JP2017202953A - Encapsulation material laminate and conjugate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an encapsulation material capable of suppressing breakage of members caused by residual stress during conjugating a low expansion member and a high expansion member.SOLUTION: There is provided an encapsulation material laminate 3 manufactured by conjugating an encapsulation material layer 1 having thermal expansion coefficient αand a second encapsulation material layer 2 having thermal expansion coefficient αeach other, satisfying a relationship of -25×10/K≤α≤25×10/K and α<α, and having α-α≥10×10-7/K, the first encapsulation material layer 1 and/or the second encapsulation material layer 2 contain glass, the first encapsulation material layer 1 contains β-quartz solid solution as a main crystal, and contains glass containing, by mol%, SiO:48 to 75%, AlO:5 to 25%, LiO:5 to 30%, BO:10 to 23% excluding 10%, ZnO:0 to 2.5% excluding 2.5% as a composition. There is provided a conjugation 100 having the encapsulation material laminate 3 inclusion conjugated between a first member 10 and a second member 20.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a sealing material laminate suitable for joining a low expansion member and a high expansion member, and a joined body using the same.

  Quartz glass, crystallized glass, low expansion ceramics and the like have a low coefficient of thermal expansion and are excellent in heat resistance, and are therefore widely used as structural members for high temperature processing jigs, heaters, engines, and the like. When these members made of a low expansion material are incorporated into various devices, it may be necessary to join the high expansion member made of metal or the like. Examples of such joining include welding and joining with a sealing material such as glass frit. However, since welding has a safety problem and large-area processing is difficult, joining with a sealing material is preferably used.

  Since the above structural member is often used at high temperatures, the sealing material also requires high heat resistance. As a sealing material excellent in heat resistance, a glass sealing material, particularly a crystalline glass sealing material has been proposed (for example, see Patent Document 1).

Japanese Patent No. 2715138

  When joining a low expansion member and a high expansion member with a sealing material, matching of thermal expansion coefficients between materials becomes a problem. That is, when the thermal expansion coefficients of the low expansion member and the sealing material are matched, the difference in thermal expansion coefficient between the sealing material and the high expansion member becomes large. On the other hand, when the thermal expansion coefficients of the high expansion member and the sealing material are matched, the difference in thermal expansion coefficient between the sealing material and the low expansion member becomes large. When the difference in coefficient of thermal expansion between the member and the sealing material becomes large, residual stress is generated at the time of joining, and breakage easily occurs.

  In view of the above, an object of the present invention is to provide a sealing material capable of suppressing damage to a member due to residual stress when joining a low expansion member and a high expansion member.

  As a result of intensive studies by the present inventors, it has been found that the above problems can be solved by a sealing material having a specific laminated structure.

That is, the present invention provides a sealing material laminate second sealing material layer having a first sealing material layer and the thermal expansion coefficient alpha ₂ having a thermal expansion coefficient alpha ₁ is formed by joining together, It is related with the sealing material laminated body characterized by satisfying the relationship of −25 × 10 ⁻⁷ / K ≦ α ₁ ≦ 25 × 10 ⁻⁷ / K and α ₁ <α ₂ .

  Thus, by joining the two types of members having different thermal expansion coefficients by adopting a laminated structure in which the thermal expansion coefficient of the sealing material layer increases stepwise, the interface between each member and each sealing material layer The difference in coefficient of thermal expansion can be reduced. As a result, the residual stress generated between each member and each sealing material layer can be reduced, and damage to the member can be suppressed. In addition, in this invention, a thermal expansion coefficient shows the value in the temperature range of 30-380 degreeC.

In the sealing material laminate of the present invention, α ₂ −α ₁ ≧ 10 × 10 ⁻⁷ / K is preferable. In this way, even when the difference in thermal expansion between the two types of members is relatively large, it becomes possible to reduce the difference in thermal expansion coefficient at the interface between each member and each sealing material layer. It becomes easy to suppress the damage of the member.

  The sealing material laminated body of this invention WHEREIN: It is preferable that a 1st sealing material layer and a 2nd sealing material layer contain glass. If it does in this way, the heat resistance of a sealing part can be improved.

  In the sealing material laminate of the present invention, a material containing, for example, crystallized glass can be used as the first sealing material layer. If it does in this way, the low expansion of the 1st sealing material layer will become easy, and it will become easy to match a thermal expansion coefficient with a low expansion member.

  In the sealing material laminate of the present invention, it is preferable that the first sealing material layer contains a β-quartz solid solution as a main crystal.

In the sealing material laminate of the present invention, the first sealing material layer has a composition of mol%, SiO ₂ 48 to 75%, Al ₂ O ₃ 5 to 25%, Li ₂ O 5 to 30%, It is preferable to include glass containing 10 to 23% (excluding 10%) of B ₂ O ₃ (excluding 10%) and 0 to 2.5% (excluding 2.5%) of ZnO. Glass having this composition is likely to precipitate a β-quartz solid solution by heat treatment.

  In the sealing material laminate of the present invention, it is preferable that the first sealing material layer and the second sealing material layer are made of a powder sintered body. If it does in this way, the failure | damage of the sealing material layer resulting from the interface stress of a 1st sealing material layer and a 2nd sealing material layer can be suppressed. This is presumably because the voids contained in the powder sintered body play a role of relaxing stress.

  The joined body of the present invention includes the first member and the second member, and the above-described sealing material laminate interposed between the first member and the second member, and the first member and the first member. The sealing material layer and the second member and the second sealing material layer are bonded to each other.

In the joined body of the present invention, the difference in thermal expansion coefficient between the first member and the second member is preferably 20 × 10 ⁻⁷ / K or more. In this case, it becomes easy to enjoy the effect of using the sealing material laminate of the present invention.

In the joined body of the present invention, the difference in thermal expansion coefficient between the first member and the first sealing material layer and the difference in thermal expansion coefficient between the second member and the second sealing material layer are each 20 × 10. It is preferably ⁻⁷ / K or less. If it does in this way, the stress which generate | occur | produces between each member and a sealing material layer can be reduced, and it becomes possible to suppress the failure | damage of a member.

  In the joined body of the present invention, for example, quartz glass, crystallized glass, or low expansion ceramics can be used as the first member.

  In the joined body of the present invention, for example, metal, glass, or high expansion ceramics can be used as the second member.

  The method for manufacturing a joined body according to the present invention is a method for producing the above joined body, wherein the first member is fired in a state where the first sealing material is disposed on the first member. Forming a first sealing material layer on the first sealing material layer; arranging a second sealing material on the first sealing material layer; and further arranging a second member on the second sealing material And firing the product in a state where the second sealing material layer is formed and joining the first sealing material layer and the second member with the second sealing material layer. And In the present invention, “arranging” the sealing material includes forms such as placement and application.

  The method for producing a joined body according to the present invention is a method for producing the above joined body, wherein the second member is fired in a state where the second sealing material is disposed on the second member. A step of forming a second sealing material layer thereon, a first sealing material is disposed on the second sealing material layer, and a first member is further disposed on the first sealing material. And bake in the state of forming the first sealing material layer, and joining the second sealing material layer and the first member with the first sealing material layer. And

  If the sealing material laminated body of this invention is used, in joining a low expansion member and a high expansion member, the residual stress produced between each member and each sealing material layer can be made small, and the failure | damage of a member is suppressed. Is possible.

It is typical sectional drawing which shows one Embodiment of the conjugate | zygote of this invention. It is typical sectional drawing which shows 1st Embodiment of the manufacturing method of the conjugate | zygote of this invention. It is typical sectional drawing which shows 2nd Embodiment of the manufacturing method of the conjugate | zygote of this invention. It is typical sectional drawing which shows 3rd Embodiment of the manufacturing method of the conjugate | zygote of this invention.

Sealing material laminate of the present invention is one in which the second sealing material layer having a first sealing material layer and the thermal expansion coefficient alpha ₂ having a thermal expansion coefficient alpha ₁ is formed by joining together. Here, α ₁ and α ₂ satisfy the relationship of α ₁ <α ₂ .

The thermal expansion coefficient α1 of the _first sealing material layer is −25 × 10 ^{−7 to} 25 × 10 ⁻⁷ / K, −15 × 10 ⁻⁷ to 15 × 10 ⁻⁷ / K, particularly −10 ×. is preferably ^{10 -7 ~10 × 10 -7 / K} . If it does in this way, since a thermal expansion coefficient with a low expansion member can be matched, generation | occurrence | production of the crack in a member can be suppressed at the time of joining.

The second sealing material layer, not particularly limited as long as the thermal expansion coefficient alpha ₂ is greater than the thermal expansion coefficient alpha ₁ of the first sealing material layer. Preferably, α ₂ -α ₁ is 10 × 10 ⁻⁷ / K or more, 15 × 10 ⁻⁷ / K or more, particularly 20 × 10 ⁻⁷ / K or more. In this way, even if the difference in thermal expansion between the two types of members to be joined is relatively large, it becomes possible to reduce the difference in thermal expansion coefficient at the interface between each member and each sealing material layer. It becomes easy to suppress damage of each member at the time. However, if α ₂ −α ₁ is too large, cracks are generated at the interface between the first sealing material layer and the second sealing material layer, or the two are not bonded together, so that 30 × 10 ⁻⁷ / K. Hereinafter, it is particularly preferably 25 × 10 ⁻⁷ / K or less.

  The thicknesses of the first sealing material layer and the second sealing material layer are not particularly limited. However, if the thickness is too small, the mechanical strength of the sealing material layer tends to decrease. On the other hand, when the thickness is too large, the residual stress in the encapsulant layer may increase and the mechanical strength may decrease. Furthermore, the size of the entire joined body tends to increase. Therefore, the thickness of the first sealing material layer and the second sealing material layer is preferably 1 μm to 5 mm, particularly preferably 10 μm to 3 mm.

  In addition, between the 1st sealing material layer and the 2nd sealing material layer, a thermal expansion coefficient is higher than a 1st sealing material layer, and a thermal expansion coefficient is lower than a 2nd sealing material layer. 3 sealing material layers may be provided. In this case, since the third sealing material layer serves as a buffer material, even if the difference in thermal expansion coefficient between the first sealing material layer and the second sealing material layer is large. It is possible to suppress the occurrence of defects such as cracks.

  Both the first sealing material layer and the second sealing material layer are preferably made of glass. If it does in this way, the heat resistance of a sealing part can be improved. In particular, when the first sealing material layer contains crystallized glass, it is easy to reduce the expansion, and it is easy to match the thermal expansion coefficient with the low expansion member. Specifically, the first sealing material layer preferably contains a β-quartz solid solution that is a low expansion crystal. The content of β-quartz solid solution in the first sealing material layer is preferably 75 to 99% by mass, 80 to 97% by mass, and particularly preferably 85 to 95% by mass. When there is too little content of (beta) -quartz solid solution, there exists a tendency for the low expansion of a sealing part to become difficult. On the other hand, if the content of β-quartz solid solution is too large, the fluidity at the time of joining tends to decrease. In addition, the sealing material layer containing crystallized glass is obtained by heat-processing the sealing material containing crystalline glass.

As a specific example of the first sealing material layer, the composition is mol%, SiO ₂ 48 to 75%, Al ₂ O ₃ 5 to 25%, Li ₂ O 5 to 30%, B ₂ O ₃ 10 to 10%. Examples include those containing glass containing 23% (however, not including 10%) and ZnO 0-2.5% (not including 2.5%). The reason for this composition will be described below. In the following description of the content of each component, “%” means “mol%” unless otherwise specified.

SiO ₂ is a component that forms a glass skeleton, and is a constituent component of the β-quartz solid solution. The content of SiO ₂ is preferably 48 to 75%, 53 to 70%, particularly 58 to 65%. When the content of SiO ₂ is too small, the amount of β-quartz solid solution precipitated becomes small, and it becomes difficult to obtain low thermal expansion characteristics. On the other hand, when the SiO ₂ is too large, the softening point increases, softening fluidity by heat treatment at the time of sealing tends to decrease.

Al ₂ O ₃ is a constituent component of the β-quartz solid solution. The content of Al ₂ O ₃ is preferably 5 to 25%, 7 to 15%, particularly preferably 7 to 13%. When Al ₂ content of O ₃ is too small, beta-precipitation amount of quartz solid solution is reduced, the low thermal expansion characteristics are difficult to obtain. On the other hand, when the Al ₂ O ₃ is too large, since the softening point is raised, softening fluidity by heat treatment at the time of sealing it tends to decrease.

Li ₂ O is a component of the β-quartz solid solution and a component that lowers the softening point. The content of Li ₂ O is preferably 5 to 30%, 10 to 25%, particularly 10 to 20%. When Li 2 _O content is too small, beta-precipitation amount of quartz solid solution is reduced, the low thermal expansion characteristics are difficult to obtain. Moreover, since the softening point rises, the softening fluidity due to heat treatment during sealing tends to decrease. On the other hand, if the content of Li ₂ O is too large, the content of Li ₂ O in the residual glass after heat treatment increases and the coefficient of thermal expansion of the residual glass increases. As a result, it is difficult to obtain low thermal expansion characteristics. Become.

B ₂ O ₃ is a component that forms a glass skeleton and a component that lowers the softening point. The content of B ₂ O ₃ is preferably 10 to 23% (excluding 10%), 12 to 16%, and particularly preferably 13 to 15%. If the content of B ₂ O ₃ is too small, the softening point increases, the difference between the crystallization temperature and the softening point is reduced. Therefore, crystals tend to precipitate before the softening flow by heat treatment at the time of sealing, and the fluidity tends to decrease. On the other hand, if the content of B ₂ O ₃ is too large, the proportion of the residual glass phase after heat treatment increases (the amount of β-quartz solid solution deposited decreases), and the thermal expansion coefficient of the residual glass phase increases. As a result, low thermal expansion characteristics are difficult to obtain.

Incidentally, by suitably adjusting the proportion of B ₂ O ₃ and Li 2 content of each _O, low thermal expansion characteristics are easily obtained. Specifically, it is preferable to adjust the value of B ₂ O ₃ / Li ₂ O to 0.5 to 1, 0.7 to 1, particularly 0.8 to 1. Incidentally, _{"B 2 O} 3 / Li 2 _O" means the molar ratio of each _B 2 _{O 3} content and Li ₂ O.

  ZnO is a component that improves weather resistance. Moreover, there exists an effect which improves the softening fluidity | liquidity by the heat processing at the time of sealing. The ZnO content is preferably 0 to 2.5% (excluding 2.5%), particularly preferably 0 to 2%. When the content of ZnO is too large, the amount of β-quartz solid solution precipitated is reduced, or dissimilar crystals that do not contribute to low expansion, such as Zn—Al-based crystals, are likely to precipitate. Moreover, the thermal expansion coefficient of the residual glass after heat treatment tends to increase. As a result, the thermal expansion coefficient tends to increase.

  In addition, you may contain MgO, CaO, SrO, or BaO as a component which improves a weather resistance. These components also have the effect of improving the softening fluidity by heat treatment during sealing. The content of MgO + CaO + SrO + BaO is preferably 0 to 10%, 0 to 5%, particularly preferably 0.1 to 2%. When the content of MgO + CaO + SrO + BaO is too large, the amount of β-quartz solid solution precipitated tends to decrease or the thermal expansion coefficient of the residual glass phase after heat treatment tends to increase. As a result, the thermal expansion coefficient tends to increase.

Similarly, La ₂ O ₃ , ZrO ₂ or Bi ₂ O ₃ may be included as a component for improving weather resistance. Among these, ZrO ₂ and Bi ₂ O ₃ also have an effect of improving softening fluidity by heat treatment during sealing. The content of La ₂ O ₃ + ZrO ₂ + Bi ₂ O ₃ is preferably 0 to 10%, 0 to 5%, particularly preferably 0.1 to 2%. When La ₂ O ₃ + content of _ZrO 2 + _Bi 2 _{O 3} is too large, or fewer precipitation amount of β- quartz solid solution, tends to thermal expansion coefficient of the residual glassy phase after the heat treatment increases. In particular, when the content of La ₂ O ₃ is too large, heterogeneous crystals that do not contribute to low expansion, such as La-B crystals, are likely to precipitate. As a result, the thermal expansion coefficient tends to increase.

In addition to the above components, the total amount of Na ₂ O, K ₂ O, MnO, P ₂ O ₅ , MoO ₂ , TiO ₂ , V ₂ O _{5 and the} like is 30% or less in a range not impairing the effects of the present invention. It is possible to make it contain in 20% or less, Furthermore, 10% or less of range.

The second sealing material layer, not particularly limited as long as the thermal expansion coefficient alpha ₂ is greater than the thermal expansion coefficient alpha ₁ of the first sealing material layer. Preferably, α ₂ -α ₁ is 10 × 10 ⁻⁷ / K or more, 15 × 10 ⁻⁷ / K or more, particularly 20 × 10 ⁻⁷ / K or more. In this way, even if the difference in thermal expansion between the two types of members to be joined is relatively large, it becomes possible to reduce the difference in thermal expansion coefficient at the interface between each member and each sealing material layer. It becomes easy to suppress damage of each member at the time.

  The second sealing material layer is made of glass such as borosilicate glass, bismuth glass, phosphate glass, tin phosphate glass, vanadium glass, lead glass, borate glass, or alkali silicate glass. Including.

  The first sealing material layer and the second sealing material layer are preferably made of a powder sintered body. In this case, since the voids contained in the powder sintered body relieve stress, the sealing material layer is damaged due to the interface stress between the first sealing material layer and the second sealing material layer. Can be suppressed.

  Note that the first sealing material layer and the second sealing material layer may contain a refractory filler powder for adjusting the thermal expansion coefficient. The content of the refractory filler in the first sealing material layer and the second sealing material layer is preferably 0 to 30% by mass, 0.1 to 20% by mass, and particularly preferably 1 to 10% by mass. When there is too much content of a refractory filler powder, the bondability with respect to a to-be-joined member will fall easily.

  As the refractory filler powder, cordierite, willemite, alumina, zirconium phosphate, zircon, zirconia, tin oxide, mullite, silica, β-eucryptite, β-spodumene, β-quartz solid solution, zirconium tungstate phosphate Etc. can be used.

  Next, a bonded body using the sealing material laminate of the present invention will be described.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of the joined body of the present invention. The joined body 100 includes a first member 10 and a second member 20, and a sealing material laminate 3 composed of the first sealing material layer 1 and the second sealing material layer 2 interposed therebetween. I have. Here, the 1st member 10 and the 1st sealing material layer 1, and the 2nd member 20 and the 2nd sealing material layer 1 are arrange | positioned so that each may join.

The first member is a low expansion member, and the second member is a high expansion member. The difference in thermal expansion coefficient between the first member and the second member is, for example, 20 × 10 ⁻⁷ / K or more, 25 × 10 ⁻⁷ / K or more, and further 30 × 10 ⁻⁷ / K or more. Since the present invention aims to join members having a large difference in thermal expansion coefficient without damaging them, when the difference in thermal expansion coefficient between the first member and the second member is large, It becomes easy to enjoy the effect of using the sealing material laminate. However, if the difference in coefficient of thermal expansion between the first member and the second member is too large, joining tends to be difficult, so it is 60 × 10 ⁻⁷ / K or less, particularly 50 × 10 ⁻⁷ / K or less. Preferably there is.

The difference in thermal expansion coefficient between the first member and the first sealing material layer and the difference in thermal expansion coefficient between the second member and the second sealing material layer are each 20 × 10 ⁻⁷ / K or less, respectively. It is preferable that it is 18 * 10 < ^-7 > / K or less, especially 15 * 10 < ^-7 > / K or less respectively. If it does in this way, the stress which generate | occur | produces between each member and a sealing material layer can be reduced, and it becomes possible to suppress the failure | damage of a member.

The thermal expansion coefficient of the first member is, for example, −25 × 10 ^{−7 to} 25 × 10 ⁻⁷ / K, −15 × 10 ⁻⁷ to 15 × 10 ⁻⁷ / K, particularly −10 × 10 ⁻⁷ to 10 × 10 ⁻⁷ / K. Specific examples of the first member include quartz glass, crystallized glass, and low expansion ceramics.

The thermal expansion coefficient of the second member is, for example, 25 × 10 ^{−7 to} 60 × 10 ⁻⁷ / K, 25 × 10 ^{−7 to} 55 × 10 ⁻⁷ / K, particularly 25 × 10 ⁻⁷ to 50 × 10 ^{− 7} / K. Specific examples of the second member include metal, glass, high expansion ceramics, and the like.

  FIG. 2 is a schematic cross-sectional view showing a first embodiment of a method for producing a joined body according to the present invention.

  First, a first sealing material 1 ′ that becomes the first sealing material layer 1 by firing is disposed on the first member 10 (a in FIG. 2). By firing in this state, the first sealing material layer 1 is formed on the first member 10 (b in FIG. 2).

  Next, on the first sealing material layer 1, a second sealing material 2 ′ that becomes the second sealing material layer 2 by firing is disposed, and further on the second sealing material 2 ′. Two members 20 are arranged (c in FIG. 2). By firing in this state, the second sealing material layer 2 is formed, and the first sealing material layer 1 and the second member 20 are joined by the second sealing material layer 2 (FIG. 2). D).

  FIG. 3 is a schematic cross-sectional view showing a second embodiment of the method for producing a joined body according to the present invention.

  First, the second sealing material 2 ′ that becomes the second sealing material layer 2 by firing is disposed on the second member 20 (a in FIG. 3). By firing in this state, the second sealing material layer 2 is formed on the second member 20 (b in FIG. 3).

  Next, a first sealing material 1 ′ that becomes the first sealing material layer 1 by firing is disposed on the second sealing material layer 2, and the first sealing material 1 ′ is further disposed on the first sealing material 1 ′. 1 member 10 is arranged (c in FIG. 3). By firing in this state, the first sealing material layer 1 is formed, and the second sealing material layer 2 and the first member 10 are joined by the first sealing material layer 1 (FIG. 3). D).

  The manufacturing method of the first embodiment is applied when the first sealing material 1 ′ has a higher softening point (higher firing temperature) than the second sealing material 2 ′. On the other hand, the manufacturing method of the second embodiment is applied when the second sealing material 2 ′ has a higher softening point (higher firing temperature) than the first sealing material 1 ′. That is, firing is performed in order from the sealing material having the higher softening point (firing temperature). When a sealing material layer is formed by firing a sealing material having a low softening point first, when the sealing material having a high softening point is fired later, the sealing material layer having a low softening point softens and flows. This is because the sealing state may be deteriorated.

  FIG. 4 is a schematic cross-sectional view showing a third embodiment of the method for producing a joined body according to the present invention.

  First, the first sealing material 1 ′ that becomes the first sealing material layer 1 by firing is disposed on the first member 10. In addition, a second sealing material 2 ′ that becomes the second sealing material layer 2 by firing is disposed on the second member 20 (a in FIG. 4). In this state, by firing each of them, a first laminate 11 in which the first sealing material layer 1 is formed on the first member 10 and a second laminate on the second member 20. The 2nd laminated body 21 in which the sealing material layer 2 is formed is obtained (b of FIG. 4).

  Next, the 1st laminated body 11 and the 2nd laminated body 21 are laminated | stacked so that the 1st sealing material layer 1 and the 2nd sealing material layer 2 may contact | connect (c of FIG. 4). By firing in that state, the first sealing material layer 1 or the second sealing material layer 2 is softened and fluidized, whereby the first sealing material layer 1 and the second sealing material layer 2 are made to flow. They are joined (d in FIG. 4). When the first sealing material layer 1 has a softening point lower than that of the second sealing material layer 2, the firing temperature is set near the softening point of the first sealing material layer 1 and the second sealing material. When the softening point of the layer 2 is lower than that of the first sealing material layer 1, the softening point is set near the second sealing material layer 2.

  The first sealing material 1 'and the second sealing material 2' are provided in the form of powder, green compact, paste, or the like. The firing temperature is preferably within the range of the softening point ± 100 ° C., particularly the softening point ± 50 ° C. of each sealing material. If the firing temperature is too low, the softening flow becomes insufficient and the adhesive strength tends to be inferior. On the other hand, if the firing temperature is too high, the fluidity becomes excessive and joining tends to be difficult. In addition, when the sealing material is crystalline glass, a crystal transition (for example, a crystal transition from a β-quartz solid solution to a β-spodumene solid solution) may occur, and the sealing portion may be highly expanded.

The average particle diameter _{D 50} of the first sealing member 1 'and the second sealing member 2' 15 [mu] m or less, 0.5 to 10 [mu] m, particularly 0.7~5μm is preferred. When the particle size of the average particle diameter D ₅₀ is too large, the pores in the sealing material layer obtained after firing becomes too much tends to be inferior in joint strength. Here, the “average particle diameter D ₅₀ ” refers to a value measured with a laser diffractometer, and in the volume-based cumulative particle size distribution curve measured by the laser diffraction method, the accumulated amount is accumulated from the smaller particle. The particle diameter is 50%.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.

  Table 1 shows the composition and characteristics of the first and second sealing materials used in the examples.

(1) Preparation of 1st and 2nd sealing material The raw material batch was produced by preparing the raw material powder so that it might become the glass composition of Table 1, and mixing uniformly. The raw material batch was placed in a platinum crucible and melted at 1400-1600 ° C. until homogeneous. The obtained molten glass was poured between a pair of molding rollers and molded while being rapidly cooled to obtain a film-like glass. After 12-14 hours dry grinding the film-like glass using a ball mill, mesh by performing classification with a metal sieve of 100 [mu] m, the first and second sealing average particle diameter D ₅₀ is made of glass powder 8μm A stop was obtained.

(2) Measurement of thermal expansion coefficient The thermal expansion coefficient of the first sealing material (thermal expansion coefficient of the first sealing material layer) was measured as follows. Glass powder was put into a stainless steel mold (inner dimensions: 10 mm × 10 mm × 50 mm) and pressed at a pressure of 0.4 MPa to produce a green compact. The green compact was fired in a box-type electric furnace under firing conditions of 700 ° C. for 30 minutes (heating rate: 10 ° C./minute) to obtain a sintered body. A sample for measurement was produced by processing the obtained sintered body into a predetermined shape. About the obtained sample for a measurement, the thermal expansion coefficient in a 30-380 degreeC temperature range was measured using the thermomechanical analyzer (Thermo Thermo TMA8310 by Rigaku).

Incidentally, the measurement sample of the first encapsulant average particle diameter D ₅₀ was pulverized so as to be approximately 20μm with alumina mortar, by powder X-ray diffraction method using the obtained powder sample was measured However, it was confirmed that β-quartz solid solution crystals were precipitated as main crystals.

  The thermal expansion coefficient of the second sealing material was measured in the same manner as the sealing material 1 using a measurement sample obtained by molding molten glass into a predetermined shape.

(3) Production of bonded body A quartz glass substrate (thermal expansion coefficient 4 × 10 ⁻⁷ / K) and a borosilicate glass substrate (thermal expansion coefficient 38 × 10 ⁻⁷ / K; OA-10G manufactured by Nippon Electric Glass Co., Ltd.) Then, a joined body was prepared by joining with each sealing material layer described in Table 2 according to the following procedure. No. in Table 2 No. 1 is an example, no. 2 and 3 show comparative examples.

(3-1) No. 1
The first green compact was produced by putting the first sealing material into a stainless steel mold (inner diameter φ10 mm) and pressing it at a pressure of 0.4 MPa. Also, the second green compact was produced by pressing the second sealing material in the same manner.
By placing the second green compact on the borosilicate glass substrate and firing it at 900 ° C. for 10 minutes (temperature increase rate: 10 ° C./min) in a box-type electric furnace, A second sealing material layer was formed on the borosilicate glass substrate. In a state where the first green compact is disposed on the surface of the second sealing material layer opposite to the borosilicate glass substrate and the quartz glass substrate is disposed on the first green compact, it is 700 in a box-type electric furnace. Firing was performed at a temperature of 30 ° C. for 30 minutes (temperature increase rate: 10 ° C./min). Thereby, the 1st sealing material layer which consists of a powder sintered compact was formed, and the 2nd sealing material layer and the quartz glass substrate were joined via the said 1st sealing material layer. As described above, a joined body was obtained in which the quartz glass substrate and the borosilicate glass substrate were joined by the sealing material laminate including the first sealing material layer and the second sealing material layer.

  In the obtained joined body, when the interface with the sealing material layer in each substrate was observed, no crack was confirmed. Note that no cracks were observed at the interface between the first sealing material layer and the second sealing material layer.

(3-2) No. 2
With the first green compact placed on the borosilicate glass substrate and the quartz glass substrate placed on it, 700 ° C. for 30 minutes in a box-type electric furnace (heating rate: 10 ° C./min) It baked on the conditions of this. Thereby, the joined body formed by joining the borosilicate glass substrate and the quartz glass substrate by the first sealing material layer made of the powder sintered body was obtained.

  In the obtained bonded body, when the interface with the sealing material in each substrate was observed, cracks were confirmed in the borosilicate glass substrate.

(3-3) No. 3
The second green compact is placed on the borosilicate glass substrate, and further the quartz glass substrate is placed on the second green compact, and the temperature is 900 ° C. for 10 minutes in a box-type electric furnace (heating rate: 10 ° C./min. ). Thereby, the joined body formed by joining the borosilicate glass substrate and the quartz glass substrate by the second sealing material layer made of the powder sintered body was obtained.

  In the obtained joined body, when the interface with the sealing material in each substrate was observed, cracks were confirmed in the quartz glass substrate.

  The sealing material laminate of the present invention is suitable for joining a low expansion structure member used for a high temperature processing jig, a heater, an engine, or the like to a high expansion member made of metal or the like. In addition, it is also suitable for bonding a quartz bulb and a metal filament in a halogen lamp.

DESCRIPTION OF SYMBOLS 1 1st sealing material layer 1 '1st sealing material 2 2nd sealing material layer 2' 2nd sealing material 3 Sealing material laminated body 10 1st member 11 1st laminated body 20 Second member 21 Second laminate 100 Bonded body

Claims (14)

A sealant laminate second sealing material layer having a first sealing material layer and the thermal expansion coefficient alpha ₂ having a thermal expansion coefficient alpha ₁ is formed by joining together,
−25 × 10 ⁻⁷ / K ≦ α ₁ ≦ 25 × 10 ⁻⁷ / K and satisfy the relationship of α ₁ <α ₂ . It is (alpha) _{2- (} alpha) ₁ > = 10 * 10 < ^-7 > / K, The sealing material laminated body of Claim 1 characterized by the above-mentioned.   The sealing material laminate according to claim 1 or 2, wherein the first sealing material layer and / or the second sealing material layer contains glass.   The sealing material laminate according to claim 1, wherein the first sealing material layer contains crystallized glass.   The sealing material laminate according to claim 4, wherein the first sealing material layer contains β-quartz solid solution as a main crystal. First sealing material layer, a composition, in _{mol%, SiO 2 48~75%, Al} 2 O 3 5~25%, Li 2 O 5~30%, B 2 O 3 10~23% ( provided that 10), ZnO 0-2.5% (however, not including 2.5%) glass is included, The sealing as described in any one of Claims 3-5 characterized by the above-mentioned Material laminate.   The first sealing material layer and the second sealing material layer are made of a powder sintered body, and the sealing material laminate according to any one of claims 1 to 6. A joined body comprising the first member and the second member, and the sealing material laminate according to any one of claims 1 to 5 interposed between the first member and the second member. There,
A joined body, wherein the first member and the first sealing material layer, and the second member and the second sealing material layer are joined to each other. The joined body according to claim 8, wherein a difference in thermal expansion coefficient between the first member and the second member is 20 × 10 ⁻⁷ / K or more. The difference in thermal expansion coefficient between the first member and the first sealing material layer and the difference in thermal expansion coefficient between the second member and the second sealing material layer are each 20 × 10 ⁻⁷ / K or less. The joined body according to claim 8 or 9, characterized in that.   The bonded member according to any one of claims 8 to 10, wherein the first member is quartz glass, crystallized glass, or low expansion ceramics.   The joined body according to any one of claims 8 to 11, wherein the second member is metal, glass, or high expansion ceramics. A method for producing the joined body according to any one of claims 8 to 12,
Forming a first encapsulant layer on the first member by firing with the first encapsulant disposed on the first member; and
The second sealing material layer is disposed on the first sealing material layer, and the second sealing material layer is further baked in a state where the second member is disposed on the second sealing material. Forming and bonding the first sealing material layer and the second member with the second sealing material layer;
The manufacturing method of the conjugate | zygote characterized by including. A method for producing the joined body according to any one of claims 8 to 12,
A step of forming a second sealing material layer on the second member by firing in a state where the second sealing material is disposed on the second member;
The first sealing material layer is fired in a state where the first sealing material is disposed on the second sealing material layer and the first member is disposed on the first sealing material. Forming and bonding the second sealing material layer and the first member with the first sealing material layer;
The manufacturing method of the conjugate | zygote characterized by including.