WO2016108272A1 - Matériau d'étanchéité à basse température - Google Patents

Matériau d'étanchéité à basse température Download PDF

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Publication number
WO2016108272A1
WO2016108272A1 PCT/JP2015/085935 JP2015085935W WO2016108272A1 WO 2016108272 A1 WO2016108272 A1 WO 2016108272A1 JP 2015085935 W JP2015085935 W JP 2015085935W WO 2016108272 A1 WO2016108272 A1 WO 2016108272A1
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Prior art keywords
weight
glass
sealing material
powder
lead
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PCT/JP2015/085935
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English (en)
Japanese (ja)
Inventor
浩三 前田
禎隆 真弓
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日本山村硝子株式会社
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Priority to JP2016567304A priority Critical patent/JP6650885B2/ja
Publication of WO2016108272A1 publication Critical patent/WO2016108272A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/02—Containers; Seals
    • H01L23/10—Containers; Seals characterised by the material or arrangement of seals between parts, e.g. between cap and base of the container or between leads and walls of the container
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a novel low-temperature sealing material. More specifically, the present invention relates to a sealing material that can be sealed at a relatively low temperature in an electronic device such as an IC package or a crystal resonator package.
  • the sealing materials used for sealing electronic devices such as IC packages and crystal resonator packages are, in particular, 1) capable of sealing at as low a temperature as possible, and 2) the coefficient of thermal expansion of the package material (sealing material). It must have an approximate thermal expansion coefficient and 3) have sufficient fluidity during firing.
  • sealing material that can be sealed at a relatively low temperature
  • glass of PbO—B 2 O 3 system, PbO—B 2 O 3 —Bi 2 O 3 system or the like is generally used, and the thermal expansion coefficient of the package material
  • a sealing material to which a low expansion ceramic is added has been proposed.
  • Patent Document 1 includes a low-melting glass powder and a lead titanate solid solution powder, and the lead titanate solid solution powder is PbO: 60 to 73%, TiO 2 : 7 to 23%, Fe 2 O 3 , by weight percentage.
  • PbO 60 to 73%
  • TiO 2 7 to 23%
  • Fe 2 O 3 iron 2 O 3
  • a low-melting-point low-expansion sealing material characterized by having a composition of 1% or more selected from the group of 18%, CaO, SrO, and BaO: 0 to 7% is disclosed.
  • Patent Document 2 PbO: 70.3 to 92.0%, B 2 O 3 : 1.0 to 10.0%, Bi 2 O 3 : 5.2 to 20.0%, F in weight percentage 2 : 0.01 to 8.0%, ZnO: 0 to 15.0%, V 2 O 5 : 0 to 5.0%, SiO 2 : 0 to 2.0%, Al 2 O 3 : 0 to 2 0.0%, SnO 2 : 0 to 2.0%, BaO: 0 to 4.0%, and a glass powder having a B 2 O 3 / PbO ratio of 0.11 or less.
  • a low melting point sealing composition is proposed.
  • Patent Document 3 discloses a package for housing a semiconductor element in which an insulating base and a lid are joined via a sealing material, and a semiconductor element is hermetically accommodated inside a container composed of the insulating base and the lid.
  • Sealing material is lead oxide 30.0 to 50.0% by weight, lead fluoride 10.0 to 20.0% by weight, bismuth oxide 3.0 to 13.0% by weight, boron oxide 1.0 to 5.0
  • a semiconductor element housing comprising glass containing 2% to 45.0% by weight of a lead titanate compound as a filler to a glass component containing 10% by weight and 1.0 to 5.0% by weight of zinc oxide.
  • a package is disclosed.
  • Patent Document 4 discloses a low-melting-point sealing composition comprising a mixture of glass powder containing PbF 2 and a refractory filler.
  • Patent Document 5 PbO: 70 to 80%, B 2 O 3 : 5 to 12%, ZnO: 0 to 5%, SiO 2 : 0 to 1%, Al 2 O 3 : 0 to 3% by weight% SnO 2 : 0 to 1%, Bi 2 O 3 : 3 to 12%, V 2 O 5 : 0.1 to 1%, CuO: 0.1 to 5%, F: 0.1 to 3%
  • a sealing composition characterized in that 25 to 40% by volume of a refractory filler powder is contained in a glass powder containing
  • Patent Document 6 discloses a low-melting-point sealed glass composition of PbO—B 2 O 3 —Bi 2 O 3 —SiO 2 glass powder and lead titanate powder and / or ⁇ -eucryptite powder. Yes.
  • Patent Document 7 PbO 50 to 75%, PbF 2 1 to 20%, B 2 O 3 6 to 12%, TeO 2 1 to 10%, ZnO 1 to 5%, SiO 2 0.5 are expressed in terms of mass percentage.
  • Glass powder having a composition of 2%, Al 2 O 3 0.5-2%, Bi 2 O 3 0-10%, and low expansion ceramic filler powder 10-50% by volume.
  • a low temperature sealing composition is disclosed.
  • PbO is 71.0 to 90.0% by weight
  • B 2 O 3 is 3.0 to 12.0%
  • Bi 2 O 3 is 1.0 to 20.0%
  • ZnO is 0.1% by weight.
  • a low-temperature sealing composition characterized by being a low-melting glass comprising a composition of SiO 2 0-3.0%, Al 2 O 3 0-3.0% and CuO 0-3.0% Has been.
  • the glass composition does not contain fluorine, the glass has a high softening point and cannot be sealed at a low temperature. Further, although a composition containing fluorine is also disclosed, crystallization may occur due to a large PbO / Bi 2 O 3 ratio. In the low melting point sealing composition of Patent Document 2, it is necessary to contain a poison such as V 2 O 5 in order to lower the glass softening point.
  • the sealing material of Patent Document 3 has a problem that the softening temperature is high because the amount of PbO + PbF 2 is small, and the glass is easily crystallized because the amount of B 2 O 3 is small.
  • the low melting point sealing composition of Patent Document 4 has a problem that it is easy to crystallize because the valence of PbO or the like changes due to containing Fe 2 O 3 .
  • the sealing composition of Patent Document 5 has a problem that it contains V 2 O 5 which is a poisonous substance in the glass composition.
  • the low melting point sealing glass composition of Patent Document 6 has a problem that the softening point does not decrease because the fluorine content is small.
  • the low temperature sealing composition of Patent Document 7 has a problem of containing TeO 2 which is a harmful substance.
  • the low-temperature sealing composition of Patent Document 8 also has a problem that it contains Sb 2 O 3 which is a deleterious substance.
  • the main object of the present invention is to provide a material that can exhibit more excellent characteristics as a sealing material without relying on V 2 O 5 , TeO 2 , Sb 2 O 3 , Fe 2 O 3, or the like. is there.
  • Another object of the present invention is to provide a sealing material that can exhibit good fluidity because crystals are unlikely to precipitate during firing even in the presence of a solvent.
  • the present inventor has found that the above object can be achieved by adopting a glass composition having a specific composition, and has completed the present invention.
  • the present invention relates to the following low-temperature sealing material.
  • a sealing material comprising lead glass powder and lead titanate filler powder, (1)
  • the lead glass is 1) PbO: 69.0-80.0% by weight, 2) Bi 2 O 3 : 3.1 to 12.5% by weight, 3) B 2 O 3 : 3.5 to 11.5% by weight, 4) ZnO: 1.7-8.2% by weight, 5) SiO 2 : 0 to 3.5% by weight, 6) CuO: 0 to 4.0 wt% and 7)
  • F 1.3 to 5.0 wt% As a glass component, (2)
  • the weight ratio of [PbO / Bi 2 O 3 ] in the lead glass is 5.6 to 25.5.
  • a low-temperature sealing material characterized by that. 2.
  • the lead glass powder is 1) PbO: 71.0 to 80.0 wt%, 2) Bi 2 O 3 : 3.1 to 9.5 wt%, 3) B 2 O 3 : 3.5 to 11.5 wt%, 4) ZnO: 1.7 ⁇ 8.2 wt%, 5) SiO 2: 0 ⁇ 3.5 wt%, 6) CuO: 0 ⁇ 4.0 wt% and 7) F: 2 0.0 to 5.0% by weight as a glass component, (2) The weight ratio of [PbO / Bi 2 O 3 ] is 7.7 to 18.5.
  • Item 2 The low-temperature sealing material according to Item 1. 3.
  • the lead glass powder is 1) PbO: 71.0-78.0 wt%, 2) Bi 2 O 3 : 5.0-8.5 wt%, 3) B 2 O 3 : 5.5- 10.0% by weight, 4) ZnO: 1.7 to 6.5% by weight, 5) SiO 2 : 0.5 to 3.0% by weight, 6) CuO: 1.0 to 2.0% by weight and 7 ) F: 2.4 to 4.1% by weight as a glass component, (2) The weight ratio of [PbO / Bi 2 O 3 ] is 8.5 to 13.0.
  • Item 5 The item according to any one of Items 1 to 4, comprising 90 to 60 parts by weight of lead glass powder and 10 to 40 parts by weight of lead titanate filler powder in a total of 100 parts by weight of the lead glass powder and lead titanate filler powder.
  • Item 7. The low-temperature sealing material according to any one of Items 1 to 6, further comprising at least one of a solvent and an organic binder and having a paste form. 8).
  • Item 8. The low-temperature sealing material according to Item 7, wherein crystals are not precipitated when fired at 370 ° C in the air.
  • a package for housing a semiconductor element comprising the low-temperature sealing material according to any one of items 1 to 8.
  • a composition composed of a specific glass component is employed, so that more excellent characteristics can be exhibited as a sealing material. More specifically, the following effects can be obtained.
  • Crystallization of glass can be effectively suppressed. As a result, the fluidity of the glass at the time of softening can be maintained better, so that various problems caused by crystallization of the glass (sealing failure, insufficient sealing, etc.) can be avoided more reliably.
  • the reaction between glass and filler that can occur during firing can be effectively suppressed. Thereby, it is possible to suppress or prevent glass alteration (deterioration) such as glass composition variation and glass crystallization.
  • the glass is hardly crystallized even when subjected to repeated firing in the manufacturing process of a crystal resonator or the like, and a sufficient sealing effect can be obtained.
  • the sealing material is used in the form of a paste, even in the presence of a solvent, crystals are unlikely to precipitate during firing, and as a result, good fluidity can be secured, resulting in a highly reliable sealing. Can be realized.
  • the degree of freedom of the use range of the filler can be ensured, so that the thermal expansion coefficient can be controlled relatively freely. More specifically, the thermal expansion coefficient in the temperature range of 50 to 150 ° C.
  • the sealing material of the present invention has a relatively low operating temperature, and can be sealed at a relatively low temperature of 380 ° C. or lower, which is a general sealing temperature of a crystal resonator, for example.
  • the sealing material of the present invention can realize sealing excellent in mechanical strength, durability, and the like, for example, for sealing electronic devices such as IC packages and crystal resonator packages. It can be suitably used as a sealing material.
  • the low-temperature sealing material of the present invention is a sealing material containing lead glass powder and lead titanate filler powder, (1)
  • the lead glass is 1) PbO: 69.0-80.0% by weight, 2) Bi 2 O 3 : 3.1 to 12.5% by weight, 3) B 2 O 3 : 3.5 to 11.5% by weight, 4) ZnO: 1.7-8.2% by weight, 5) SiO 2 : 0 to 3.5% by weight, 6) CuO: 0 to 4.0 wt% and 7) F: 1.3 to 5.0 wt% As a glass component, (2) The weight ratio of [PbO / Bi 2 O 3 ] in the lead glass is 5.6 to 25.5. It is characterized by that.
  • the glass component in the material of the present invention has a predetermined content in terms of oxide of each component such as Pb, Bi, B, Zn, Si, Cu, and F. It is what you have. Hereinafter, each component and its content will be described.
  • PbO PbO is an oxide that forms glass, and is preferably contained in the range of 69.0 to 80.0% by weight. If the PbO content is less than 69.0% by weight, the glass may not be obtained, and even if it is obtained, the glass has a high softening point and may not be sealed at a desired temperature. When the PbO content is more than 80.0% by weight, crystallization occurs at the time of sealing, and the fluidity at the time of softening may be deteriorated. In the present invention, PbO is more preferably contained in an amount of 71.0 to 80.0% by weight, particularly 71.0 to 78.0% by weight, particularly considering the moldability of the glass and the sealing temperature. Further preferred.
  • Bi 2 O 3 Bi 2 O 3 is a component that stabilizes the glass state, and is preferably contained in the range of 3.1 to 12.5% by weight. When the Bi 2 O 3 content is less than 3.1% by weight, crystals may be precipitated. If the Bi 2 O 3 content exceeds 12.5% by weight, the glass may not be obtained, and even if the glass is obtained, the fluidity of the glass may be deteriorated. In the present invention, Bi 2 O 3 is more preferably 3.1 to 9.5% by weight, especially 5.0 to 8.5% by weight, especially considering the moldability and fluidity of the glass. More preferably.
  • B 2 O 3 B 2 O 3 is a component that forms glass, and is contained in the range of 3.5 to 11.5% by weight. If the B 2 O 3 content is less than 3.5% by weight, glass may not be obtained. When the B 2 O 3 content exceeds 11.5% by weight, the glass may not be obtained, and even if the glass is obtained, the glass softening temperature is high, and thus the fluidity of the glass may be deteriorated. is there.
  • B 2 O 3 is more preferably contained in an amount of 3.5 to 11.5% by weight, particularly considering the moldability and fluidity of the glass, and 5.5 to 10.0% by weight. More preferably.
  • ZnO ZnO is a component that improves the moldability of the glass and is preferably contained in the range of 1.7 to 8.2% by weight. If the ZnO content is less than 1.7% by weight, the glass may crystallize and not flow. If the ZnO content is more than 8.2% by weight, glass may not be obtained. In the present invention, the ZnO content is preferably 1.7 to 8.2% by weight, especially considering the moldability and flowability of the glass, and 1.7 to 6.5% by weight. It is more preferable.
  • SiO 2 SiO 2 is a component that forms glass, and is preferably contained at 0 to 3.5% by weight. When the SiO 2 content is more than 3.5% by weight, the softening temperature of the glass becomes high, so that the fluidity of the glass may be deteriorated.
  • SiO 2 is more preferably contained in an amount of 0.5 to 3.0% by weight, particularly 1.5 to 3.0% by weight, especially considering the moldability and fluidity of the glass. Is most preferred.
  • SiO 2 is more preferably contained in an amount of 0.5 to 3.0% by weight, particularly 1.5 to 3.0% by weight, especially considering the moldability and fluidity of the glass. Is most preferred.
  • the material of the present invention when used in a form containing at least a solvent, it is possible to more effectively suppress crystal precipitation that may occur in the presence of the solvent. Or can be prevented. That is, by effectively suppressing or preventing crystallization when firing the material of the present invention, good fluidity can be ensured, and as a result, highly reliable sealing can be realized more reliably
  • CuO CuO is a component for preventing crystallization of glass, and is preferably contained at 0 to 4% by weight. When there is more CuO content than 4 weight%, there exists a possibility that the fluidity
  • the fluorine component is a component that lowers the softening temperature of the glass and improves the fluidity of the glass, and is preferably contained in the range of 1.3 to 5.0% by weight.
  • the fluorine content is less than 1.3% by weight, the softening temperature of the glass becomes high and the fluidity may be deteriorated.
  • the fluorine content exceeds 5.0% by weight, it becomes easy to react with the filler, and glass may not be obtained.
  • the fluorine content is more preferably 2.0 to 5.0% by weight, particularly considering the fluidity of the glass, the reactivity with the filler, etc., and 2.4 to 4.1% by weight. More preferably.
  • TiO 2 and ZrO 2 In addition to the above components, for example, for the purpose of improving the stability during glass production, suppressing crystallization, adjusting the thermal expansion coefficient, etc., a total of at least one of TiO 2 and ZrO 2 is 0.01 to 1% by weight. It can be included.
  • Other components include, for example, alkaline earth oxides such as CaO, SrO, and BaO for the purpose of improving stability during glass production, suppressing crystallization, adjusting the thermal expansion coefficient, and the like. Can be added.
  • material at least 1 sort (s) of CoO and an alkali metal oxide can be contained in the range which does not prevent the effect of this invention as needed. By blending these components, the fluidity at the time of firing (in use) of the material of the present invention can be enhanced without relying on an increase in the amount of PbO.
  • These contents are not limited, but in general, the total content may be in the range of 0.3 to 2.0% by weight.
  • V, Te, Sb and Fe that can be highly harmful components or components to be altered are preferably 0.1% by weight or less in total.
  • the total amount is more preferably 0% by weight. That is, unlike the conventional sealing material, the material of the present invention can exhibit desired characteristics without depending on these components.
  • the weight ratio of [PbO / Bi 2 O 3] in the lead glass according to the weight ratio present invention [PbO / Bi 2 O 3] is usually set to 5.6 to 25.5, and from 7.7 to 18.5 More preferably, it is particularly preferably 8.5 to 13.0.
  • the said weight ratio is less than 5.6, there exists a possibility that the softening point of glass may become high too much.
  • the said weight ratio exceeds 25.5, there exists a possibility that the reactivity with a filler may become high.
  • the lead glass powder of the present invention can be produced by a method similar to a known method for producing a glass composition.
  • a compound serving as a supply source of each component of the glass in the present invention may be used as a starting material.
  • various starting materials that are usually used in the production of glass such as various oxides, hydroxides, carbonates, and nitrates, can be employed.
  • the raw materials are prepared and mixed at a predetermined ratio, and the mixture is put into a platinum crucible, melted at a temperature of 750 to 950 ° C. for a predetermined time (about 1 to 2 hours), and then rapidly cooled by a twin roll method to obtain a glass.
  • the flakes are obtained and poured out onto a previously heated carbon plate to produce a block. After that, the block is put into an electric furnace set at a temperature about 50 ° C. higher than the expected glass transition point, and then gradually cooled.
  • glass flakes are put in a pot mill and pulverized to obtain glass powder. This glass powder can be subjected to a treatment such as classification or sieving as required.
  • the properties of the lead glass powder of the present invention are usually used as a powder.
  • the average particle diameter (D 50 ) is not limited, but can be appropriately adjusted depending on the use form, application, etc., usually within a range of 30 ⁇ m or less.
  • the material of the present invention is prepared as a paste, it may be appropriately adjusted to the particle size described below.
  • the lead glass powder of the present invention has a characteristic that it does not have a crystallization temperature. Thereby, the fluidity is good at the time of sealing, and the effect that sealing shortage does not occur is obtained.
  • the glass transition point of the lead glass powder is not limited, but it is usually in the range of about 200 to 280 ° C., more preferably 220 to 260 ° C. Thereby, sealing can be performed at a relatively low temperature, and the thermal expansion coefficient approximate to that of the sealing material can be controlled by mixing the filler powder.
  • Lead titanate-based filler powder used in the present invention is at least a solid solution in which lead titanate (PbTiO 3 ) and a part thereof are substituted with other atoms (for example, Ca, Fe, Nb, etc.). One can be used. A well-known thing can also be used for these.
  • composition in the lead titanate or solid solution PbO: 60.0 to 70.0% by weight in terms of oxide, TiO 2 : 15.0 to 25.0% by weight, CaO: 0 to 5.0% by weight, It is desirable to employ a composition containing Fe 2 O 3 : 0 to 5% by weight and Nb 2 O 3 : 0 to 10.0% by weight. If it is the said composition range, since a thermal expansion coefficient can be made small and it is effective even if there is little content of a lead titanate filler powder, favorable fluidity
  • the average particle diameter (D 50 ) of the lead titanate filler powder is not particularly limited, but is usually preferably 7 to 30 ⁇ m, and more preferably 7 to 15 ⁇ m.
  • the average particle size is less than 7 ⁇ m, the lead titanate filler powder easily reacts with glass.
  • the average particle size exceeds 30 ⁇ m, the workability at the time of forming a paste may be deteriorated, or the precipitate may be easily separated.
  • the content of the lead titanate-based filler powder is particularly 100 parts by weight of the lead glass powder and the lead titanate-based filler powder from the viewpoint of reducing the thermal expansion coefficient of the sealing material by the lead glass powder. It is preferable to use 90 to 60 parts by weight of lead glass powder and 10 to 40 parts by weight of lead titanate filler powder. When the content of the lead titanate filler powder is less than 10 parts by weight, the effect may not be sufficiently obtained. On the other hand, when the content of the lead titanate filler powder exceeds 40 parts by weight, the amount of glass decreases, so that the fluidity is deteriorated and adhesion failure may occur.
  • the content of the lead titanate filler powder is more preferably 25 to 35 parts by weight (75 to 65 parts by weight of lead glass powder). Note that the ratio of the total of the lead glass powder and the lead titanate filler in the present invention is not limited. It can be.
  • ceramic filler can be added in addition to lead titanate filler powder for the purpose of fine adjustment of thermal expansion coefficient, improvement of strength of sealing material, and the like.
  • the ceramic filler (powder) for example, at least one of ⁇ -eucryptite, cordierite, zircon and the like can be used.
  • the addition amount of the ceramic filler can be added within a range of 50 parts by weight or less with respect to 100 parts by weight, with the total amount of the lead titanate filler powder and the lead glass composition being 100 parts by weight.
  • the material of the present invention can be obtained by mixing the lead glass powder and the lead titanate filler powder.
  • the mixing method may be either dry or wet, but it is particularly preferable to mix dry. Mixing can be carried out by using a known or commercially available mixing apparatus.
  • the material of the present invention can be used in the same usage method and form as known sealing materials.
  • the material of the present invention can be used in the form of a powder, but can be suitably used, for example, in the form of a paste.
  • the sealing material When used in a liquid form, the sealing material may be prepared by mixing at least one of a solvent and an organic binder.
  • a solvent and an organic binder For example, in the liquid (paste-like) composition that can prepare a liquid (paste-like) composition by mixing the sealing material (powder) of the present invention, a solvent and an organic binder, It is characterized in that crystals do not precipitate when it is fired at 370 ° C. That is, in the conventional paste containing a solvent, the cause is not clear, but crystals tend to precipitate during firing, so that the fluidity is also lowered.
  • the liquid composition according to the present invention is less likely to be crystallized even if it contains a solvent, and can secure a desired fluidity. As a result, highly reliable sealing can be realized. .
  • the average particle diameter (D 50 ) of the sealing material powder is not particularly limited, but is usually 2 to 30 ⁇ m, and preferably 5 to 15 ⁇ m.
  • the average particle size is less than 2 ⁇ m, a large amount of organic binder is required when preparing the paste, the volume shrinkage before and after firing is increased, and it takes a long time to burn out the binder. May decrease.
  • the average particle diameter exceeds 30 ⁇ m, there is a risk of hindering sealing.
  • the maximum particle size of the powder is not limited, but is usually 200 ⁇ m or less, preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less.
  • the organic binder is not particularly limited. Depending on the specific use (sealing material) of the sealing material, it can be appropriately selected from known or commercially available binders.
  • cellulose resins such as ethyl cellulose, copolymers (acrylic resin) of methyl methacrylate, which is a main component, and various acrylates, methacrylate, acrylamide, styrene, acrylonitrile, etc., and acrylic acid, methacrylic acid, and the like. The thing etc. which added the saturated group are mentioned.
  • the organic solvent may be appropriately selected depending on the kind of the binder, for example, alcohols such as ethanol, methanol, IPA, and terpineol ( ⁇ -terpineol or ⁇ -terpineol containing ⁇ -terpineol as a main component).
  • alcohols such as ethanol, methanol, IPA, and terpineol ( ⁇ -terpineol or ⁇ -terpineol containing ⁇ -terpineol as a main component).
  • butyl carbitol butyl carbitol acetate, ethylene glycol alkyl ether, diethylene glycol alkyl ether, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether acetate, diethylene glycol dialkyl ether acetate, triethylene glycol alkyl ether acetate, Triethylene glycol alkyl ether, propylene glycol alkyl ether, propylene glycol Phenyl ether, dipropylene glycol alkyl ether, tripropylene glycol alkyl ether, propylene glycol alkyl ether acetates, dipropylene glycol alkyl ether acetate, tripropylene glycol alkyl ether acetate, .gamma.-butyrolactone and the like.
  • solvents may be used alone or in combination of two or more.
  • liquid composition especially a paste-like composition
  • known additives such as a plasticizer, a thickener, a sensitizer, a surfactant, and a dispersant may be used as necessary. Can be appropriately blended.
  • Pb component supply source PbO
  • Bi component supply source Bi 2 O 3
  • B component supply source H 3 BO 3
  • Zn component supply source ZnO
  • Si component supply source SiO 2
  • Cu Component source CuO
  • fluorine component source PbF 2
  • Ti component source TiO 2
  • Zr component source ZrO 2
  • Test example 1 The physical properties (performance) of the lead glass powder and lead titanate filler powder obtained in each of the Examples and Comparative Examples and the physical properties (performance) of the sealing material were measured according to the following measuring methods.
  • Crystallization temperature About 60 to 80 mg of the lead glass powder is filled in a platinum cell, and the temperature is increased from room temperature to 20 ° C./minute using a DTA measuring device (Thermo Plus Thermo Plus TG8120). Whether or not (° C.) was detected was examined.
  • Lead glass flow diameter (flow diameter 1) The lead glass powder was put into a mold having an inner diameter of 20 mm, pressed and molded, and fired at 360 ° C. The diameter of the obtained sintered body was measured to obtain a flow diameter (mm). The larger the flow diameter, the better the fluidity.
  • flow diameter 2 The obtained sealing material (mixed powder of lead glass powder and lead titanate filler powder) was put into a mold having an inner diameter of 20 mm, pressed and molded, and fired at 360 ° C. The diameter of the obtained sintered body was measured to obtain a flow diameter (mm). The larger the flow diameter, the better the fluidity.
  • the difference in glass transition point from lead glass alone is a low value within a range of 10 ° C. or less (particularly 5 ° C. or less). I know that there is. This is considered due to the fact that the reaction between the lead glass and the lead titanate filler powder does not occur or is slight.
  • the difference of the glass transition point with glass alone is as high as 24 degreeC. This is presumably because the glass transition point was raised because the glass and filler reacted and the filler was taken into the glass.
  • the crystallization temperature was detected because the [PbO / Bi 2 O 3 ] ratio was not appropriate.
  • Examples 43-61 A powdery sealing material (glass powder) was prepared by uniformly mixing the components so as to have the blending ratios shown in Tables 9 to 11 in the same manner as in Example 1 except that no filler was used. .
  • Test example 2 The physical properties of the sealing materials obtained in Examples 43 to 61 were measured in the same manner as in Test Example 1. The reactivity of the sealing material with the solvent was also measured. The measurement method is as follows. These measurement results are shown in Tables 9 to 11.
  • the sealing material of the present invention can be more reliably sealed even at a relatively low temperature of 380 ° C. or lower.
  • the filler and glass do not react even in repeated firing, crystals do not precipitate, and the fluidity during glass softening is excellent, so the sealing effect is excellent in mechanical strength and durability. Can be obtained. For this reason, it can be used as a sealing material suitable for sealing electronic parts such as an IC package and a crystal resonator package.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

Le problème abordé par la présente invention est de pourvoir à un matériau d'étanchéité qui génère peu de cristaux en cours d'utilisation, a une excellente fluidité, et permet l'étanchéité en particulier à 380°C ou moins, sans se baser sur V2O5, TeO2, ou Sb2O3, etc., et sans provoquer de réaction entre une poudre de verre et une poudre de charge pendant la cuisson. La solution selon l'invention porte sur un matériau d'étanchéité à basse température qui est caractérisé en ce qu'il contient une poudre de verre au plomb et une poudre de charge à base de titanate de plomb dans lequel : (1) le verre au plomb contient, à titre de composants de verre, 1) du PbO à raison de 69,0 à 80,0 % en poids, 2) du Bi2O3 à raison de 3,1 à 12,5 % en poids, 3) du B2O3 à raison de 3,5 à 11,5 % en poids, 4) du ZnO à raison de 1,7 à 8,2 % en poids, 5) du SiO2 à raison de 0 à 3,5 % en poids, 6) du CuO à raison de 0 à 4,0 % en poids, et 7) du F à raison de 1,3 à 5,0 % en poids ; et (2) le rapport en poids [PbO/Bi2O3] dans le verre au plomb est de 5,6 à 25,5.
PCT/JP2015/085935 2014-12-28 2015-12-24 Matériau d'étanchéité à basse température WO2016108272A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2017056416A1 (fr) * 2015-09-29 2017-04-06 パナソニックＩｐマネジメント株式会社 Procédé de fabrication d'unité de panneau de verre et procédé de fabrication de fenêtre en verre
CN107673623A (zh) * 2017-08-28 2018-02-09 广州市儒兴科技开发有限公司 一种双面perc铝浆用玻璃粉及其制备方法
CN108314329A (zh) * 2018-02-28 2018-07-24 西安欣贝电子科技有限公司 含铌低温耐酸无铅无镉玻璃粉及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20230099682A (ko) 2021-12-27 2023-07-04 에이지씨 가부시키가이샤 유리, 도전 페이스트 및 태양 전지

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JPH08253345A (ja) * 1995-03-14 1996-10-01 Toshiba Glass Co Ltd 低温封着用組成物
JPH11106235A (ja) * 1997-10-03 1999-04-20 Nippon Sheet Glass Co Ltd 封着用組成物
JPH11116275A (ja) * 1997-10-13 1999-04-27 Ohara Inc 低温封着用組成物
JP2001089188A (ja) * 2000-08-03 2001-04-03 Nippon Electric Glass Co Ltd 低融点封着用組成物
JP2007009037A (ja) * 2005-06-30 2007-01-18 Nippon Electric Glass Co Ltd 封着方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08253345A (ja) * 1995-03-14 1996-10-01 Toshiba Glass Co Ltd 低温封着用組成物
JPH11106235A (ja) * 1997-10-03 1999-04-20 Nippon Sheet Glass Co Ltd 封着用組成物
JPH11116275A (ja) * 1997-10-13 1999-04-27 Ohara Inc 低温封着用組成物
JP2001089188A (ja) * 2000-08-03 2001-04-03 Nippon Electric Glass Co Ltd 低融点封着用組成物
JP2007009037A (ja) * 2005-06-30 2007-01-18 Nippon Electric Glass Co Ltd 封着方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017056416A1 (fr) * 2015-09-29 2017-04-06 パナソニックＩｐマネジメント株式会社 Procédé de fabrication d'unité de panneau de verre et procédé de fabrication de fenêtre en verre
CN107673623A (zh) * 2017-08-28 2018-02-09 广州市儒兴科技开发有限公司 一种双面perc铝浆用玻璃粉及其制备方法
CN107673623B (zh) * 2017-08-28 2020-09-15 广州市儒兴科技开发有限公司 一种双面perc铝浆用玻璃粉及其制备方法
CN108314329A (zh) * 2018-02-28 2018-07-24 西安欣贝电子科技有限公司 含铌低温耐酸无铅无镉玻璃粉及其制备方法

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