WO2021054196A1

WO2021054196A1 - Adhesive and antenna device

Info

Publication number: WO2021054196A1
Application number: PCT/JP2020/033934
Authority: WO
Inventors: 長谷川　淳; 松下　清人
Original assignee: 積水化学工業株式会社
Priority date: 2019-09-19
Filing date: 2020-09-08
Publication date: 2021-03-25
Also published as: TW202122187A; JPWO2021054196A1

Abstract

The present invention provides an adhesive which is capable of maintaining the bonding strength between substrates even if heated repeatedly, while being capable of controlling the gap of an air cavity with high accuracy.　An adhesive according to the present invention is used for the purpose of bonding a first metal part, which is on the surface of a first substrate, and a second metal part, which is on the surface of a second substrate, to each other; and with respect to this adhesive, the change ratio of the number of separation between the substrates as calculated by the evaluation test 1 described below is 20% or less.　Evaluation test 1:　The adhesive is arranged on the first metal part of the first substrate, and the second substrate, which has the second metal part on the surface, is arranged on a surface of the adhesive, said surface being on the reverse side from the first substrate, so that the metal parts face each other. Subsequently, the first substrate and the second substrate are bonded to each other by means of a reflow process, thereby obtaining a multilayer body. The thus-obtained multilayer body is subjected to the reflow process four times. The change ratio of the number of separation is calculated from the numbers of separation before and after heating.

Description

Adhesive and antenna device

The present invention relates to an adhesive for adhering two substrates. The present invention also relates to an antenna device using the above adhesive.

Various adhesives are used to bond the two adherends. Further, in order to make the thickness of the adhesive layer formed by the adhesive uniform and to control the distance (gap) between the two adherends, a spacer such as a gap material may be added to the adhesive.

In recent years, with the rapid spread of smartphones, tablet terminals, etc., a rapid increase in traffic has become an issue. For this reason, the successor system of communication systems such as LTE (Long Term Evolution) and LTE-A (LTE-Advanced) by 3GPP (Third Generation Partnership Project), and the 5th generation mobile communication system (5G) as a new wireless communication system. ) Is under consideration.

For example, in the 5th generation mobile communication system (5G), in order to realize high-speed transmission using a wider band, it is considered to communicate using a higher carrier frequency as compared with LTE and LTE-A. There is. However, when communicating at a high carrier frequency, the conventional antenna device may not be able to sufficiently exhibit its performance. The conventional antenna device is disclosed in, for example, Patent Document 1 below.

Patent Document 1 below discloses an antenna device including an antenna and a multilayer high-frequency substrate. The antenna has a power feeding conductor on the back surface. The multilayer high-frequency substrate is configured by laminating a plurality of strip lines having lands on the surface thereof. The land is electrically connected to the strip conductor via a through hole. In the multilayer high frequency substrate, the lands of the strip lines to be laminated are joined by an anisotropic conductive adhesive. In the antenna device, the power feeding conductor of the antenna and the land on the surface of the multilayer high frequency substrate are joined by an anisotropic conductive adhesive.

Japanese Unexamined Patent Publication No. 2015-185550

For the antennas of base stations and terminals for the 5th generation mobile communication system (5G), improvement of communication speed and improvement of communication quality are required. In order to improve the communication speed and the communication quality, it is considered to provide an air cavity (space) in the antenna. By providing an air cavity (space) in the antenna, it is possible to improve the bandwidth and reduce electromagnetic noise. As a result, the communication speed and communication quality of the antenna can be improved.

Conventional antenna devices do not require a high level of communication speed and communication quality, and there are cases where an air cavity (space) is not provided inside the antenna. The air cavity (space) is formed, for example, by maintaining a uniform and constant distance (gap) between the high-frequency substrate and the substrate constituting the antenna. In order to improve the communication speed and communication quality of the antenna, it is required to control the interval (gap) of the air cavity (space) with high accuracy.

Further, when an antenna device is obtained by adhering two substrates so as to form an air cavity (space) in the antenna using an adhesive, the antenna device may be repeatedly heated. Repeated heating of the antenna device may reduce the adhesive strength between the two substrates. If the adhesive strength between the two substrates is low, peeling or the like may occur between the substrates due to vibration or impact from the outside due to dropping or the like. If peeling or the like occurs between the substrates, it may not be possible to control the gap between the air cavities (spaces) with high accuracy, and it may be difficult to improve the communication speed and communication quality of the antenna.

An object of the present invention is to provide an adhesive capable of maintaining the adhesive strength between substrates even when repeatedly heated and controlling the gap of the air cavity with high accuracy. Another object of the present invention is to provide an antenna device using the above adhesive.

According to a broad aspect of the present invention, in a first substrate having a first metal portion on the surface and a second substrate having a second metal portion on the surface, the first metal portion and the second metal portion. An adhesive for adhering to a metal portion of the above material, wherein the rate of change in the number of peelings between substrates calculated by the following evaluation test 1 is 20% or less.

Evaluation test 1:
A first substrate having a first metal portion on the surface, a second substrate having a second metal portion on the surface, and an adhesive are prepared. The adhesive is placed on the first metal portion of the first substrate, and the second substrate is placed on the surface of the adhesive opposite to the first substrate side. The metal portion and the second metal portion are arranged so as to face each other. Then, the first substrate and the second substrate are adhered to each other by performing a reflow treatment under the reflow conditions specified in JEDEC J-STD-020 to obtain a laminated body. Using the obtained laminate, the number of times until the substrates are peeled off under the conditions conforming to JEDEC JESD22-B111 is measured and used as the number of times of peeling before heating. After that, the obtained laminate was reflowed four times under the reflow conditions specified by JEDEC J-STD-020, and the laminate after the reflow treatment was used to make a substrate under the conditions conforming to JEDEC JESD22-B111. The number of times until the gap is peeled off is measured and used as the number of times of peeling after heating. From the number of peels before and after heating, the rate of change in the number of peels is calculated by the following formula (1).

Rate of change in the number of peels = [(Number of peels before heating-Number of peels after heating) / Number of peels before heating] x 100 Formula (1)

In a specific aspect of the adhesive according to the present invention, the rate of change in adhesive strength between substrates calculated by the following evaluation test 2 is 10% or less.

Evaluation test 2:
A first substrate having a first metal portion on the surface, a second substrate having a second metal portion on the surface, and an adhesive are prepared. The adhesive is placed on the first metal portion of the first substrate, and the second substrate is placed on the surface of the adhesive opposite to the first substrate side. The metal portion and the second metal portion are arranged so as to face each other. Then, the first substrate and the second substrate are adhered to each other by performing a reflow treatment under the reflow conditions specified in JEDEC J-STD-020 to obtain a laminated body. Using the obtained laminate, the adhesive strength between the substrates is measured under the conditions conforming to MIL STD-883G, and the adhesive strength before heating is used. After that, the obtained laminated body was reflowed four times under the reflow conditions specified by JEDEC J-STD-020, and the laminated body after the reflow treatment was used as a substrate under the conditions compliant with MIL STD-883G. The adhesive strength between them is measured and used as the adhesive strength after heating. From the adhesive strength before and after heating, the rate of change in the adhesive strength is calculated by the following formula (2).

Rate of change in adhesive strength = [(Adhesive strength before heating-Adhesive strength after heating) / Adhesive strength before heating] x 100 Formula (2)

In a specific aspect of the adhesive according to the present invention, the first substrate is a glass epoxy substrate or a ceramic substrate, and the second substrate is a glass epoxy substrate, a ceramic substrate or a silicon substrate.

In certain aspects of the adhesive according to the invention, the first metal part is either made of copper or nickel / gold plated and the second metal part is made of copper. It is formed or formed by nickel / gold plating.

In certain aspects of the adhesive according to the present invention, the adhesive comprises metal particles.

In a specific aspect of the adhesive according to the present invention, the metal particles have a base material particles and a metal layer arranged on the surface of the base material particles.

In certain aspects of the adhesive according to the present invention, the metal layer is arranged on the surface of the second metal layer and the second metal layer arranged on the surface of the base particle. It has one metal layer, and the first metal layer is a solder layer.

According to a broad aspect of the present invention, a first substrate having a first metal portion on the surface, a second substrate having a second metal portion on the surface, the first substrate and the second substrate. The material of the adhesive portion is the above-mentioned adhesive, and the first metal portion and the second metal portion are adhered to each other by the adhesive portion. An antenna device is provided in which an air cavity is formed by the first substrate, the second substrate, and the adhesive portion.

In a specific aspect of the antenna device according to the present invention, the first substrate is a glass epoxy substrate or a ceramic substrate, and the second substrate is a glass epoxy substrate, a ceramic substrate or a silicon substrate.

In certain aspects of the antenna device according to the present invention, the first metal part is made of copper or nickel / gold plated, and the second metal part is made of copper. It is formed or formed by nickel / gold plating.

The adhesive according to the present invention comprises a first substrate having a first metal portion on the surface and a second substrate having a second metal portion on the surface, the first metal portion and the second metal portion. It is an adhesive for adhering to a metal part. In the adhesive according to the present invention, the rate of change in the number of peelings between the substrates calculated by the evaluation test 1 is 20% or less. Since the adhesive according to the present invention has the above-mentioned structure, the adhesive strength between the substrates can be maintained even when the adhesive is repeatedly heated, and the gap of the air cavity can be controlled with high accuracy. ..

FIG. 1 is a cross-sectional view showing a first example of metal particles that can be used in an adhesive according to an embodiment of the present invention. FIG. 2 is a cross-sectional view showing a second example of metal particles that can be used in the adhesive according to the embodiment of the present invention. FIG. 3 is a cross-sectional view showing an example of an antenna device using the adhesive according to the present invention. FIG. 4 is an enlarged cross-sectional view showing the bonded portion between the metal particles and the metal portion in the antenna device shown in FIG.

The details of the present invention will be described below.

(adhesive)
The adhesive according to the present invention comprises a first substrate having a first metal portion on the surface and a second substrate having a second metal portion on the surface, the first metal portion and the second metal portion. It is an adhesive for adhering to a metal part. In the adhesive according to the present invention, the rate of change in the number of peelings between substrates calculated by the following evaluation test 1 is 20% or less.

Evaluation test 1:
A first substrate having a first metal portion on the surface, a second substrate having a second metal portion on the surface, and an adhesive are prepared. The adhesive is placed on the first metal portion of the first substrate, and the second substrate is placed on the surface of the adhesive opposite to the first substrate side. The metal portion and the second metal portion are arranged so as to face each other. Then, the first substrate and the second substrate are adhered to each other by performing a reflow treatment under the reflow conditions specified in JEDEC J-STD-020 to obtain a laminated body. Using the obtained laminate, the number of times until the substrates are peeled off under the conditions conforming to JEDEC JESD22-B111 is measured and used as the number of times of peeling before heating. That is, the number of peelings before heating means the number of peelings before the laminate is heated. After that, the obtained laminate was reflowed four times under the reflow conditions specified by JEDEC J-STD-020, and the laminate after the reflow treatment was used to make a substrate under the conditions conforming to JEDEC JESD22-B111. The number of times until the gap is peeled off is measured and used as the number of times of peeling after heating. That is, the number of peels after heating means the number of peels after the laminate is heated four times. From the number of peels before and after heating, the rate of change in the number of peels is calculated by the following formula (1).

In the evaluation test 1, the adhesive is preferably arranged so that the gap between the substrates of the laminate (laminate before the reflow treatment) is 60 μm or more, and the adhesive is 850 μm or less. Is preferably arranged.

Since the adhesive according to the present invention has the above-mentioned structure, the adhesive strength between the substrates can be maintained even when the adhesive is repeatedly heated, and the gap of the air cavity can be controlled with high accuracy. ..

When an antenna device is obtained by adhering two substrates so as to form an air cavity (space) in the antenna using an adhesive, the antenna device may be repeatedly heated. In an antenna device obtained by using a conventional adhesive, the adhesive strength between two substrates may decrease due to repeated heating of the antenna device. If the adhesive strength between the two substrates is low, peeling or the like may occur between the substrates due to vibration or impact from the outside due to dropping or the like. If peeling or the like occurs between the substrates, it may not be possible to control the gap between the air cavities (spaces) with high accuracy, and it may be difficult to improve the communication speed and communication quality of the antenna.

On the other hand, since the adhesive according to the present invention has the above-mentioned structure, the adhesive strength between the substrates can be maintained even when the adhesive is repeatedly heated, and the space between the air cavities (spaces) can be maintained. (Gap) can be controlled with high precision. As a result, the communication speed and communication quality of the antenna can be further improved.

The adhesive according to the present invention comprises a first substrate having a first metal portion on the surface and a second substrate having a second metal portion on the surface, the first metal portion and the second metal portion. It is an adhesive for adhering to a metal part. The adhesive according to the present invention is an adhesive for adhering two substrates. The adhesive according to the present invention is preferably an adhesive for adhering metal portions on two substrates.

In the adhesive according to the present invention, the rate of change in the number of peelings between the substrates calculated by the evaluation test 1 is 20% or less. The rate of change in the number of peelings between the substrates calculated by the evaluation test 1 is preferably 15% or less, more preferably 10% or less. When the rate of change in the number of peelings between the substrates calculated by the evaluation test 1 is not more than the above upper limit, the adhesive strength between the substrates can be maintained even when repeatedly heated, and the gap between the air cavities can be made highly accurate. Can be controlled to.

In the evaluation test 1, the number of peelings before heating is preferably 50 times or more, more preferably 100 times or more. When the number of peelings before heating is equal to or greater than the above lower limit, the adhesive strength between the substrates can be maintained even when the substrates are repeatedly heated, and the gap between the air cavities can be controlled with high accuracy.

With the above adhesive, the rate of change in adhesive strength between substrates calculated by the following evaluation test 2 is preferably 10% or less, more preferably 3% or less. When the rate of change in the adhesive strength between the substrates calculated by the following evaluation test 2 is not more than the above upper limit, the adhesive strength between the substrates can be maintained even when repeatedly heated, and the gap between the air cavities is increased. It can be controlled with precision.

In the evaluation test 2, the adhesive is preferably arranged so that the gap between the substrates of the laminate (laminate before the reflow treatment) is 60 μm or more, and the adhesive is 850 μm or less. Is preferably arranged.

In the evaluation test 2, the adhesive strength before heating is preferably 1.5 kgf or more, more preferably 2.0 kgf or more. When the adhesive strength before heating is at least the above lower limit, the adhesive strength between the substrates can be maintained even when the substrates are repeatedly heated, and the gap of the air cavity can be controlled with high accuracy.

In the evaluation test 1 and the evaluation test 2, the first substrate is preferably a glass epoxy substrate or a ceramic substrate. In the evaluation test 1 and the evaluation test 2, the second substrate is preferably a glass epoxy substrate, a ceramic substrate, or a silicon substrate.

In the evaluation test 1 and the evaluation test 2, the first metal portion is preferably formed of copper or nickel / gold plating. In the evaluation test 1 and the evaluation test 2, the second metal portion is preferably formed of copper or nickel / gold plating.

The evaluation test 1 and the evaluation test 2 are performed to calculate the rate of change in the number of peelings and the rate of change in the adhesive strength. When the adhesive is actually used, it does not have to be treated under the conditions specified in the evaluation test 1 and the evaluation test 2. For example, when the above adhesive is actually used, the reflow treatment may not be performed under the reflow conditions specified in JEDEC J-STD-020.

The adhesive preferably contains metal particles from the viewpoint of maintaining the adhesive strength between the substrates even when repeatedly heated and controlling the gap of the air cavity with high accuracy. The adhesive may or may not contain components other than the metal particles. The adhesive may contain only the metal particles from the viewpoint of further maintaining the adhesive strength between the substrates even when repeatedly heated and controlling the gap of the air cavity with higher accuracy. It is preferably a particle group of a plurality of metal particles.

The above adhesive can bond two adherends, for example. The adherend is preferably a substrate, and more preferably a substrate having a metal portion on the surface. The adhesive is preferably used to bond the two substrates together. The adhesive is preferably used to bond two metal parts to each other. Further, the adhesive is preferably used to control the gap between the two substrates. The adhesive is preferably used to control the gap between the two substrates.

The above adhesive may be used for conductive connection or may not be used for conductive connection. The adhesive is preferably used in an antenna device. The adhesive is preferably used to form an air cavity. The adhesive is preferably used in the antenna device to form an air cavity. The adhesive is preferably used in the antenna device to keep the distance (gap) between the high-frequency substrate and the substrate constituting the antenna uniform and constant. The adhesive is preferably used in an antenna device to form an air cavity and improve the communication speed, communication quality, and the like of the antenna.

(Metal particles)
The adhesive according to the present invention preferably contains metal particles. The metal particles mean particles containing metal. The metal particles may have components other than metal. The metal particles preferably have a role of regulating the distance (gap) between two substrates, for example. It is preferable that the metal particles are not solder particles formed only by solder. The metal particles preferably have a base material particles and a metal layer arranged on the surface of the base material particles. The metal layer may have a single layer structure or a multi-layer structure having two or more layers.

The metal particles preferably have solder on the outer surface portion of the metal layer. It is preferable that the base material particles are not solder particles formed only by solder. When the metal particles are solder particles formed by solder in both the central portion and the outer surface portion of the metal layer, when the metal particles are repeatedly heated, the solder gets wet and spreads due to the heating, so that air is used. It can be difficult to control the cavity gap. When the metal particles are metal particles having a base material particles not formed by solder and a metal layer (solder layer) arranged on the surface of the base material particles, even if they are repeatedly heated, they may be heated repeatedly. Since it is possible to suppress excessive wetting and spreading of the solder due to heating, it is possible to control the gap of the air cavity with high accuracy. Therefore, it is preferable that the metal particles are not solder particles formed by solder. It is preferable that neither the central portion nor the outer surface portion of the metal layer of the metal particles is solder particles formed of solder.

The average particle size of the metal particles is not particularly limited. The average particle size of the metal particles can be appropriately selected according to the gap of the target air cavity. The average particle size of the metal particles may be, for example, 80 μm or more, or 900 μm or less.

The average particle size of the metal particles is preferably a number average particle size. The average particle size of the metal particles can be determined by, for example, observing 50 arbitrary metal particles with an electron microscope or an optical microscope, calculating the average value of the particle size of each metal particle, or measuring the particle size distribution by laser diffraction. Required by doing. In observation with an electron microscope or an optical microscope, the particle size of each metal particle is determined as the particle size in a circle-equivalent diameter. In observation with an electron microscope or an optical microscope, the average particle diameter of any 50 metal particles in the equivalent circle diameter is substantially equal to the average particle diameter in the equivalent diameter of the sphere. In the laser diffraction type particle size distribution measurement, the particle size of each metal particle is obtained as the particle size in the equivalent sphere diameter.

The coefficient of variation (CV value) of the particle size of the metal particles is preferably 10% or less, more preferably 5% or less. When the coefficient of variation of the particle size of the metal particles is not more than the above upper limit, the gap of the air cavity can be controlled with higher accuracy.

The coefficient of variation (CV value) can be measured as follows.

CV value (%) = (ρ / Dn) × 100
ρ: Standard deviation of particle size of metal particles Dn: Mean value of particle size of metal particles

The shape of the metal particles is not particularly limited. The shape of the metal particles may be spherical, non-spherical, flat or the like.

Next, a specific example of metal particles will be described with reference to the drawings.

FIG. 1 is a cross-sectional view showing a first example of metal particles that can be used in an adhesive according to an embodiment of the present invention.

The metal particle 1 shown in FIG. 1 has a base particle 2 and a metal layer 3 arranged on the surface of the base particle 2. The metal layer 3 covers the surface of the base particle 2. The metal particles 1 are coated particles in which the surface of the base particles 2 is coated with the metal layer 3.

The metal layer 3 has a second metal layer 3A and a solder layer 3B (first metal layer). The metal particles 1 include a second metal layer 3A between the base particles 2 and the solder layer 3B. Therefore, the metal particles 1 include the base material particles 2, the second metal layer 3A arranged on the surface of the base material particles 2, and the solder layer 3B arranged on the outer surface of the second metal layer 3A. To be equipped. As described above, the metal layer 3 may have a multi-layer structure of two or more layers, or may have a multi-layer structure.

FIG. 2 is a cross-sectional view showing a second example of metal particles that can be used in the adhesive according to the embodiment of the present invention.

The metal layer 3 of the metal particles 1 in FIG. 1 has a two-layer structure. The metal particles 1A shown in FIG. 2 have a solder layer 4 as a single metal layer. The metal particles 1A include a base particle 2 and a solder layer 4 arranged on the surface of the base particle 2.

The other details of the metal particles will be described below.

Base particle:
Examples of the base material particles include resin particles, inorganic particles excluding metal-containing particles, organic-inorganic hybrid particles, and metal-containing particles. The base material particles are preferably base particle particles excluding metal-containing particles, and more preferably inorganic particles excluding resin particles and metal-containing particles, or organic-inorganic hybrid particles. The base particle may be a core-shell particle having a core and a shell arranged on the surface of the core. The core may be an organic core, and the shell may be an inorganic shell.

Various organic substances are preferably used as the material for the resin particles. Examples of the material of the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethylmethacrylate and polymethylacrylate; polycarbonate, polyamide, and phenolformaldehyde. Resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polysulfone, polyphenylene oxide, polyacetal, polyimide, Examples thereof include polypropyleneimide, polyether ether ketone, polyether sulfone, divinylbenzene polymer, and divinylbenzene-based copolymer. Examples of the divinylbenzene-based copolymer and the like include a divinylbenzene-styrene copolymer and a divinylbenzene- (meth) acrylic acid ester copolymer. Since the hardness of the resin particles can be easily controlled within a suitable range, the material of the resin particles must be a polymer obtained by polymerizing one or more polymerizable monomers having an ethylenically unsaturated group. Is preferable.

When the resin particles are obtained by polymerizing a polymerizable monomer having an ethylenically unsaturated group, the polymerizable monomer having an ethylenically unsaturated group is a non-crosslinkable monomer. Examples thereof include crosslinkable monomers.

Examples of the non-crosslinkable monomer include styrene-based monomers such as styrene and α-methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; and methyl ( Meta) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) Alkyl (meth) acrylate compounds such as meta) acrylate and isobornyl (meth) acrylate; such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, and glycidyl (meth) acrylate. Oxygen atom-containing (meth) acrylate compound; nitrile-containing monomer such as (meth) acrylonitrile; vinyl ether compound such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate, etc. Acid vinyl ester compounds; unsaturated hydrocarbons such as ethylene, propylene, isoprene, and butadiene; halogens such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride, and chlorostyrene. Examples include containing monomers.

Examples of the crosslinkable monomer include tetramethylolmethanetetra (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanedi (meth) acrylate, trimethylolpropanetri (meth) acrylate, and dipentaerythritol hexa. (Meta) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, Polyfunctional (meth) acrylate compounds such as (poly) tetramethylene glycol di (meth) acrylate and 1,4-butanediol di (meth) acrylate; triallyl (iso) cyanurate, trimethyloltrimethylolate, divinylbenzene, diallyl. Examples thereof include phthalates, diallylacrylamides, diallyl ethers, and silane-containing monomers such as γ- (meth) acryloxipropyltrimethoxysilane, trimethoxysilylstyrene, and vinyltrimethoxysilane.

The term "(meth) acrylate" refers to acrylate and methacrylate. The term "(meth) acrylic" refers to acrylic and methacrylic. The term "(meth) acryloyl" refers to acryloyl and methacryloyl.

The resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, a method of swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles, and the like.

When the base material particles are inorganic particles other than metal-containing particles or organic-inorganic hybrid particles, examples of the inorganic substances for forming the base material particles include silica, alumina, barium titanate, zirconia, and carbon black. Be done. The inorganic substance is preferably not a metal. The particles formed of the silica are not particularly limited, but for example, after hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups to form crosslinked polymer particles, firing is performed if necessary. Examples include particles obtained by doing so. Examples of the organic-inorganic hybrid particles include organic-inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.

The organic-inorganic hybrid particles are preferably core-shell type organic-inorganic hybrid particles having a core and a shell arranged on the surface of the core. It is preferable that the core is an organic core. It is preferable that the shell is an inorganic shell. From the viewpoint of further effectively lowering the connection resistance between the electrodes, the base particle is preferably an organic-inorganic hybrid particle having an organic core and an inorganic shell arranged on the surface of the organic core. ..

Examples of the material of the organic core include the material of the resin particles described above.

Examples of the material of the inorganic shell include the above-mentioned inorganic substances as the material of the base particle. The material of the inorganic shell is preferably silica. The inorganic shell is preferably formed by forming a metal alkoxide into a shell-like material by a sol-gel method on the surface of the core and then firing the shell-like material. The metal alkoxide is preferably a silane alkoxide. The inorganic shell is preferably formed of silane alkoxide.

When the base material particles are metal-containing particles, examples of the metal that is the material of the metal-containing particles include silver, copper, nickel, silicon, gold, and titanium.

The particle size of the base particle is not particularly limited. The particle size of the base material particles can be appropriately selected according to the gap of the target air cavity. The particle size of the base particles may be, for example, 80 μm or more, or 900 μm or less.

The particle size of the base material particles indicates the diameter when the base material particles are spherical, and indicates the equivalent sphere diameter when the base material particles are not spherical.

The particle size of the base particle is preferably a number average particle size. The particle size of the base particle is determined by using a particle size distribution measuring device or the like. The particle size of the base particles is preferably determined by observing 50 arbitrary base particles with an electron microscope or an optical microscope and calculating an average value. In observation with an electron microscope or an optical microscope, the particle size of each substrate particle is determined as the particle size in a circle-equivalent diameter. In observation with an electron microscope or an optical microscope, the average particle diameter of any 50 substrate particles in the equivalent circle diameter is substantially equal to the average particle diameter in the equivalent diameter of the sphere. In the laser diffraction type particle size distribution measurement, the particle size of each base particle is determined as the particle size in the equivalent sphere diameter.

Metal layer:
The metal particles preferably have a base material particles and a metal layer arranged on the surface of the base material particles. The metal layer may have a single layer structure or a multi-layer structure having two or more layers. When the metal layer has a multi-layer structure of two or more layers, the metal particles include a base material particle, a second metal layer arranged on the surface of the base material particle, and the second metal layer. It is preferable to have a solder layer (first metal layer) arranged on the surface of the above. The metal particles preferably have solder on the outer surface portion of the metal layer.

The metal layer contains metal. The metal constituting the metal layer is not particularly limited. Examples of the metal include gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and alloys thereof. Further, as the metal, tin-doped indium oxide (ITO) and solder may be used. Only one kind of the above metal may be used, or two or more kinds may be used in combination. From the viewpoint of controlling the gap of the air cavity with higher accuracy and further increasing the adhesive strength between the substrates, the metal contained in the outermost metal layer is preferably solder.

The melting point of the base particles is preferably higher than the melting point of the metal layer. The melting point of the base particles preferably exceeds 160 ° C., more preferably exceeds 300 ° C., further preferably exceeds 400 ° C., and particularly preferably exceeds 450 ° C. The melting point of the base particles may be less than 400 ° C. The melting point of the base particles may be 160 ° C. or lower. The softening point of the base particles is preferably 260 ° C. or higher. The softening point of the base particles may be less than 260 ° C.

The metal particles may have a single layer of solder. The metal particles may have a plurality of metal layers (second metal layer and solder layer (first metal layer)). That is, in the above metal particles, two or more metal layers may be laminated. When the metal layer is two or more layers, it is preferable that the metal particles have solder on the outer surface portion of the metal layer.

The solder is preferably a metal having a melting point of 450 ° C. or lower (low melting point metal). The solder layer is preferably a metal layer having a melting point of 450 ° C. or lower (low melting point metal layer). The low melting point metal layer is a layer containing a low melting point metal. The solder in the metal particles is preferably a metal having a melting point of 450 ° C. or lower (low melting point metal). The low melting point metal means a metal having a melting point of 450 ° C. or lower. The melting point of the low melting point metal is preferably 300 ° C. or lower, more preferably 220 ° C. or lower.

The melting point of the low melting point metal can be determined by differential scanning calorimetry (DSC). Examples of the differential scanning calorimetry (DSC) device include "EXSTAR DSC7020" manufactured by SII.

Further, the solder in the metal particles preferably contains tin. The tin content in 100% by weight of the metal contained in the solder in the metal particles is preferably 30% by weight or more, more preferably 40% by weight or more, still more preferably 70% by weight or more, and particularly preferably 90% by weight or more. Is. When the content of tin contained in the solder in the metal particles is at least the above lower limit, the adhesive strength between the substrates can be further increased.

The tin content is determined by using a high-frequency inductively coupled plasma emission spectroscopic analyzer (“ICP-AES” manufactured by Horiba, Ltd.) or a fluorescent X-ray analyzer (“EDX-800HS” manufactured by Shimadzu Corporation). Can be measured.

When an adhesive containing metal particles having the solder on the outer surface of the metal layer is used to bond the metal parts formed on the two substrates, the solder is melted and joined to the metal part. Can be made to. For example, since the solder and the metal portion are likely to come into surface contact rather than point contact, the adhesive strength between the substrates can be further increased, and the contact area between the metal particles and the metal portion can be sufficiently increased. ..

The low melting point metal constituting the solder in the solder layer and the metal particles is not particularly limited. The low melting point metal is preferably tin or an alloy containing tin. Examples of the alloy include tin-silver alloy, tin-copper alloy, tin-silver-copper alloy, tin-bismuth alloy, tin-zinc alloy, tin-indium alloy and the like. The low melting point metal is preferably tin, tin-silver alloy, tin-silver-copper alloy, tin-bismuth alloy, or tin-indium alloy because it is excellent in wettability to metal parts.

The material constituting the solder in the solder layer and the metal particles is preferably a filler material having a liquidus line of 450 ° C. or lower based on JIS Z3001: welding terminology. Examples of the composition of the solder include a metal composition containing zinc, gold, silver, lead, copper, tin, bismuth, indium and the like.

In order to further increase the bonding strength between the solder in the metal particles and the metal part, the solder in the metal particles is nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, It may contain metals such as bismuth, manganese, chromium, molybdenum and palladium. Further, from the viewpoint of further increasing the adhesive strength between the solder in the metal particles and the metal portion, the solder in the metal particles preferably contains nickel, copper, or antimony. From the viewpoint of further increasing the adhesive strength between the solder and the metal portion in the metal particles, the content of these metals for increasing the adhesive strength is preferably 0.001 weight in 100% by weight of the solder in the metal particles. % Or more, preferably 1% by weight or less.

The metal particles preferably have a base material particles, a second metal layer arranged on the surface of the base material particles, and a solder layer arranged on the surface of the second metal layer.

The melting point of the second metal layer is preferably higher than the melting point of the solder layer. The melting point of the second metal layer preferably exceeds 220 ° C., more preferably exceeds 300 ° C., further preferably exceeds 400 ° C., further preferably exceeds 450 ° C., and particularly preferably exceeds 500 ° C. Most preferably, it exceeds 600 ° C. Since the solder layer has a low melting point, it is preferable that the solder layer melts when forming an air cavity. It is preferable that the second metal layer does not melt when forming the air cavity. The metal particles are preferably used by melting the solder, preferably by melting the solder layer, and are used by melting the solder layer and not melting the second metal layer. Is preferable. Since the melting point of the second metal layer is higher than the melting point of the solder layer, it is possible to melt only the solder layer without melting the second metal layer when forming the air cavity. ..

The absolute value of the difference between the melting point of the solder layer and the melting point of the second metal layer exceeds 0 ° C., preferably 5 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 30 ° C. or higher, particularly preferably. Is 50 ° C. or higher, most preferably 100 ° C. or higher.

The second metal layer contains metal. The metal constituting the second metal layer is not particularly limited. Examples of the metal include gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and alloys thereof. Further, tin-doped indium oxide (ITO) may be used as the metal. Only one kind of the above metal may be used, or two or more kinds may be used in combination.

The second metal layer is preferably a nickel layer, a palladium layer, a copper layer or a gold layer, more preferably a nickel layer, a gold layer or a copper layer, and even more preferably a copper layer. The metal particles preferably have a nickel layer, a palladium layer, a copper layer or a gold layer, more preferably have a nickel layer, a gold layer or a copper layer, and further preferably have a copper layer. By adhering the two substrates using an adhesive containing metal particles having these preferable metal layers, the gap of the air cavity can be controlled with even higher accuracy. Further, a solder layer can be formed more easily on the surface of these preferable metal layers.

The thickness of the metal layer is preferably 3.5 μm or more, more preferably 8 μm or more, preferably 80 μm or less, more preferably 65 μm or less, still more preferably 50 μm or less. When the thickness of the metal layer is at least the above lower limit and at least the above upper limit, the adhesive strength between the substrates can be further increased.

The thickness of the second metal layer is preferably 0.5 μm or more, more preferably 3 μm or more, preferably 30 μm or less, more preferably 25 μm or less, still more preferably 20 μm or less. When the thickness of the second metal layer is at least the above lower limit and at least the above upper limit, the adhesive strength between the substrates can be further increased.

The thickness of the solder layer (first metal layer) is preferably 3 μm or more, more preferably 5 μm or more, preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less. When the thickness of the solder layer is at least the above lower limit and at least the above upper limit, the adhesive strength between the substrates can be further increased.

The thickness of the metal layer, the thickness of the second metal layer, and the thickness of the solder layer can be measured by observing the cross section of the metal particles using, for example, a transmission electron microscope (TEM).

The method of forming the metal layer on the surface of the base material particles is not particularly limited. Examples of the method for forming the metal layer include electroless plating, electroplating, physical collision, mechanochemical reaction, physical vapor deposition or physical adsorption, and metal powder or metal powder. Examples thereof include a method of coating the surface of the substrate particles with a paste containing the binder and the binder. The method for forming the metal layer is preferably electroless plating, electroplating, or a method by physical collision. Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering. Further, in the above-mentioned physical collision method, for example, a seater composer (manufactured by Tokuju Kosakusho Co., Ltd.) or the like is used.

(Antenna device)
The antenna device according to the present invention includes a first substrate having a first metal portion on the surface, a second substrate having a second metal portion on the surface, the first substrate, and the second substrate. It is provided with an adhesive portion for adhering the above. In the antenna device according to the present invention, the material of the adhesive portion is the above-mentioned adhesive. In the antenna device according to the present invention, the first metal portion and the second metal portion are adhered to each other by the adhesive portion. In the antenna device according to the present invention, an air cavity is formed by the first substrate, the second substrate, and the adhesive portion.

The first substrate is preferably a glass epoxy substrate or a ceramic substrate. The second substrate is preferably a glass epoxy substrate, a ceramic substrate, or a silicon substrate. The substrate may be a high-frequency substrate, a substrate constituting an antenna, or the like. The first metal portion is preferably formed of copper or nickel / gold plating. The second metal portion is preferably formed of copper or nickel / gold plating. The first metal portion and the second metal portion may be formed of copper or may be formed of nickel / gold plating.

FIG. 3 is a cross-sectional view showing an example of an antenna device using the adhesive according to the present invention.

The antenna device 11 shown in FIG. 3 includes an adhesive portion that adheres the first substrate 12, the second substrate 13, and the first substrate 12 and the second substrate 13. The material of the adhesive portion is the above-mentioned adhesive. In the present embodiment, the material of the adhesive portion is metal particles 1. The adhesive portion is preferably formed of the metal particles.

The first substrate 12 has a plurality of first metal portions 12a on the surface (upper surface). The second substrate 13 has a plurality of second metal portions 13a on the surface (lower surface). The first metal portion 12a and the second metal portion 13a are bonded by one or a plurality of metal particles 1 (adhesive portion). In the antenna device 11, the air cavity 14 is formed by the first substrate 12, the second substrate 13, and the metal particles 1 (adhesive portion). The metal particles 1 (adhesive portion) keep the distance (gap) between the first substrate 12 and the second substrate 13 constant. The gap of the air cavity 14 is controlled by the metal particles 1 (adhesive portion).

The gap in the antenna device may be set according to the frequency band targeted by the antenna device.

The manufacturing method of the antenna device is not particularly limited. As an example of a method for manufacturing an antenna device, a method in which the above-mentioned adhesive is placed between the first metal portion and the second metal portion to obtain a laminate, and then the laminate is heated and pressurized. And so on. The pressurizing pressure is about 9.8 × 10 ⁴ Pa to 4.9 × 10 ⁶ Pa. The heating temperature is about 120 ° C. to 250 ° C. From the viewpoint of controlling the gap of the air cavity with higher accuracy, it is preferable not to pressurize during the manufacture of the antenna device. By not applying pressure during the manufacture of the antenna device, the solder layer of the molten metal particles does not excessively wet and spread to the first metal portion and the second metal portion, so that the gap of the air cavity is opened. It can be controlled with even higher precision.

FIG. 4 is an enlarged cross-sectional view showing the bonded portion between the metal particles and the metal portion in the antenna device shown in FIG.

As shown in FIG. 4, in the antenna device 11, after the solder layer 3B of the metal particles 1 is melted by heating the laminated body, the melted solder layer portion 3Ba becomes the first metal portion 12a and the second metal portion 12a. Sufficient contact with the metal portion 13a. By using the metal particles 1 in which the outermost layer is a solder layer, the metal particles 1 and the first metal portion 12a and the first metal portion 12a are compared with the case where the outermost layer is a metal particle such as nickel, gold or copper. The contact area with the second metal portion 13a can be increased, and the gap of the air cavity can be controlled with higher accuracy. Further, by using the metal particles 1 which are not the solder particles formed by the solder, the central portion and the outer surface portion of the metal layer are repeatedly heated as compared with the case where the solder particles formed by the solder are used. Even if this is done, it is possible to suppress excessive wetting and spreading of the solder due to heating, and it is possible to control the gap of the air cavity with even higher precision.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

(Metal particle 1)
50 parts by weight of divinylbenzene and 50 parts by weight of tetramethylolmethane tetraacrylate were copolymerized to prepare base particles (average particle size 240 μm, CV value 1.85%) as resin particles. The obtained base material particles were electroless nickel-plated, and a base nickel plating layer having a thickness of 0.3 μm was formed on the surface of the base material particles. Next, the base material particles on which the underlying nickel plating layer was formed were electrolytically copper-plated to form a copper layer having a thickness of 10 μm. Further, electroplating was performed to form a solder layer containing tin having a thickness of 25 μm. In this way, a copper layer having a thickness of 10 μm is formed on the surface of the base particle, and a solder layer having a thickness of 25 μm (tin: silver = 96.5% by weight: 3.5% by weight) is formed on the surface of the copper layer. ) Is formed in the metal particles 1 (average particle diameter 310 μm, CV value 2.85%).

(Metal particles 2)
Base particles (average particle diameter 260 μm, CV value 1.92%) which are resin particles were prepared in the same manner as the metal particles 1. The obtained base material particles were electroless nickel-plated, and a base nickel plating layer having a thickness of 0.3 μm was formed on the surface of the base material particles. Next, the base material particles on which the underlying nickel plating layer was formed were electrolytically copper-plated to form a copper layer having a thickness of 5 μm. Further, electroplating was performed to form a solder layer containing tin having a thickness of 20 μm. In this way, a copper layer having a thickness of 5 μm is formed on the surface of the base particle, and a solder layer having a thickness of 20 μm (tin: silver = 96.5% by weight: 3.5% by weight) is formed on the surface of the copper layer. ) Is formed in the metal particles 2 (average particle diameter 310 μm, CV value 2.76%).

(Metal particles 3)
Base particles (average particle diameter 210 μm, CV value 1.68%) which are resin particles were prepared in the same manner as the metal particles 1. The obtained base material particles were electroless nickel-plated, and a base nickel plating layer having a thickness of 0.3 μm was formed on the surface of the base material particles. Next, the base material particles on which the underlying nickel plating layer was formed were electrolytically copper-plated to form a copper layer having a thickness of 10 μm. Further, electroplating was performed to form a solder layer containing tin having a thickness of 40 μm. In this way, a copper layer having a thickness of 10 μm is formed on the surface of the base particle, and a solder layer having a thickness of 40 μm (tin: silver = 96.5% by weight: 3.5% by weight) is formed on the surface of the copper layer. ) Is formed in the metal particles 3 (average particle diameter 310 μm, CV value 3.21%).

(Metal particles X1)
A solder ball (“M705” manufactured by Senju Metal Industry Co., Ltd., tin: silver: copper = 96.5% by weight: 3% by weight: 0.5% by weight) formed of solder containing tin, silver and copper is used as a metal. The particles were X1 (average particle diameter 300 μm).

(Average particle size of metal particles)
The average particle size of the metal particles was measured by the method described above using a digital microscope (“VHX-5000” manufactured by KEYENCE CORPORATION).

(Example 1)
The obtained metal particles 1 themselves were used as an adhesive without using any adhesive components other than the metal particles 1.

(Manufacturing of antenna device A)
As the first substrate, a glass epoxy substrate having 20 metal portions (first metal portions) made of copper was prepared. As the second substrate, a glass epoxy substrate having 20 metal portions (second metal portions) made of copper was prepared. The metal part is a metal part for forming an antenna circuit. Flux (“WS-9160-M7” manufactured by Cookson Electronics Co., Ltd.) was applied onto the surface of the first metal portion of the first substrate. Next, the metal particles 1 were placed on the surface of the applied flux, and reflow treatment (heating temperature 250 ° C. and heating time 30 seconds) was performed to bond the metal particles 1 and the first metal portion. Next, a solder paste (“M705-GRN360-K2-V” manufactured by Senju Metal Industry Co., Ltd.) was applied onto the surface of the second metal portion of the second substrate. The adhesive structure of the first substrate, the metal particles 1, and the second substrate coated with the solder paste are arranged so that the first metal portion and the second metal portion face each other. , Reflow treatment (heating temperature 250 ° C. and heating time 30 seconds) was performed. In this way, the antenna device A in which the first metal portion and the second metal portion are adhered to each other via the adhesive portion formed by the metal particles 1 is produced.

(Manufacturing of antenna device B)
The antenna device is the same as the manufacturing method of the antenna device A, except that a glass epoxy board having 20 metal parts (second metal parts) formed by nickel / gold plating is used as the second board. B was prepared.

(Manufacturing of antenna device C)
Similar to the manufacturing method of the antenna device A, except that a glass epoxy substrate having 20 metal parts (second metal parts) formed by nickel / gold plating was used as the first substrate and the second substrate. The antenna device C was manufactured.

(Example 2)
Antenna devices A, B, and C were produced in the same manner as in Example 1 except that the metal particles 2 were used instead of the metal particles 1 as the adhesive.

(Example 3)
Antenna devices A, B, and C were produced in the same manner as in Example 1 except that the metal particles 3 were used instead of the metal particles 1 as the adhesive.

(Comparative Example 1)
Antenna devices A, B, and C were produced in the same manner as in Example 1 except that the metal particles X1 were used instead of the metal particles 1 as the adhesive.

(Evaluation)
(1) Rate of change in the number of peelings between substrates (evaluation test 1)
(1-1) The obtained metal particles (adhesive) were prepared. Further, a first substrate (glass epoxy substrate) having a first metal portion formed of copper on the surface was prepared. A second substrate (glass epoxy substrate) having a second metal portion formed of copper on the surface was prepared. Using the prepared metal particles (adhesive), the first substrate, and the second substrate, the rate of change in the number of peelings between the substrates was calculated by the method described above.

(1-2) The obtained metal particles (adhesive) were prepared. Further, a first substrate (glass epoxy substrate) having a first metal portion formed of copper on the surface was prepared. A second substrate (glass epoxy substrate) having a second metal portion formed by nickel / gold plating on the surface was prepared. Using the prepared metal particles (adhesive), the first substrate, and the second substrate, the rate of change in the number of peelings between the substrates was calculated by the method described above.

(1-3) The obtained metal particles (adhesive) were prepared. Further, a first substrate (glass epoxy substrate) having a first metal portion formed by nickel / gold plating on the surface was prepared. A second substrate (glass epoxy substrate) having a second metal portion formed by nickel / gold plating on the surface was prepared. Using the prepared metal particles (adhesive), the first substrate, and the second substrate, the rate of change in the number of peelings between the substrates was calculated by the method described above.

[Criteria for determining the rate of change in the number of peelings between substrates]
〇: The rate of change in the number of peels is 20% or less ×: The rate of change in the number of peels exceeds 20%

(2) Rate of change in adhesive strength between substrates (evaluation test 2)
(2-1) The obtained metal particles (adhesive) were prepared. Further, a first substrate (glass epoxy substrate) having a first metal portion formed of copper on the surface was prepared. A second substrate (glass epoxy substrate) having a second metal portion formed of copper on the surface was prepared. Using the prepared metal particles (adhesive), the first substrate and the second substrate, the rate of change in the adhesive strength between the substrates was calculated by the method described above.

(2-2) The obtained metal particles (adhesive) were prepared. Further, a first substrate (glass epoxy substrate) having a first metal portion formed of copper on the surface was prepared. A second substrate (glass epoxy substrate) having a second metal portion formed by nickel / gold plating on the surface was prepared. Using the prepared metal particles (adhesive), the first substrate and the second substrate, the rate of change in the adhesive strength between the substrates was calculated by the method described above.

(2-3) The obtained metal particles (adhesive) were prepared. Further, a first substrate (glass epoxy substrate) having a first metal portion formed by nickel / gold plating on the surface was prepared. A second substrate (glass epoxy substrate) having a second metal portion formed by nickel / gold plating on the surface was prepared. Using the prepared metal particles (adhesive), the first substrate and the second substrate, the rate of change in the adhesive strength between the substrates was calculated by the method described above.

[Criteria for determining the rate of change in adhesive strength between substrates]
〇: Change rate of adhesive strength is 10% or less ×: Change rate of adhesive strength exceeds 10%

(3) Gap controllability With respect to the obtained five antenna devices A, the thickness of the air cavity was measured using a stereomicroscope (“SMZ-10” manufactured by Nikon Corporation), and the air cavity in the five antenna devices A was measured. The average thickness of each was calculated. From the difference between the maximum value of the average thickness and the minimum value of the average thickness, the gap controllability was determined according to the following criteria. The same evaluation was performed on the obtained antenna devices B and C.

[Gap controllability criteria]
◯: The difference between the maximum value of the average thickness of the air cavity and the minimum value of the average thickness is less than 10 μm ×: The difference between the maximum value of the average thickness of the air cavity and the minimum value of the average thickness is 10 μm or more.

The results are shown in Table 1 below.

The same tendency was observed even when a ceramic substrate or a silicon substrate was used instead of the glass epoxy substrate as the first substrate and the second substrate.

1,1A ... Metal particles 2 ... Base particles 3 ... Metal layer 3A ... Second metal layer 3B ... Solder layer (first metal layer)
3Ba ... Solder layer part 4 ... Solder layer 11 ... Antenna device 12 ... First substrate 12a ... First metal part 13 ... Second substrate 13a ... Second metal part 14 ... Air cavity

Claims

For adhering the first metal portion and the second metal portion in a first substrate having a first metal portion on the surface and a second substrate having a second metal portion on the surface. It is an adhesive and
An adhesive having a rate of change in the number of peelings between substrates calculated by the following evaluation test 1 of 20% or less.
Evaluation test 1:
A first substrate having a first metal portion on the surface, a second substrate having a second metal portion on the surface, and an adhesive are prepared. The adhesive is placed on the first metal portion of the first substrate, and the second substrate is placed on the surface of the adhesive opposite to the first substrate side. The metal portion and the second metal portion are arranged so as to face each other. Then, the first substrate and the second substrate are adhered to each other by performing a reflow treatment under the reflow conditions specified in JEDEC J-STD-020 to obtain a laminated body. Using the obtained laminate, the number of times until the substrates are peeled off under the conditions conforming to JEDEC JESD22-B111 is measured and used as the number of times of peeling before heating. After that, the obtained laminate was reflowed four times under the reflow conditions specified by JEDEC J-STD-020, and the laminate after the reflow treatment was used to make a substrate under the conditions conforming to JEDEC JESD22-B111. The number of times until the gap is peeled off is measured and used as the number of times of peeling after heating. From the number of peels before and after heating, the rate of change in the number of peels is calculated by the following formula (1).
Rate of change in the number of peels = [(Number of peels before heating-Number of peels after heating) / Number of peels before heating] x 100 Equation (1)
The adhesive according to claim 1, wherein the rate of change in adhesive strength between substrates calculated by the following evaluation test 2 is 10% or less.
Evaluation test 2:
A first substrate having a first metal portion on the surface, a second substrate having a second metal portion on the surface, and an adhesive are prepared. The adhesive is placed on the first metal portion of the first substrate, and the second substrate is placed on the surface of the adhesive opposite to the first substrate side. The metal portion and the second metal portion are arranged so as to face each other. Then, the first substrate and the second substrate are adhered to each other by performing a reflow treatment under the reflow conditions specified in JEDEC J-STD-020 to obtain a laminated body. Using the obtained laminate, the adhesive strength between the substrates is measured under the conditions conforming to MIL STD-883G, and the adhesive strength before heating is used. After that, the obtained laminated body was reflowed four times under the reflow conditions specified by JEDEC J-STD-020, and the laminated body after the reflow treatment was used as a substrate under the conditions compliant with MIL STD-883G. The adhesive strength between them is measured and used as the adhesive strength after heating. From the adhesive strength before and after heating, the rate of change in the adhesive strength is calculated by the following formula (2).
Rate of change in adhesive strength = [(Adhesive strength before heating-Adhesive strength after heating) / Adhesive strength before heating] x 100 formula (2)
The first substrate is a glass epoxy substrate or a ceramic substrate.
The adhesive according to claim 1 or 2, wherein the second substrate is a glass epoxy substrate, a ceramic substrate, or a silicon substrate.
The first metal portion is formed of copper or nickel / gold plating.
The adhesive according to any one of claims 1 to 3, wherein the second metal portion is formed of copper or nickel / gold plating.
The adhesive according to any one of claims 1 to 4, which contains metal particles.
The adhesive according to claim 5, wherein the metal particles have a base material particles and a metal layer arranged on the surface of the base material particles.
The metal layer has a second metal layer arranged on the surface of the base material particles and a first metal layer arranged on the surface of the second metal layer.
The adhesive according to claim 6, wherein the first metal layer is a solder layer.
A first substrate having a first metal portion on its surface,
A second substrate having a second metal portion on its surface,
It is provided with an adhesive portion for adhering the first substrate and the second substrate.
The material of the adhesive portion is the adhesive according to any one of claims 1 to 7.
The first metal portion and the second metal portion are adhered to each other by the adhesive portion.
An antenna device in which an air cavity is formed by the first substrate, the second substrate, and the adhesive portion.
The first substrate is a glass epoxy substrate or a ceramic substrate.
The antenna device according to claim 8, wherein the second substrate is a glass epoxy substrate, a ceramic substrate, or a silicon substrate.
The first metal portion is formed of copper or nickel / gold plating.
The antenna device according to claim 8 or 9, wherein the second metal portion is formed of copper or nickel / gold plating.