is ensured by this glass 20, even when a high voltage is applied between the metal tube 14 and the metal plate 16, there is no possibility that the insulation is impaired. As a result, the metal tube 14 and the metal plate 16 made of aluminum or copper that need to be bonded at a relatively low temperature can be appropriately bonded with high bonding strength while ensuring excellent insulation, water resistance, and airtightness. it can.

  In addition, when either one or both of the metal tube 14 and the metal plate 16 is aluminum, if the matrix of the glass 20 contains a Si component, the Si component reacts with the aluminum to foam and the bonding strength is hindered. However, in this embodiment, since the matrix of the glass 20 does not contain a Si component, the bonding strength can be appropriately ensured.

Moreover, since the matrix of the glass 20 is bismuth borate glass and contains leucite crystals in the range of 10 to 70 wt%, and the thermal expansion coefficient is in the range of 12 to 26 × 10 ⁻⁶ / K. The thermal expansion coefficient of aluminum (about 23 to 25 × 10 ⁻⁶ / K) and the thermal expansion coefficient of copper (about 16 to 18 × 10 ⁻⁶ / K) are slightly lower. Thereby, the influence of the stress etc. by the thermal expansion difference between the metal tube 14 or the metal plate 16 made of aluminum or copper and the glass 20 can be appropriately suppressed, and the mixtures 22 and 24 of the thermosetting resin and the ceramic powder are interposed. Combined with this, it is possible to ensure excellent bonding strength, adhesion, airtightness, and thermal durability.

  In addition, since the first mixture 22 and the second mixture 24 have a ceramic powder content in the range of 30 to 90 wt%, the mixture 22 and 24 have a low temperature bonding performance with the thermosetting resin. The thermal expansion coefficient can be reduced appropriately, the difference in thermal expansion between the metal tube 14 and the metal plate 16 made of aluminum or copper is reduced, and the bonding strength, adhesion, air tightness, and thermal durability are appropriately improved. Can be made.

  Next, regarding the bismuth borate glass used as the matrix of the glass 20, the results of experiments conducted by the inventors on the thermal expansion coefficient, bonding temperature, and water resistance of No1 to No14 shown in Table 1 are shown. explain.

  Table 2 shows the results of examining the thermal expansion coefficient, bonding temperature, and water resistance of each of the compositions No1 to No14. The coefficient of thermal expansion was determined by pressing each glass powder into 20 mm x 4 mm x 4 mm rod-shaped samples, calcined at a temperature that did not round the corners of the samples, and then TMA (thermomechanical analysis). ). Regarding bonding temperature and water resistance, bismuth borate glass frit of each composition No. 1 to No. 14 is filled in a φ8 mm mold and press-molded, followed by vacuum firing at 700 ° C. for 10 minutes to prepare a bismuth borate glass sample The test was conducted using the glass sample. The bonding temperature was obtained by placing the glass sample on an aluminum substrate and firing at various temperatures in air for 20 minutes, and determining the lowest temperature at which bonding was possible as the bonding temperature. The water resistance was determined by immersing the prepared glass sample in warm water at 80 ° C. and measuring the weight change after 24 hours to determine the weight reduction rate (%).

From the results Table 2, the thermal expansion coefficient in the range of both 9 to 16 × 10 ^-6 / K, which is a range that can be adjusted to 12 to 26 × about 10 ^-6 / K by the addition of leucite crystals Yes, it can be used as a matrix for the glass 20. About joining temperature, all were 550 degrees C or less except composition No13. In the present invention, since the first mixture 22 and the second mixture 24 containing the thermosetting resin are interposed between the metal tube 14 and the metal plate 16, the bonding temperature of the matrix of the glass 20 is a problem. It has not been, it was described as a reference. As for water resistance, the weight reduction rate is 1% or less except for composition No5. Especially, compositions No1 to No3, No6, No7, No9, and No10 cannot measure weight change, and high high temperature water resistance is obtained. It was. Regarding composition No. 5, the content of R ₂ O (R is an alkali component) is as high as 28.55 mol%, while the contents of ZnO, B ₂ O ₃ and Bi ₂ O ₃ are relatively low. Acid glass cannot be used under conditions where high temperature water resistance is required. From the results of this such as the Bisumasuhou silicate glass used as the matrix glass 20, R ₂ O (R is an alkali component) 0~23mol% to, ZnO and 23~30mol%, B ₂ O ₃ to 13～18Mol%, Those containing 40 to 53 mol% Bi ₂ O ₃ are considered appropriate. Incidentally, R ₂ for O (R is an alkali component), if 24 mol% or less even exceed 23 mol% and a weight reduction rate is 1% or less, it is sufficiently possible to use as the matrix glass 20 is there. In the column of water resistance, “耐” means excellent (less than 0.5%), and “x” means not possible (more than 5%).

  Next, the results obtained by adding leucite crystals to the bismuth borate glass having the composition No. 1 in Table 1 and examining the addition amount, that is, the mixing ratio will be described. Table 3 shows the blending ratio (wt%) of bismuth borate glass and leucite crystal, and six types of samples (preparation 1 to blending 6) having different blending ratios were prepared. In these preparations 1 to 6, bismuth borate glass frit and leucite crystals of composition No. 1 were prepared and mixed at respective preparation ratios, and 1.5 g of the mixed powder was filled into a φ8 mm mold and press-molded. Then, the molded object of the leucite addition bismuth borate glass was obtained by performing vacuum baking for 10 minutes at 700 degreeC.

  Table 4 shows the results of examining the thermal expansion coefficient and water resistance for each of the above Formulation 1 to Formulation 6. The thermal expansion coefficient was measured by TMA in the same manner as in Table 2 above. About water resistance, it tested similarly to the case of the said Table 2 using the said molded object. “◯” in the column of water resistance means good (over 0.5% and 1% or less), and “Δ” means good (above 1% and 5% or less).

From the results of Table 4, for Formulation 2 to Formulation 6, the thermal expansion coefficient is as high as 12.8 to 26 × 10 ⁻⁶ / K, and the thermal expansion coefficient of aluminum (23 to 25 × 10 ⁻⁶ / K) The coefficient of thermal expansion of copper (16 to 18 × 10 ⁻⁶ / K) is only as low as or slightly lower than that of copper. Therefore, excellent bonding strength, adhesion and airtightness can be expected. Formulation 1 having a leucite crystal content of 0 wt% has a low coefficient of thermal expansion of 10.8 × 10 ⁻⁶ / K and cannot be used as the glass 20. Regarding water resistance, all of Formulations 1 to 4 having a relatively small content of leucite crystals have a weight reduction rate of 0.5% or less, and particularly excellent high-temperature water resistance is obtained. Also for Formulation 5 having a leucite crystal content of 55 wt%, the weight reduction rate is 1% or less, and excellent high-temperature water resistance is obtained. Formulation 6 with a leucite crystal content of 70 wt% has a relatively large weight loss rate of 2.0% and can be used as glass 20, but it can be used under conditions that require high temperature water resistance. Not suitable for. From this result, the content of the leucite crystal of the bismuth borate glass used as the glass 20 is suitably in the range of 10 to 70 wt%, and particularly preferably in the range of 10 to 60 wt%.

Next, while using the above leucite-added bismuth borate glass as glass 20, while using epoxy resin, phenol resin, urea resin, or melamine resin as thermosetting resin, Al ₂ O ₃ , YSZ, MgO, Alternatively, the metal tube 14 and the metal plate 16 are joined using the first mixture 22 and the second mixture 24 in which ZnO is mixed at a predetermined content, and each of the leak test, dielectric breakdown test, and thermal durability test is performed. And the results of measuring the bonding strength will be described. In Examples 1 to 6 in Table 5, the metal tube 14 and the metal plate 16 are both aluminum (Al), and the glass 20 contains a ratio of Formula 4 to the bismuth borate glass having the composition No. 1, that is, a leucite crystal. It is added at 40 wt%, and its thermal expansion coefficient is 21.6 × 10 ⁻⁶ / K. The first mixture 22 and the second mixture 24 have the same composition in each of Examples 1 to 6, and in Examples 1 to 3, Al ₂ O ₃ is mixed with an epoxy resin in a content of ₃₀ to 70 wt%. In Example 4, a phenol resin mixed with YSZ at a content of 57 wt% was used, and in Example 5, a urea resin mixed with a content of MgO at 63 wt% was used. In Example 6, what mixed ZnO with the content of 46 wt% was used for the melamine resin.

  The leak test is related to airtightness. The metal joint component 10 is held in water and 0.2 MPa of pressure air is supplied into the metal tube 14 to examine whether or not bubbles are generated from the joint portion. . “◯” means pass (no bubbles), and “x” means fail (bubbles). The dielectric breakdown test was related to insulation, and a voltage of 2.6 kV was applied between the metal tube 14 and the metal plate 16 to examine whether or not the insulation state was maintained. “◯” means pass (maintains insulation), and “x” means fail (conducts and breaks down). The thermal endurance test relates to a difference in thermal expansion. Here, the heat cycle temperature width ΔT is 200 ° C. Specifically, after a temperature change (heat cycle) of −40 to + 160 ° C. is repeated 100 times, cracks and peeling occur. It was examined whether or not a bubble was generated in the leak test. “O” means pass, that is, there is no crack or peeling and no bubble in the leak test, and “x” means fail, that is, crack or peeling occurs, or a bubble is generated in the leak test. Further, the bonding strength is a tensile strength measured by a tensile tester, “120” or more is “◎”, “60” or more and less than 120 MPa is “◯”, and less than 60 MPa is “x”. The pass / fail result in the “leak test” column is a test result in the initial state where the metal tube 14 and the metal plate 16 are joined, that is, before the thermal durability test or the like is performed.

  As apparent from Table 5 above, Examples 1 to 6 passed all leak tests, dielectric breakdown tests, and thermal durability tests, and excellent airtightness, insulating properties, and thermal durability were obtained. Also, the bonding strength is “◎” (good) or “◯” (possible), and aluminum can be bonded with high bonding strength.

In Examples 7 to 12 of Table 6, the metal tube 14 and the metal plate 16 are both copper (Cu), and the glass 20 contains the ratio of Formulation 3 in the bismuth borate glass having the composition No. 1, that is, the leucite crystal. It is added at 25 wt%, and its thermal expansion coefficient is 17.3 × 10 ⁻⁶ / K. The first mixture 22 and the second mixture 24 have the same composition in each of Examples 7 to 12, and in Examples 7 to 9, Al ₂ O ₃ was mixed with an epoxy resin at a content of 50 to 90 wt%. In Example 10, an epoxy resin mixed with YSZ at a content of 75 wt% was used, and in Example 11, an epoxy resin mixed with MgO at a content of 85 wt% was used. In Example 12, an epoxy resin in which ZnO is mixed at a content of 60 wt% is used. Since copper has a lower coefficient of thermal expansion than aluminum, the content of ceramic powder is increased compared to Examples 1 to 6 in Table 5 above. Then, each test of a leak test, a dielectric breakdown test, and a thermal durability test was performed in the same manner as in Table 5 above, and the bonding strength was measured.

  As is clear from Table 6 above, Examples 7 to 12 passed all leak tests, dielectric breakdown tests, and thermal durability tests, and excellent airtightness, insulating properties, and thermal durability were obtained. Also, the bonding strength is all “◯” (possible), and copper can be bonded with high bonding strength.

  On the other hand, Table 7 is a comparative example, Comparative Example 1 is a case where the metal tube 14 and the metal plate 16 are both aluminum (Al), and the glass 20 is the same as in Examples 1 to 6 in Table 5 above. Instead of the mixture 22 and the second mixture 24, an epoxy resin containing no ceramic powder is used. Moreover, the comparative example 2 is a case where both the metal tube 14 and the metal plate 16 are copper (Cu), and the glass 20 is the same as Examples 7 to 12 in Table 6 above, and the first mixture 22 and the second mixture. Instead of 24, an epoxy resin containing no ceramic powder is used. In the same manner as in Tables 5 and 6, leakage tests, dielectric breakdown tests, and thermal durability tests were performed, and the bonding strength was measured.

  As is clear from Table 7, the airtightness and insulation of both Comparative Examples 1 and 2 were acceptable, but the heat durability was unacceptable, and the bonding strength was less than 60 MPa. That is, since the thermal expansion coefficient of the epoxy resin interposed between the glass 20 and the metal tube 14 and the metal plate 16 is high and the thermal expansion difference is large, sufficient bonding strength cannot be obtained and peeling or the like is caused by heat cycle. Will occur. For this reason, it cannot be used for joining parts used under severe conditions such as in-vehicle electronic parts where the heat cycle temperature width ΔT reaches 200 ° C.

In Examples 13 to 17 of Table 8, when the metal tube 14 is copper (Cu) and the metal plate 16 is aluminum (Al), the first mixture 22 has an Al ₂ O ₃ content of 70 wt% in the epoxy resin. While using a mixture, and using a mixture of Al ₂ O ₃ in an epoxy resin with a content of 50 wt% as the second mixture 24, the content of leucite crystals in the glass 20 is variously changed to form a metal bonded part 10 was produced. The matrix of the glass 20 is bismuth borate glass having the composition No1. And each test of a leak test, a dielectric breakdown test, and a thermal durability test was performed in the same manner as in each of the above examples, and the bonding strength was measured.

As apparent from Table 8 above, Examples 13 to 17 passed all leak tests, dielectric breakdown tests, and thermal durability tests, and excellent airtightness, insulating properties, and thermal durability were obtained. Also, the bonding strength is all “◯” (possible), and copper and aluminum can be bonded with high bonding strength. That is, since the first mixture 22 and the second mixture 24 in which the ceramic powder is mixed with the thermosetting resin are interposed between the glass 20, the copper metal tube 14, and the aluminum metal plate 16, respectively. Even if the content of leucite crystals in the glass 20 changes in the range of 10 to 70 wt% and its thermal expansion coefficient varies in the range of 12.8 to 26 × 10 ⁻⁶ / K, excellent airtightness and insulating properties , Thermal durability and bonding strength can be obtained.

Examples 18 to 22 in Table 9 contain 50 wt% of Al ₂ O ₃ in the epoxy resin as the first mixture 22 and the second mixture 24 when the metal tube 14 and the metal plate 16 are both aluminum (Al). While using what was mixed by the quantity, the content of the leucite crystal of the glass 20 was changed variously, and the metal joining component 10 was produced. The matrix of the glass 20 is bismuth borate glass having the composition No1. And each test of a leak test, a dielectric breakdown test, and a thermal durability test was performed in the same manner as in each of the above examples, and the bonding strength was measured.

As is clear from Table 9 above, Examples 18 to 22 passed all leak tests, dielectric breakdown tests, and thermal durability tests, and excellent airtightness, insulating properties, and thermal durability were obtained. Also, the bonding strength is all “◯” (possible), and aluminum can be bonded with high bonding strength. That is, since the first mixture 22 and the second mixture 24 in which ceramic powder is mixed with a thermosetting resin are interposed between the glass 20 and the aluminum metal tube 14 and the metal plate 16, the glass 20. Even if the content of the leucite crystal varies in the range of 10 to 70 wt% and its thermal expansion coefficient varies in the range of 12.8 to 26 × 10 ⁻⁶ / K, excellent airtightness, insulation, heat Durability and bonding strength are obtained.

Examples 23 to 27 in Table 10 contain 70 wt% of Al ₂ O ₃ in the epoxy resin as the first mixture 22 and the second mixture 24 when the metal tube 14 and the metal plate 16 are both copper (Cu). While using what was mixed by the quantity, the content of the leucite crystal of the glass 20 was changed variously, and the metal joining component 10 was produced. The matrix of the glass 20 is bismuth borate glass having the composition No1. And each test of a leak test, a dielectric breakdown test, and a thermal durability test was performed in the same manner as in each of the above examples, and the bonding strength was measured.

As is clear from Table 10 above, Examples 23 to 27 passed all leak tests, dielectric breakdown tests, and thermal durability tests, and excellent airtightness, insulating properties, and thermal durability were obtained. Also, the bonding strength is all “◯” (possible), and copper can be bonded with high bonding strength. That is, since the first mixture 22 and the second mixture 24 in which the ceramic powder is mixed with the thermosetting resin are interposed between the glass 20 and the copper metal tube 14 and the metal plate 16, Even if the content of leucite crystal changes in the range of 10 to 70 wt% and the thermal expansion coefficient varies in the range of 12.8 to 26 × 10 ⁻⁶ / K, excellent airtightness, insulation, and heat durability And bonding strength can be obtained.

  As mentioned above, although the Example of this invention was described in detail based on drawing, these are one Embodiment to the last, This invention is implemented in the aspect which added the various change and improvement based on the knowledge of those skilled in the art. be able to.

  DESCRIPTION OF SYMBOLS 10: Metal joining part 12: Joining material for metals 14: Metal pipe (metal member) 16: Metal plate (metal member) 20: Glass 22: 1st mixture 24: 2nd mixture

Claims (7)

A metal joint part in which a pair of metal members made of aluminum or copper are joined in an insulated state while ensuring airtightness and water resistance,
Glass containing leucite crystals;
A mixture of a pair of thermosetting resin and ceramic powder respectively interposed between the glass and the pair of metal members and integrally fixing the glass and the pair of metal members;
And the pair of metal members are integrally joined to each other with the glass sandwiched through the pair of mixtures ,
And the said glass has the content of the said leucite crystal in the range of 10-70 wt%, The metal joining component characterized by the above-mentioned. The thermosetting resin of the pair of the mixture, phenolic resin, epoxy resin, urea resin, according to claim 1, characterized in that it consists of one or more members selected from among melamine resin, and alkyd resin Metal joint parts. The metal joined component according to claim 1 or 2 , wherein at least one of the pair of metal members is aluminum , and the glass does not contain a Si component in the matrix. The metal joint component according to any one of claims 1 to 3 , wherein the glass has a coefficient of thermal expansion within a range of 12 to 26 × 10 ^-6 / K. The metal joint component according to any one of claims 1 to 4 , wherein the mixture has a content of the ceramic powder in a range of 30 to 90 wt%. Matrix of said glass, Z nO the 23~30mol%, B ₂ O ₃ to 13~18mol%, the Bi ₂ O ₃ is contained 40~53mol%, and, R ₂ O (R is an alkali component) It is a bismuth borate glass added as an arbitrary component in the range of 23 mol% or less . The metal joint component according to any one of claims 1 to 5 . A metal bonding material for bonding a pair of metal members made of aluminum or copper while ensuring airtightness and water resistance in an insulated state,
Glass containing leucite crystals;
A mixture of a pair of thermosetting resin and ceramic powder, which is interposed between the glass and the pair of metal members, respectively, and integrally bonds the glass and the pair of metal members;
And the glass has a content of the leucite crystal in the range of 10 to 70 wt% .

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