WO2021060525A1 - 電磁波シールド用組成物、電磁波シールド用シート、電磁波シールド用焼結体及び電子部品装置 - Google Patents

電磁波シールド用組成物、電磁波シールド用シート、電磁波シールド用焼結体及び電子部品装置 Download PDF

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WO2021060525A1
WO2021060525A1 PCT/JP2020/036419 JP2020036419W WO2021060525A1 WO 2021060525 A1 WO2021060525 A1 WO 2021060525A1 JP 2020036419 W JP2020036419 W JP 2020036419W WO 2021060525 A1 WO2021060525 A1 WO 2021060525A1
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Prior art keywords
electromagnetic wave
wave shielding
metal particles
composition
mass
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English (en)
French (fr)
Japanese (ja)
Inventor
秀明 山岸
宏 増田
圭太 曽根
振一郎 須方
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Resonac Corp
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Showa Denko Materials Co Ltd
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Priority to JP2021548458A priority Critical patent/JPWO2021060525A1/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C12/00—Alloys based on antimony or bismuth

Definitions

  • the present disclosure relates to an electromagnetic wave shielding composition, an electromagnetic wave shielding sheet, an electromagnetic wave shielding sintered body, and an electronic component device.
  • an electromagnetic wave shielding material that shields unnecessary electromagnetic waves from the outside is used in electronic devices.
  • Electro waves shielding materials are made of metal and reflect electromagnetic waves to shield electronic devices from electromagnetic waves.
  • Examples of conventional electromagnetic wave shielding materials include metal plating, metal housings, metal paints, and the like.
  • metal plating has a long processing time and tends to be expensive.
  • the electronic device is miniaturized, it is necessary to miniaturize the metal housing, which tends to make it difficult to process the metal housing.
  • the metal paint contains metal particles, resin and solvent, and conduction is obtained by contact of the metal particles.
  • the present disclosure has been made in view of the above-mentioned conventional circumstances, and is an electromagnetic wave shielding composition capable of forming an electromagnetic wave shielding sintered body having an excellent electromagnetic wave shielding effect, and an electromagnetic wave using this electromagnetic wave shielding composition. It is an object of the present invention to provide a shield sheet, an electromagnetic wave shield sintered body, and an electronic component device.
  • a metal particle A, a metal particle B having a melting point lower than that of the metal particle A, and a resin are contained.
  • An electromagnetic wave shielding composition capable of transitional liquid phase sintering between the metal particles A and the metal particles B.
  • the ratio of the Cu content to the Sn content (Cu content / Sn content) on a mass basis in the total of the metal particles A and the metal particles B is 0.6 to 21.
  • the ratio of the Cu content to the Sn content (Cu content / Sn content) on a mass basis in the total of the metal particles A and the metal particles B is 1.6 to 64.
  • the metal particles B further contain Bi, and the metal particles B further contain Bi.
  • the ratio of the Cu content to the Bi content (Cu content / Bi content) based on the mass of the metal particles A and the metal particles B is 1.1 to 44 ⁇ 3.
  • ⁇ 7> The composition for electromagnetic wave shielding according to any one of ⁇ 1> to ⁇ 6>, wherein the total ratio of the metal particles A and the metal particles B to the total solid content is 96% by mass or less.
  • the resin contains a thermosetting resin.
  • ⁇ 9> The composition for electromagnetic wave shielding according to ⁇ 8>, which further contains a curing agent.
  • ⁇ 12> The composition for electromagnetic wave shielding according to ⁇ 11>, wherein the flux component contains at least one of rosin and an activator.
  • ⁇ 13> The composition for electromagnetic wave shielding according to ⁇ 12>, wherein the rosin contains 2,2-bis (hydroxymethyl) propionic acid and the activator contains triethanolamine.
  • ⁇ 14> When the temperature at which the flux component changes in phase is ⁇ (° C.) and the melting point of the metal particles B is ⁇ (° C.), ⁇ -20 ⁇ ⁇ ⁇ + 20 is satisfied.
  • composition for electromagnetic wave shielding according to ⁇ 14> wherein the temperature at which the flux component changes in phase is 130 ° C. to 160 ° C.
  • Composition. ⁇ 17> The composition for electromagnetic wave shielding according to any one of ⁇ 1> to ⁇ 16>, which further contains a solvent.
  • ⁇ 19> The electromagnetic wave shielding composition according to any one of ⁇ 1> to ⁇ 17> or the electromagnetic wave shielding sintered body which is the sintered body of the electromagnetic wave shielding sheet according to ⁇ 18>.
  • ⁇ 20> The sintered body for electromagnetic wave shielding according to ⁇ 19>, wherein the volume resistivity is 3 ⁇ 10 -4 ⁇ ⁇ cm or less.
  • ⁇ 21> An electronic component device having a region covered by the sintered body for electromagnetic wave shielding according to ⁇ 19> or ⁇ 20>.
  • an electromagnetic wave shielding composition capable of forming an electromagnetic wave shielding sintered body having an excellent electromagnetic wave shielding effect, an electromagnetic wave shielding sheet using this electromagnetic wave shielding composition, an electromagnetic wave shielding sintered body, and the like.
  • Electronic component devices can be provided.
  • the term "process” includes not only a process independent of other processes but also the process if the purpose of the process is achieved even if the process cannot be clearly distinguished from the other process. ..
  • the numerical range indicated by using "-" in the present disclosure includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. ..
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
  • each component may contain a plurality of applicable substances.
  • the content of each component means the total content of the plurality of substances present in the composition unless otherwise specified.
  • the particles corresponding to each component may include a plurality of types of particles.
  • the particle size of each component means a value for a mixture of the plurality of particles present in the composition unless otherwise specified.
  • the term "layer” or “membrane” is used only in a part of the region in addition to the case where the layer or the membrane is formed in the entire region when the region in which the layer or the membrane is present is observed. The case where it is formed is also included.
  • the average thickness of a layer or film is a value given as an arithmetic mean value obtained by measuring the thickness of five points of the target layer or film.
  • the thickness of the layer or film can be measured using a micrometer or the like.
  • the measurement when measuring the thickness of a layer or a film can be directly measured, it is measured using a micrometer.
  • the measurement may be performed by observing the cross section of the measurement target using an electron microscope.
  • the "solid content" refers to the balance obtained by removing the solvent component from the composition for electromagnetic wave shielding.
  • the content of the solvent in the electromagnetic wave shielding composition can be determined by applying an analysis method such as gas chromatography-mass spectrometry (GC / MS) to the volatile content of the electromagnetic wave shielding composition. If the composition of the electromagnetic wave shielding composition is known, the solvent content may be obtained from the composition of the electromagnetic wave shielding composition. By multiplying the mass of the electromagnetic wave shielding composition by the solvent content, the ratio of the remaining portion of the electromagnetic wave shielding composition can be obtained.
  • an analysis method such as gas chromatography-mass spectrometry (GC / MS)
  • the composition for electromagnetic wave shielding of the present disclosure contains metal particles A, metal particles B having a melting point lower than that of the metal particles A, and a resin, and is used between the metal particles A and the metal particles B. Transitional liquid phase sintering is possible.
  • the composition for electromagnetic wave shielding may contain other components other than the above components.
  • a sintered body of metal particles A and metal particles B is formed by heating by utilizing the transitional liquid phase sintering generated between the metal particles A and the metal particles B. Can be formed.
  • the sintered body to be formed tends to have low interfacial resistance and excellent conductivity as compared with the case where metal particles come into contact with each other.
  • the electromagnetic wave shielding sintered body formed by using the electromagnetic wave shielding composition of the present disclosure has a low volume resistivity and is excellent in the electromagnetic wave shielding effect.
  • the electromagnetic wave shielding composition of the present disclosure contains metal particles A and metal particles B having a melting point lower than that of the metal particles A. Transitional liquid phase sintering is possible between the metal particles A and the metal particles B.
  • the "transitional liquid phase sintering" in the present disclosure is also referred to as Transient Alloy Phase Sintering (TLPS), and is a liquid phase by heating at the particle interface of a metal having a relatively low melting point (low melting point metal) among metals having different melting points. It refers to a phenomenon in which the formation (alloying) of a metal compound by both metals proceeds due to the transition to the above and the reaction diffusion of a metal having a relatively high melting point (high melting point metal) into the liquid phase.
  • TLPS Transient Alloy Phase Sintering
  • the metal particles A and the metal particles B can be sintered, and all the metal components can be sintered. No need.
  • the metal particles B may contain a metal component such as Bi that does not contribute to the reaction during sintering.
  • Examples of the metal component capable of transitional liquid phase sintering include a combination of metals having different melting points (combination of low melting point metal and high melting point metal) capable of transitional liquid phase sintering.
  • the combination of metals capable of transitional liquid phase sintering is not particularly limited.
  • a combination in which a low melting point metal and a high melting point metal are Sn and Cu
  • a combination in which Zn and Cu are used, and In and Au are used.
  • Examples thereof include a combination of Sn and Co, and a combination of Sn and Ni.
  • the combination of metals capable of transitional liquid phase sintering may be a combination of two kinds of metals or a combination of three or more kinds of metals.
  • the melting point of the metal particles A is preferably higher than 300 ° C, more preferably 500 ° C or higher, and even more preferably 800 ° C or higher.
  • the composition for electromagnetic wave shielding of the present disclosure may contain two or more types of metal particles A, and may contain, for example, two or more types of metal particles A having melting points higher than 300 ° C.
  • the melting point of the metal particles B is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, and even more preferably 200 ° C. or lower. , 150 ° C. or lower is particularly preferable.
  • the composition for electromagnetic wave shielding of the present disclosure may contain two or more types of metal particles B, and may contain, for example, two or more types of metal particles B having a melting point of 300 ° C. or lower.
  • the metal particles A and the metal particles B are not particularly limited.
  • the metal particles A and the metal particles B may each be in the state of a single metal, or one or both of the metal particles A and the metal particles B may be in the state of an alloy.
  • the metal particles A are in the state of a single metal and the metal particles B are in the state of an alloy.
  • the metal particles A and the metal particles B may each consist of only one kind of metal or two or more kinds of metals.
  • the metal particle A or the metal particle B is composed of two or more kinds of metals, even if the metal particles are a combination (mixture) of metal particles containing each of the two or more kinds of metals, the two or more kinds of metals are the same metal. It may be contained in the particles or may be a combination thereof.
  • the composition of the metal particles containing two or more kinds of metals in the same metal particles is not particularly limited.
  • it may be a metal particle composed of an alloy of two or more kinds of metals, or a metal particle composed of a simple substance of two or more kinds of metals.
  • Metal particles composed of simple substances of two or more kinds of metals can be obtained, for example, by forming a layer containing the other metal on the surface of the metal particles containing one metal by plating, vapor deposition, or the like. Further, the same metal particles are formed by applying a dry type particle containing the other metal to the surface of the metal particle containing one metal by using a force mainly composed of an impact force in a high-speed airflow to combine the two. It is also possible to obtain metal particles containing two or more kinds of metals therein.
  • the metal particles A are preferably metal particles containing at least one selected from the group consisting of Cu, Au, Ag, Co, Ni and Fe, and are Cu, Au, Ag, Co, Ni or Fe particles. Is more preferable.
  • the metal particles B are preferably metal particles containing Sn, Zn or In, and more preferably alloy particles containing Sn, Zn or In and the metal component X described later.
  • Examples of the combination of the metal particles A and the metal particles B having a lower melting point than the metal particles A include (metal particles containing Cu, metal particles containing Sn), and (including Cu). Metal particles, metal particles containing Zn), (metal particles containing Au, metal particles containing In), (metal particles containing Co, metal particles containing Sn) and (metal particles containing Ni, metal particles containing Sn). ).
  • the combination of the metal particles A and the metal particles B is a combination of the metal particles containing Cu and the metal particles containing Sn, at least one of the metal particles containing Cu and the metal particles containing Sn is at least one of Ag and Ni.
  • the metal particles B contain at least one metal component X selected from the group consisting of Bi, In, Zn, Cd, Pb, Ag, and Cu from the viewpoint of lowering the temperature at which transitional liquid phase sintering is possible. It is preferable to contain Sn, and it is more preferable to contain the metal component X.
  • the metal component X preferably contains at least one selected from the group consisting of Bi, In, Cd, Pb, Ag, and Cu, and the metal particle B contains In.
  • the metal component X preferably contains at least one selected from the group consisting of Bi, Zn, Cd, Pb, Ag, and Cu.
  • the metal component X more preferably contains at least one selected from the group consisting of Bi, In, Zn, Cd, Ag, and Cu, from the viewpoint of further lowering the temperature at which transitional liquid phase sintering is possible. , Bi, In, Zn, and Cd.
  • the metal particles B are composed of the metal component X in the entire metal particles B from the viewpoint of lowering the temperature at which transitional liquid phase sintering is possible and from the viewpoint of preferably lowering the mass resistance of the sintered body for electromagnetic shielding.
  • the ratio is preferably 3% by mass to 80% by mass, more preferably 5% by mass to 15% by mass, 20% by mass to 30% by mass, or 50% by mass to 60% by mass.
  • Examples of the case where the metal particles B are in the state of an alloy containing Sn include SnBi alloy, SnIn alloy, SnZn alloy, SnPb alloy, SnCd alloy and the like. Of these, SnBi alloys are preferable from the viewpoint of lowering the temperature at which transitional liquid phase sintering is possible.
  • the metal particles A preferably contain Cu (melting point: 1085 ° C.), the metal particles B preferably contain Sn (melting point: 232 ° C.), and the metal particles A contain Cu (melting point: 1085 ° C.). It is preferable that the metal particles B are an alloy containing Sn (melting point: less than 232 ° C, for example, 138 ° C). Cu and Sn form a copper-tin metal compound (Cu 6 Sn 5 ) by sintering. Since this formation reaction proceeds at around 150 ° C., sintering can be performed by general equipment such as a reflow furnace.
  • Cu particles may be used as the metal particles A
  • alloy particles containing Su may be used as the metal particles B.
  • Sn is in an alloy state
  • examples of the case where Sn is in an alloy state include an alloy composed of Su, Ag and Cu (SAC), an alloy composed of Sn and Bi (SnBi), and the like.
  • the composition of the SnBi alloy is not particularly limited, and examples thereof include Sn-Bi58.
  • the alloy represented by Sn—XA indicates that the element X is contained in A mass% in the alloy containing Sn.
  • the melting point (liquid phase transition temperature) of the alloy represented by Sn—Bi58 is about 138 ° C.
  • the ratio of the Cu content and the Sn content on a mass basis to the total of the metal particles A and the metal particles B is preferably 0.6 to 21, more preferably 0.8 to 9.5, and even more preferably 1.0 to 5.6 in some embodiments.
  • the ratio (Cu content / Sn content) is 1.5 to 64. It is preferably 20 to 50, more preferably 25 to 40. When the ratio (Cu content / Sn content) is in the range of 25 to 64, it tends to be possible to form a sintered body having excellent temperature-resistant cycle characteristics of volume resistivity.
  • the ratio (Cu content / Sn content) is 0.
  • the ratio (Cu content / Sn content) is preferably 1.6 to 64, more preferably 1.7 to 40, and 1.8 to 21. Is even more preferable.
  • the ratio (Cu content / Sn content) is in the range of 1.6 to 64, it tends to be possible to form a sintered body having excellent temperature-resistant cycle characteristics of volume resistivity. The reason is not clear, but it can be inferred as follows.
  • the ratio (Cu content / Sn content) is in the range of 1.6 to 64, the Cu content on a mass basis in the entire metal particles A and B is sufficiently higher than the Sn content.
  • transitional liquid phase sintering occurs between the metal particles A and the metal particles B, the unreacted Sn component is unlikely to remain in the sintered body.
  • transitional liquid phase sintering occurs between the metal particles A and the metal particles B, a copper-tin alloy is formed around the copper, so that the grain boundary diameter of the copper-tin alloy depends on the particle size of the copper. To do. If a large amount of unreacted Sn component is present in the sintered body, mutual diffusion will proceed between the unreacted Sn component and the copper-tin alloy when the sintered body is subjected to a temperature cycle test, and copper tin will be present.
  • the ratio of the Cu content and the Bi content on a mass basis to the total of the metal particle A and the metal particle B (Cu).
  • the content rate / Bi content rate) is preferably 1.1 to 44, more preferably 2.3 to 44, further preferably 3 to 20, and particularly preferably 5 to 10. preferable.
  • the ratio (Cu content / Bi content) is 1.1 to 44, it tends to be possible to form a sintered body having excellent temperature resistivity and temperature cycle characteristics.
  • the ratio of the metal particles B to the metal particles A is preferably 10/90 to 90/10, more preferably 20/80 to 80/20, on a mass basis. It is more preferably 30/70 to 70/30.
  • the average particle size of the metal particles A and the metal particles B is not particularly limited.
  • the average particle size of the metal particles A and B may be 0.1 ⁇ m to 10 ⁇ m, 1 ⁇ m to 5 ⁇ m, or 2 ⁇ m to 3 ⁇ m, respectively. ..
  • the average particle size of the metal particles A is preferably 0.05 ⁇ m to 10 ⁇ m, more preferably 0.1 ⁇ m to 2 ⁇ m, and even more preferably 0.15 ⁇ m to 1 ⁇ m. ..
  • the average particle size of the metal particles A is 2 ⁇ m or less, it is possible to reduce the amount of the metal particles A that have not been liquid-phase sintered after the transitional liquid-phase sintering, and as a result, the baking for electromagnetic wave shielding. There is a tendency that the volume resistance of the body can be preferably reduced.
  • the average particle size of the metal particles B is preferably 0.01 ⁇ m to 4 ⁇ m, preferably 0.05 ⁇ m to 1 ⁇ m or 2 ⁇ m to 3 ⁇ m, from the viewpoint of the metal filling rate in the electromagnetic wave shielding composition. More preferably.
  • the average particle size of the metal particles A is preferably 0.2 ⁇ m or more, preferably 0.8 ⁇ m or more, from the viewpoint of further reducing the volume resistivity of the sintered body for electromagnetic wave shielding described later. It is more preferably present, and further preferably 2 ⁇ m or more. Further, from the viewpoint of improving the smoothness of the surface of the sintered body for electromagnetic wave shielding, which will be described later, the average particle size of the metal particles A is preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less, and 0.8 ⁇ m or less. Is more preferable.
  • the relationship between the sizes of the metal particles A and the metal particles B is not particularly limited.
  • the metal particles A and the metal particles B are packed as densely as possible before sintering.
  • the value of the average particle size of the metal particles A / the average particle size of the metal particles B is preferably larger than 1, more preferably larger than 1.1, and even more preferably larger than 1.2. ..
  • the upper limit of the value of the average particle size of the metal particles A / the average particle size of the metal particles B is not particularly limited, but may be, for example, 3 or less.
  • the average particle size of the metal particles A is 10 ⁇ m to 50 ⁇ m, the average particle size of the metal particles B is 5 ⁇ m to 30 ⁇ m, and the average particle size of the metal particles A / the average particle size of the metal particles B.
  • the value of may be more than 1 and 10 or less.
  • the average particle size of the metal particles A is 0.01 ⁇ m to 10 ⁇ m, the average particle size of the metal particles B is 5 ⁇ m to 30 ⁇ m, and the average particle size of the metal particles A / the average of the metal particles B.
  • the particle size value may be 0.002 or more and less than 1.
  • the average particle size of the metal particles A is 4 ⁇ m to 10 ⁇ m
  • the average particle size of the metal particles B is 3 ⁇ m to 10 ⁇ m
  • the average particle size of the metal particles A / the average particle size of the metal particles B The value of may be 0.5 to 2.
  • the average particle size of the metal particles A is 0.01 ⁇ m to 10 ⁇ m
  • the average particle size of the metal particles B is 0.01 ⁇ m to 5 ⁇ m
  • the average particle size of the metal particles A / the metal particles B The value of the average particle size of is 0.05 to 2.
  • the average particle size of metal particles refers to the volume average particle size measured by a laser diffraction type particle size distribution meter (for example, Beckman Coulter Co., Ltd., LS 13 320 type laser scattering diffraction method particle size distribution measuring device). Specifically, metal particles are added to 125 g of a solvent (terpineol) in the range of 0.01% by mass to 0.3% by mass to prepare a dispersion. About 100 ml of this dispersion is injected into the cell and measured at 25 ° C. The particle size distribution is measured with the refractive index of the solvent as 1.48.
  • a solvent terpineol
  • the total content of the metal particles A and the metal particles B in the electromagnetic wave shielding composition is not particularly limited.
  • the ratio of the total mass of the metal particles A and the metal particles B to the total solid content of the electromagnetic wave shielding composition is preferably 96% by mass or less, more preferably 95% by mass or less. It is more preferably 94% by mass or less. Further, the ratio of the total mass of the metal particles A and the metal particles B to the total solid content of the electromagnetic wave shielding composition may be 65% by mass or more.
  • the total content of the metal particles A and the metal particles B in the electromagnetic wave shielding composition is not particularly limited.
  • the ratio of the total mass of the metal particles A and the metal particles B to the entire composition for electromagnetic wave shielding is preferably 96% by mass or less, more preferably 95% by mass or less, and 94% by mass. The following is more preferable. Further, the ratio of the total mass of the metal particles A and the metal particles B to the entire composition for electromagnetic wave shielding may be 65% by mass or more.
  • the electromagnetic wave shielding composition of the present disclosure contains a resin.
  • the composition for electromagnetic wave shielding contains a resin, the voids in the sintered body of the metal particles A and the metal particles B are filled with the resin, and the stress relaxation property and the adhesive force tend to be improved.
  • the resin contained in the composition for electromagnetic wave shielding may be a thermoplastic resin, a thermosetting resin, or a combination thereof. Further, the resin may be in the state of a monomer having a functional group capable of causing a polymerization reaction by heating, or in the state of a polymer that has already been polymerized.
  • the composition for electromagnetic wave shielding preferably contains a thermosetting resin as the resin.
  • the thermosetting resin include resins having a functional group such as an epoxy group, an acryloyl group, a methacryloyl group, a hydroxy group, a vinyl group, a carboxy group, an amino group, a maleimide group, an acid anhydride group, a thiol group and a thionyl group. Be done.
  • thermosetting resin examples include epoxy resin, oxazine resin, bismaleimide resin, phenol resin, unsaturated polyester resin, and silicone resin. Of these, epoxy resin is preferable.
  • the epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalene type epoxy resin, and biphenol type epoxy resin.
  • examples thereof include biphenyl novolac type epoxy resin and cyclic aliphatic epoxy resin.
  • One type of resin component may be used alone, or two or more types may be used in combination.
  • the content of the resin in the composition for electromagnetic wave shielding is not particularly limited.
  • the ratio of the resin to the total solid content of the electromagnetic wave shielding composition is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, and 1 It is more preferably mass% to 15% by mass.
  • the proportion of the resin in the solid content of the electromagnetic wave shielding composition excluding the metal particles A and the metal particles B is preferably 10% by mass to 90% by mass, and preferably 20% by mass to 80% by mass. More preferably, it is more preferably 30% by mass to 70% by mass.
  • the content of the resin in the composition for electromagnetic wave shielding is not particularly limited.
  • the proportion of the resin in the entire composition for electromagnetic wave shielding is preferably 0.1% by mass to 5% by mass, more preferably 0.2% by mass to 3% by mass, and 0.3. It is more preferably from% to 1% by mass.
  • the proportion of the resin in the electromagnetic wave shielding composition excluding the metal particles A and the metal particles B is preferably 0.5% by mass to 10% by mass, and is preferably 0.8% by mass to 5% by mass. Is more preferable, and 1% by mass to 3% by mass is further preferable.
  • the electromagnetic wave shielding composition may contain a curing agent that cures the thermosetting resin.
  • the type of the curing agent is not particularly limited, and is appropriately selected depending on the type of the thermosetting resin.
  • thermosetting resin is an epoxy resin
  • examples of the curing agent include amine-based curing agents, phenol-based curing agents, and acid anhydride-based curing agents.
  • the curing agent can be either liquid or solid.
  • one type may be used alone, or two or more types may be used in combination.
  • amine-based curing agent examples include chain aliphatic amines, cyclic aliphatic amines, aliphatic aromatic amines, and aromatic amines.
  • Specific examples of the amine-based curing agent include m-phenylenediamine, 1,3-diaminotoluene, 1,4-diaminotoluene, 2,4-diaminotoluene, and 3,5-diethyl-2,4-diaminotoluene.
  • Aromatic amine curing agent with two aromatic rings such as 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane; hydrolyzed condensate of aromatic amine curing agent; polytetramethylene oxide di- Aromatic amine curing agent having a polyether structure such as p-aminobenzoic acid ester, polyt
  • Examples of the acid anhydride-based curing agent include phthalic anhydride, maleic anhydride, methyl hymic acid anhydride, hymic acid anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, and methyltetrahydro.
  • Phthalic anhydride 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride maleic anhydride, benzophenone tetracarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, Examples thereof include various cyclic acid anhydrides such as trialkyltetrahydrophthalic anhydride and dodecenyl succinic anhydride obtained by the deal alder reaction from hydride methylnadic acid anhydride, maleic anhydride and diene compound, and having a plurality of alkyl groups. ..
  • the phenolic curing agent is selected from the group consisting of phenol compounds (eg, phenol, cresol, xylenol, resorcin, catechol, bisphenol A and bisphenol F) and naphthol compounds (eg, ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene).
  • Novolak resin obtained by condensing or co-condensing at least one of the above with an aldehyde compound (for example, formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde) under an acidic catalyst; phenol-aralkyl resin; biphenyl-aralkyl. Resin; naphthol-aralkyl resin; and the like.
  • the ratio to the equivalent number of the epoxy resin is preferably set in the range of 0.6 to 1.4, and is set in the range of 0.7 to 1.3. It is more preferable to set the value in the range of 0.8 to 1.2.
  • the composition for electromagnetic wave shielding contains a thermosetting resin
  • the composition for electromagnetic wave shielding contains a curing accelerator that accelerates the curing reaction of the thermosetting resin or the curing reaction between the thermosetting resin and the curing agent. May be good.
  • the type of the curing accelerator is not particularly limited, and is appropriately selected depending on the type of the thermosetting resin and the curing agent.
  • the curing accelerator examples include 1,8-diaza-bicyclo [5.4.0] undecene-7, 1,5-diaza-bicyclo [4.3.0] nonene, and 5,6-dibutyl.
  • Cycloamidine compounds such as amino-1,8-diaza-bicyclo [5.4.0] undecene-7; cycloamidine compounds include maleic anhydride, 1,4-benzoquinone, 2,5-turquinone, 1,4-naphthoquinone.
  • 2,3-Didimethylbenzoquinone 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone Kinone compounds such as, diazophenylmethane, compounds having intramolecular polarization formed by adding a compound having a ⁇ bond such as phenol resin; benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, etc.
  • Tertiary amine compounds Tertiary amine compounds; derivatives of tertiary amine compounds; imidazole compounds such as imidazole, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole; derivatives of imidazole compounds; tetraphenylphosphonium tetraphenylborate, Tetraphenylborate salts such as triphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazolium tetraphenylborate, N-methylmorpholinium tetraphenylborate; derivatives of tetraphenylborate salt; triphenylphosphine-triphenylborane Examples thereof include a triphenylboran complex such as a complex and a morpholin-triphenylboran complex; and the like.
  • the curing accelerator one type may be used alone, or two or more types may be used in combination.
  • the content of the curing accelerator is preferably 0.1% by mass to 15% by mass with respect to the total amount of the thermosetting resin and the curing agent.
  • the electromagnetic wave shielding composition of the present disclosure may contain a flux component.
  • the flux component means an organic compound capable of exerting a flux action (removal action of an oxide film), and the type thereof is not particularly limited.
  • the flux component may function as a curing agent for an epoxy resin which is a thermosetting resin.
  • a component that functions as both a flux component and a curing agent for an epoxy resin is referred to as a flux component.
  • Specific examples of the flux component include rosin, activator, thixotropy, antioxidant and the like.
  • One type of flux component may be used alone, or two or more types may be used in combination.
  • rosin examples include dehydroabietic acid, dihydroabietic acid, neoavietic acid, dihydropimaric acid, pimaric acid, isopimaric acid, tetrahydroabietic acid, palastolic acid, 2,2-bis (hydroxymethyl) propionate (BHPA), and the like. Can be mentioned.
  • aminodecanoic acid pentane-1,5-dicarboxylic acid, triethanolamine, diethanolamine, ethanolamine diphenylacetic acid, sebacic acid, phthalic acid, benzoic acid, dibromosalicylic acid, anisic acid, iodosalicylic acid, picolin Acids, propionic acids, 4-aminosalicylic acid, ethyl 3- (benzylamino) propionate and the like can be mentioned.
  • thixo agent examples include 12-hydroxystearic acid, 12-hydroxystearic acid triglyceride, ethylenebisstearic acid amide, hexamethylenebisoleic acid amide, N, N'-distearyl adipic acid amide and the like.
  • antioxidant examples include hindered phenol-based antioxidants, phosphorus-based antioxidants, hydroxylamine-based antioxidants, and the like.
  • the composition for electromagnetic wave shielding contains a flux component
  • the rosin contains BHPA and the activator contains triethanolamine.
  • the flux component it is more preferable to use BHPA and triethanolamine in combination.
  • the composition for electromagnetic wave shielding contains a flux component, in one embodiment, ⁇ -20 ⁇ ⁇ , where the temperature at which the flux component changes phase is ⁇ (° C.) and the melting point of the metal particles B is ⁇ (° C.). It is preferable to include a flux component (specific flux component) that satisfies ⁇ ⁇ + 20.
  • the "temperature at which the flux component undergoes a phase change” means the temperature at which the flux component undergoes a phase change from a liquid to a gas, from a solid to a liquid, or the like.
  • the "temperature at which the flux component changes phase” may be the melting point of the flux component or the boiling point of the flux component.
  • the temperature at which the specific flux component changes phase does not become too high with respect to the melting point of the metal particles B, and the specific flux is generated when transitional liquid phase sintering is performed at a low temperature. It becomes an active state and tends to be able to efficiently suppress the oxidation of the surface of the sintered body.
  • the specific flux component satisfies ⁇ -20 ⁇ ⁇
  • the temperature at which the specific flux component changes in phase does not become too low with respect to the melting point of the metal particles B, and the composition for shielding an electromagnetic wave is excellent in storage stability.
  • oxidation of the surface of the sintered body when sintering in an air atmosphere can be suitably suppressed while suppressing an adverse effect on the production of the sintered body.
  • the specific flux component may satisfy ⁇ ⁇ ⁇ + 15 or may satisfy ⁇ ⁇ ⁇ + 10.
  • the specific flux component may satisfy ⁇ -10 ⁇ ⁇ or ⁇ ⁇ ⁇ .
  • the specific flux component include components satisfying ⁇ -20 ⁇ ⁇ ⁇ + 20 among rosin, activator, thixotropy, antioxidant and the like.
  • the specific flux component one type may be used alone, or two or more types may be used in combination.
  • the specific flux component may be appropriately selected from rosin, activator, thixotropic agent, antioxidant and the like in relation to the melting point of the metal particles B and the temperature at which the specific flux component changes in phase.
  • the temperature at which the specific flux component undergoes a phase change is, for example, preferably 130 ° C. to 160 ° C., more preferably 135 ° C. to 155 ° C.
  • the specific flux component is preferably at least one selected from the group consisting of propionic acid, 4-aminosalicylic acid and ethyl 3- (benzylamino) propionate.
  • the ratio of the flux component to the total solid content of the electromagnetic wave shielding composition is, for example, preferably 0.1% by mass to 50% by mass, and is preferably 0.5. It is more preferably from mass% to 40% by mass, and even more preferably from 1% by mass to 30% by mass.
  • the ratio of the flux component to the solid content of the electromagnetic wave shielding composition excluding the metal particles A and the metal particles B is preferably 5% by mass to 60% by mass, and more preferably 10% by mass to 50% by mass. It is preferable, and it is more preferably 15% by mass to 40% by mass.
  • the ratio of the specific flux component to the entire electromagnetic wave shielding composition is preferably, for example, 1% by mass to 20% by mass, and 3% by mass to 15% by mass. It is more preferably%, and further preferably 4% by mass to 10% by mass.
  • the ratio of the specific flux component to the electromagnetic wave shielding composition excluding the metal particles A and the metal particles B is preferably 5% by mass to 70% by mass. It is more preferably 10% by mass to 50% by mass, and further preferably 15% by mass to 30% by mass.
  • the electromagnetic wave shielding composition contains a specific flux component
  • the electromagnetic wave shielding composition, together with the specific flux component is also referred to as a flux component that does not satisfy ⁇ -20 ⁇ ⁇ ⁇ ⁇ + 20 (hereinafter, also referred to as “other flux component”). ) May not be included, and may be included.
  • Other flux components are determined in relation to the melting point of the metal particles B, and can be specifically selected from the above-mentioned specific examples of rosin, activator, thixotropy and antioxidant.
  • the ratio of the other flux component to the total of the specific flux component and other flux components in the composition for electromagnetic wave shielding may be 80% by mass or less. It may be 50% by mass or less.
  • the electromagnetic wave shielding composition of the present disclosure may contain a solvent.
  • the solvent is preferably a polar solvent, and has a boiling point of 200 ° C. or higher from the viewpoint of suppressing drying of the electromagnetic wave shielding composition in the step of applying the electromagnetic wave shielding composition. It is preferably a solvent, and more preferably a solvent having a boiling point of 300 ° C. or lower from the viewpoint of suppressing the generation of voids during sintering.
  • solvents examples include terpineol, stearyl alcohol, tripropylene glycol methyl ether, diethylene glycol, diethylene glycol monoethyl ether (also known as ethoxyethoxyethanol), diethylene glycol monohexyl ether (also known as hexyl carbitol), diethylene glycol monomethyl ether, and dipropylene glycol.
  • ketones such as isophorone
  • lactams such as N-methyl-2-pyrrolidone
  • nitriles such as phenyl acetonitrile
  • the ratio of the solvent in the electromagnetic wave shielding composition is preferably an amount that makes the electromagnetic wave shielding composition have a viscosity suitable for an application method such as a screen printing method or a spray coating method.
  • the proportion of the solvent in the electromagnetic wave shielding composition is preferably, for example, 0.1% by mass to 50% by mass, and 0.5% by mass, based on the entire electromagnetic wave shielding composition. It is more preferably about 30% by mass, and even more preferably 1% by mass to 10% by mass.
  • the proportion of the solvent in the electromagnetic wave shielding composition is preferably, for example, 0.1% by mass to 25% by mass, and 0.2% by mass, based on the entire electromagnetic wave shielding composition. It is more preferably about 20% by mass, and even more preferably 0.3% by mass to 15% by mass.
  • the method for producing the electromagnetic wave shielding composition of the present disclosure is not particularly limited. It can be obtained by mixing the components constituting the electromagnetic wave shielding composition and further performing treatments such as stirring, dissolution, and dispersion.
  • the device for mixing, stirring, dispersing, etc. of these is not particularly limited, and a three-roll mill, a planetary mixer, a planetary mixer, a rotating / revolving stirrer, a shearing machine, a twin-screw kneader, and the like.
  • a thin layer shear disperser or the like can be used. Moreover, you may use these devices in combination as appropriate.
  • During the above treatment it may be heated if necessary.
  • the maximum particle size of the electromagnetic wave shielding composition may be adjusted by filtration. Filtration can be performed using a filtration device. Examples of the filter for filtration include a metal mesh, a metal filter and a nylon mesh.
  • the electromagnetic wave shielding sheet of the present disclosure has a resin composition layer containing the electromagnetic wave shielding composition of the present disclosure.
  • the electromagnetic wave shielding sheet of the present disclosure may be further composed of a release film, if necessary.
  • a varnish-like composition for electromagnetic wave shielding (hereinafter, also referred to as “resin varnish”) prepared by adding a solvent to the electromagnetic wave shielding composition of the present disclosure is used as a polyethylene terephthalate film or a polyimide film. It can be produced by applying it on a release film such as varnish and drying it.
  • the application of the resin varnish can be carried out by a known method. Specific examples thereof include a method such as a comma coat, a die coat, a lip coat, a gravure coat, a stencil coat, and a spray coat, and a method using an applicator.
  • a method of applying the resin varnish for forming the resin composition layer to a predetermined thickness a comma coating method in which the object to be coated is passed between the gaps, a die coating method in which the resin varnish whose flow rate is adjusted from the nozzle is applied, and the like are used. Can be mentioned.
  • the thickness of the resin composition layer before drying is 50 ⁇ m to 500 ⁇ m, it is preferable to use the comma coating method.
  • the drying method is not particularly limited as long as at least a part of the solvent contained in the resin varnish can be removed, and can be appropriately selected from the commonly used drying methods.
  • a drying method drying by leaving at room temperature (for example, 25 ° C.), heat drying or vacuum drying can be used.
  • heat drying or vacuum drying hot plate, warm air dryer, hot air heating furnace, nitrogen dryer, infrared dryer, infrared heating furnace, far infrared heating furnace, microwave heating device, laser heating device, electromagnetic heating device , A heater heating device, a steam heating furnace, etc. can be used.
  • the temperature and time for drying can be appropriately adjusted according to the type and amount of the solvent used, and for example, it is preferable to dry at 40 ° C. to 180 ° C. for 1 minute to 120 minutes.
  • the average thickness of the resin composition layer is preferably 3 ⁇ m to 300 ⁇ m, more preferably 5 ⁇ m to 100 ⁇ m, and even more preferably 10 ⁇ m to 50 ⁇ m.
  • the electromagnetic wave shielding sintered body of the present disclosure is a sintered body of the electromagnetic wave shielding composition of the present disclosure or the electromagnetic wave shielding sheet of the present disclosure.
  • the shape of the sintered body for electromagnetic wave shielding is not particularly limited, and it may be in the form of a layer provided on the support member or in the form of a sheet.
  • the electromagnetic wave shielding sintered body of the present disclosure heats the electromagnetic wave shielding composition of the present disclosure or the electromagnetic wave shielding sheet of the present disclosure to transition between the metal particles A and the metal particles B contained in the electromagnetic wave shielding composition. It can be manufactured by subjecting it to liquid phase sintering.
  • the transitional liquid phase sintering may be performed by heat treatment or heat and pressure treatment.
  • heat treatment hot plate, hot air dryer, hot air heater, nitrogen dryer, infrared dryer, infrared heater, far infrared heater, microwave heater, laser heater, electromagnetic heater, heater heating An apparatus, a steam heating furnace, or the like can be used.
  • a hot plate press device or the like may be used, or the above-mentioned heat treatment may be performed while pressurizing.
  • the heating temperature in the transitional liquid phase sintering depends on the type of metal particles, but is preferably 140 ° C. or higher, more preferably 190 ° C. or higher, and further preferably 220 ° C. or higher.
  • the upper limit of the heating temperature is not particularly limited, but is, for example, 300 ° C. or lower.
  • the heating time in the transitional liquid phase sintering depends on the type of metal particles, but is preferably 5 seconds to 10 hours, more preferably 1 minute to 30 minutes, and preferably 3 minutes to 10 minutes. More preferred.
  • Transitional liquid phase sintering is preferably performed in an atmosphere with a low oxygen concentration.
  • the low oxygen concentration atmosphere means a state in which the oxygen concentration on a volume basis is 1000 ppm or less, preferably 500 ppm or less.
  • the transitional liquid phase sintering may be performed in an atmosphere of low oxygen concentration or in an air atmosphere.
  • the volume resistivity of the sintered body for electromagnetic wave shielding is preferably 3 ⁇ 10 -4 ⁇ ⁇ cm or less, more preferably 9 ⁇ 10 -5 ⁇ ⁇ cm or less, and 8 ⁇ 10 -5 ⁇ ⁇ cm. It is more preferably cm or less, and particularly preferably 7 ⁇ 10 -5 ⁇ ⁇ cm or less.
  • the volume resistivity of the sintered body for electromagnetic wave shielding may be 1 ⁇ 10 -5 ⁇ ⁇ cm or more. In the present disclosure, the volume resistivity means a value measured by the following method.
  • a regular quadrangular plate-shaped sample with a side length of 15 mm is cut out from a sheet-shaped sintered body for electromagnetic wave shielding, and a high-precision resistivity meter Lorester GP (manufactured by Nittoseiko Analytech Co., Ltd.) is placed in the center of the plate-shaped sample. Press the 4 probes of.
  • the volume resistivity ⁇ ( ⁇ ⁇ cm) is obtained from the obtained surface resistivity and film thickness.
  • five plate-shaped samples are measured, and the average value thereof is taken as the volume resistivity of the sintered body for electromagnetic wave shielding.
  • the average thickness of the electromagnetic wave shielding sintered body is preferably 3 ⁇ m to 30 ⁇ m, more preferably 4 ⁇ m to 20 ⁇ m, and even more preferably 5 ⁇ m to 10 ⁇ m.
  • the electronic component device of the present disclosure has a region covered by the sintered body for electromagnetic wave shielding of the present disclosure.
  • Electronic component devices include lead frames, pre-wired tape carriers, wiring boards, glass, support members such as silicon wafers, active elements such as semiconductor chips, transistors, diodes, and thyristors, capacitors, resistors, resistor arrays, and coils. , Those equipped with electronic components such as passive elements such as switches.
  • the electronic component device of the present disclosure can be obtained by covering a portion of the electronic component and the support member that generates an electromagnetic wave or a portion that is easily affected by the electromagnetic wave with the sintered body for electromagnetic wave shielding of the present disclosure.
  • Examples of the method of covering the electronic component or the support member with the electromagnetic wave shielding sintered body include a method in which a varnish-like electromagnetic wave shielding composition is applied to a portion to be covered with the electromagnetic wave shielding sintered body, dried, and heated. ..
  • Examples of the application method include a screen printing method and a spray coating method.
  • the drying conditions and drying method are the same as the conditions and methods for producing the electromagnetic wave shielding sheet described above.
  • the heating conditions and the heating method are the same as the conditions and methods for producing the above-mentioned sintered body for electromagnetic wave shielding.
  • a method of arranging the electromagnetic wave shielding sheet of the present disclosure at a place to be covered with the electromagnetic wave shielding sintered body and heating it can also be mentioned.
  • the heating conditions and heating method of the electromagnetic wave shielding sheet are the same as the conditions and methods for manufacturing the electromagnetic wave shielding sintered body described above.
  • the electronic component device of the present disclosure includes a support member, an electronic component arranged on the support member, a cured product of a sealing material for sealing the electronic component, and a book arranged on the surface of the cured product of the sealing material. It may be provided with the disclosed electromagnetic wave shielding sintered body.
  • the electromagnetic wave shielding sintered body When the electromagnetic wave shielding sintered body is placed on the surface of the cured product of the encapsulant, the electromagnetic wave shielding sintered body may be formed on the surface of the cured material of the encapsulant after the encapsulant is cured.
  • An electromagnetic wave shielding composition or an electromagnetic wave shielding sheet may be placed on the surface of the sealing material before curing, and the sealing material may be cured and the electromagnetic wave shielding sintered body may be formed at the same time.
  • the electronic component device may further include a housing that houses the electronic component and the support member.
  • the electronic component device of the present disclosure can be obtained by covering at least one of the inner surface and the outer surface of the housing with the sintered body for electromagnetic wave shielding of the present disclosure. it can.
  • the method of covering the inner surface or the outer surface of the housing with the electromagnetic wave shielding sintered body is the same as the method of covering the electronic component or the support member with the electromagnetic wave shielding sintered body.
  • a member (covering member) covered with the electromagnetic wave shielding sintered body such as an electronic component, a support member, and a housing, and an electromagnetic wave shielding sintered body. From the viewpoint of adhesive strength, it is preferable that no voids or the like are formed at the interface. In the present disclosure, when the interface between the covering member and the sintered body for electromagnetic wave shielding is observed in the region covered with the sintered body for electromagnetic wave shielding, the covering member and the electromagnetic wave occupy the length of the interface in the observation region.
  • the ratio of the length of the portion where the shield sintered body is not adhered (hereinafter, may be referred to as porosity) is preferably 5% or less, more preferably 3% or less. It is more preferably 1% or less.
  • the length of the interface in the observation area and the length of the part where the covering member and the sintered body for electromagnetic wave shielding do not adhere to each other in the length of the interface in the observation area are covered with the sintered body for electromagnetic wave shielding.
  • the cross section of the damaged region can be obtained from an image taken under a condition of 3000 times using a scanning electron microscope (SEM).
  • Example 1A Cu particles (product name: 1400YM, Mitsui Metal Mining Co., Ltd., average particle diameter: 4 ⁇ m) are 61 parts by mass as metal particles A, and Sn-Bi58 particles (product name: STC-3, Mitsui Metal Mining Co., Ltd., average) as metal particles B.
  • Particle size (3 ⁇ m) is 30 parts by mass
  • epoxy resin is 4 parts by mass as resin
  • BHPA is 0.7 parts by mass as rosin
  • triethanolamine is 1.8 parts by mass as activator
  • imidazole is 0.
  • Resin varnish 1A was prepared by mixing 2 parts by mass and 2.3 parts by mass of hexylcarbitol as a solvent.
  • a resin varnish 1A was applied onto a polyimide film with an applicator having a gap of 50 ⁇ m to prepare a coating film. Then, it was dried at 100 ° C. for 30 minutes and heat-treated at 150 ° C. for 10 minutes in a nitrogen atmosphere reflow furnace to obtain a sintered body. The average thickness of the sintered body was 15 ⁇ m. A part of this sintered body was joined to the ground to prepare a test piece.
  • Example 2A 30 parts by mass of Cu particles (product name: CH-0200, Mitsui Metal Mining Co., Ltd., average particle diameter: 0.2 ⁇ m) as metal particles A, Sn-Bi58 particles (product name: STC-3, Mitsui Metal Mining Co., Ltd.) as metal particles B Co., Ltd., average particle size: 3 ⁇ m) is 60 parts by mass, epoxy resin is 4 parts by mass as resin, BHPA is 0.7 parts by mass as rosin, triethanolamine is 2.8 parts by mass as activator, and as a curing accelerator.
  • Resin varnish 2A was prepared by mixing 0.2 parts by mass of imidazole and 2.3 parts by mass of hexylcarbitol as a solvent.
  • a resin varnish 2A was applied onto a polyimide film with an applicator having a gap of 10 ⁇ m to prepare a coating film. Then, it was dried at 100 ° C. for 30 minutes and heat-treated at 150 ° C. for 10 minutes in a nitrogen atmosphere reflow furnace to obtain a sintered body. The average thickness of the sintered body was 9 ⁇ m. A part of this sintered body was joined to the ground to prepare a test piece.
  • Example 3A 21 parts by mass of Cu particles (product name: CH-0200, Mitsui Metal Mining Co., Ltd., average particle diameter: 0.2 ⁇ m) as metal particles A, Sn particles (product names: Sn100, STC-3,) as the first metal particles B, Mitsui Metal Mining Co., Ltd., average particle size: 3 ⁇ m) is 34 parts by mass, and Sn-Bi58 particles (product names: SnBi58, STC-3, Mitsui Metal Mining Co., Ltd., average particle size: 3 ⁇ m) are used as the second metal particles B.
  • Cu particles product name: CH-0200, Mitsui Metal Mining Co., Ltd., average particle diameter: 0.2 ⁇ m
  • Sn particles product names: Sn100, STC-3,
  • Sn-Bi58 particles product names: SnBi58, STC-3, Mitsui Metal Mining Co., Ltd., average particle
  • a resin varnish 3A was prepared by mixing 0.3 parts by mass of hexyl carbitol as a solvent.
  • a resin varnish 3A was applied onto a polyimide film with an applicator having a gap of 50 ⁇ m to prepare a coating film. Then, it was dried at 100 ° C. for 30 minutes and heat-treated at 150 ° C. for 10 minutes in a nitrogen atmosphere reflow furnace to obtain a sintered body. The average thickness of the sintered body was 15 ⁇ m. A part of this sintered body was joined to the ground to prepare a test piece.
  • the resin varnish 3 was applied onto the polyimide film with an applicator having a gap of 200 ⁇ m to prepare a coating film. Then, it dried at 50 degreeC for 1 hour, and heat-treated at 150 degreeC for 1 hour to obtain a sintered body. The average thickness of the sintered body was 15 ⁇ m. A part of this sintered body was joined to the ground to prepare a test piece.
  • the electromagnetic wave shielding effect was evaluated by the KEC method shown below.
  • the obtained test piece was installed in the measuring section of the electromagnetic wave shielding effect measuring device (KEC Kansai Electronics Industry Promotion Center), and the test piece was sandwiched and fixed from above and below.
  • the device can generate both an electromagnetic wave having a large electric field component and an electromagnetic wave having a large magnetic field component.
  • the electromagnetic wave shielding effect was evaluated from the ratio of the intensity of the received electromagnetic wave when there was no test piece to the intensity of the received electromagnetic wave when the test piece was installed.
  • the volume resistivity of the obtained sintered body was measured by the above-mentioned method in an environment of 25 ° C.
  • the volume resistivity of the sintered body of Example 1A is 6 ⁇ 10 -5 ⁇ ⁇ cm
  • the volume resistivity of the sintered body of Example 2A is 9 ⁇ 10 -5 ⁇ ⁇ cm.
  • the volume resistivity of the sintered body was 9 ⁇ 10 -5 ⁇ ⁇ cm
  • the volume resistivity of the sintered body of Comparative Example 1 was 6 ⁇ 10 -4 ⁇ ⁇ cm.
  • FIG. 1 shows the measurement results of the electromagnetic wave shielding effect of the sintered bodies produced in Examples 1A and 2A and Comparative Example 1. It can be seen that the sintered body of the example in which the metal particles are sintered using TLPS can obtain a higher electromagnetic wave shielding effect than the sintered body of Comparative Example 1.
  • Example 1B Cu particles (product name: 1400YM, Mitsui Metal Mining Co., Ltd., average particle diameter: 4 ⁇ m) are 19.5 parts by mass as metal particles A, and Sn-Bi58 particles (product name: STC-3, Mitsui Metal Mining Co., Ltd.) are used as metal particles B. , Average particle size: 3 ⁇ m, melting point: 138 ° C.) by 54.3 parts by mass, epoxy resin as resin by 0.4 parts by mass, propionic acid (boiling point: 141 ° C.) by 4.4 parts by mass as flux component, activator As, triethanolamine (melting point: 20.5 ° C., boiling point: 335 ° C., (208 ° C.
  • Example 1B ⁇ (° C.) is 141 ° C. and ⁇ (° C.) is 138 ° C., so that ⁇ -20 ⁇ ⁇ ⁇ + 20 is satisfied.
  • Example 2B In Example 1B, a resin varnish 2B was prepared in the same manner as in Example 1B except that the flux component was changed from propionic acid to 4-aminosalicylic acid (melting point: 150 ° C.), and then sintered using the resin varnish 2B. A body and a test piece were obtained.
  • ⁇ (° C.) is 150 ° C.
  • ⁇ (° C.) is 138 ° C., so that ⁇ -20 ⁇ ⁇ ⁇ + 20 is satisfied.
  • Example 3B In Example 1B, a resin varnish 3B was prepared in the same manner as in Example 1B except that the flux component was changed from propionic acid to 2,2-bis (hydroxymethyl) propionic acid (BHPA, melting point: 185 ° C.), and then resin varnish 3B was prepared. , Resin varnish 3B was used to obtain a sintered body and a test piece.
  • ⁇ (° C.) is 185 ° C.
  • ⁇ (° C.) is 138 ° C., so ⁇ -20 ⁇ ⁇ ⁇ + 20 is not satisfied.
  • the sintered bodies prepared in Examples 1B and 2B had surface oxidation suppressed as compared with the sintered bodies prepared in Example 3B. Further, the sintered body prepared in Examples 1B and 2B and the sintered body prepared in Example 3B had the same volume resistivity when the high temperature and high humidity test was not performed. On the other hand, regarding the volume resistivity after the high temperature and high humidity test, the sintered bodies prepared in Examples 1B and 2B have lower volume resistivity values than the sintered bodies prepared in Example 3B. The deterioration of the characteristics was suppressed. When the sintering treatment was performed in the same manner as in Example 1A using the electromagnetic wave shielding compositions of Examples 1B, 2B and 3B, they were produced in Examples 1B and 2B.
  • the sintered body and the sintered body produced in Example 3B have the same volume resistivity when the high temperature and high humidity test is not performed. Further, the surface oxidation of the sintered body produced in Example 3B is suppressed as in the sintered body produced in Examples 1B and 2B.
  • Example 1C Cu particles (product name: 1400YM, Mitsui Metal Mining Co., Ltd., average particle diameter: 4 ⁇ m) are 82.2 parts by mass as metal particles A, and Sn-Bi58 particles (product name: STC-3, Mitsui Metal Mining Co., Ltd.) are used as metal particles B. , Average particle size: 3 ⁇ m) by 17.8 parts by mass, epoxy resin as resin by 4 parts by mass, rosin by BHPA by 0.7 parts by mass, triethanolamine as activator by 2.8 parts by mass, as curing accelerator Resin varnish 1C was prepared by mixing 0.2 parts by mass of imidazole and 2.3 parts by mass of hexylcarbitol as a solvent.
  • the resin varnish 1C was applied onto the polyimide film with an applicator having a gap of 50 ⁇ m to prepare a coating film. Then, it was dried at 100 ° C. for 30 minutes and heat-treated at 150 ° C. for 10 minutes in a nitrogen atmosphere reflow furnace to obtain a sintered body. The average thickness of the sintered body was 15 ⁇ m. A part of this sintered body was joined to the ground to prepare a test piece.
  • Example 2C 30 parts by mass of Cu particles (product name: 1400YM, Mitsui Metal Mining Co., Ltd., average particle diameter: 4 ⁇ m) as metal particles A, Sn-Bi58 particles (product name: STC-3, Mitsui Metal Mining Co., Ltd., average) as metal particles B Particle size (3 ⁇ m) is 60 parts by mass, epoxy resin is 4 parts by mass as resin, BHPA is 0.3 parts by mass as rosin, triethanolamine is 2.8 parts by mass as activator, and imidazole is 0.
  • Resin varnish 2C was prepared by mixing 2 parts by mass and 2.3 parts by mass of hexylcarbitol as a solvent.
  • the resin varnish 2C was applied onto the polyimide film with an applicator having a gap of 50 ⁇ m to prepare a coating film. Then, it was dried at 100 ° C. for 30 minutes and heat-treated at 150 ° C. for 10 minutes in a nitrogen atmosphere reflow furnace to obtain a sintered body. The average thickness of the sintered body was 15 ⁇ m. A part of this sintered body was joined to the ground to prepare a test piece.
  • the sintered body prepared in Example 1C is more suppressed from the increase in volume resistivity due to the increase in the number of cycles of the temperature cycle test than the sintered body prepared in Example 2C. It was excellent in temperature resistivity and temperature resistance cycle characteristics.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
PCT/JP2020/036419 2019-09-27 2020-09-25 電磁波シールド用組成物、電磁波シールド用シート、電磁波シールド用焼結体及び電子部品装置 Ceased WO2021060525A1 (ja)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022093168A (ja) * 2020-12-11 2022-06-23 昭和電工マテリアルズ株式会社 電子部品装置及び電子部品装置の製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013510240A (ja) * 2009-11-05 2013-03-21 オーメット サーキッツ インク 冶金ネットワーク組成物の調製およびその使用方法
WO2018168187A1 (ja) * 2017-03-15 2018-09-20 日立化成株式会社 接合用金属ペースト、接合体及びその製造方法、並びに半導体装置及びその製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013510240A (ja) * 2009-11-05 2013-03-21 オーメット サーキッツ インク 冶金ネットワーク組成物の調製およびその使用方法
WO2018168187A1 (ja) * 2017-03-15 2018-09-20 日立化成株式会社 接合用金属ペースト、接合体及びその製造方法、並びに半導体装置及びその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022093168A (ja) * 2020-12-11 2022-06-23 昭和電工マテリアルズ株式会社 電子部品装置及び電子部品装置の製造方法
JP7676763B2 (ja) 2020-12-11 2025-05-15 株式会社レゾナック 電子部品装置及び電子部品装置の製造方法

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