JP3116726B2 - Resin composition with excellent vibration damping properties - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive resin composition having excellent vibration damping properties and fatigue resistance. For example, the present invention relates to an automobile body, particularly doors, hoods, trunk lids, pillars, floors, roofs, side member fronts. The present invention relates to an adhesive resin composition having excellent vibration damping properties and fatigue resistance, which can be used for bonding structures such as a side member rear, a hood rich reinforcement and a side sill.

[0002]

2. Description of the Related Art Conventionally, epoxy resin-based adhesives have been widely used as structural adhesives in, for example, automobile manufacturing processes because of their excellent adhesiveness and durability.
In particular, it is widely used for the purpose of eliminating spot welding to a hemming portion such as a hood, a trunk lid and a door, and a flange portion such as a side sill and a pillar, and providing rigidity and vibration damping.

In particular, as a technique for imparting vibration damping properties to a structure, a damping steel sheet in which a resin is sandwiched between steel sheets, a joint structure using a damping adhesive, and a damping material are applied. An outer panel or the like using a panel reinforcing plate is used. All of these technologies are intended to convert mechanical vibration characteristics into thermal energy by viscous elastic characteristics peculiar to resin, and there is a limit in control of vibration damping characteristics.

In consideration of the damping characteristics of an automobile, the frequency of the vibration to be attenuated varies in various ways depending on the source and location of the vibration, so that controlling the damping characteristics is regarded as an important technique. As a technique for achieving control of this vibration damping property, a polymer material is filled with piezoelectric particles and conductive particles, vibration energy is extracted as an electric potential by piezoelectric conversion, and a current is passed through the conductive path formed by the conductive particles to produce joules. A polymer composite vibration damping material to be consumed as heat has been devised.
96 (8) 863-67 (1988), The Ceramic Society of Japan 99 (11) 1135-1137 (19)
91), POLYMER PREPRINT, JAPAN
N VOL. 40 NO. 4).

[0005]

However, as described above, in the composite vibration damping material in which the polymer material is filled with the piezoelectric particles and the conductive particles, a large amount of the polymer material is required in order to obtain a desired vibration damping effect. Must be filled.
This adversely affects the physical properties of the composite damping material. For example, when an epoxy resin is used as a polymer material, a large amount of piezoelectric particles causes a starting point of destruction in the epoxy matrix when an external stress is applied. Has the disadvantage of lowering

On the other hand, if the piezoelectric particle loading is too large, the paste viscosity of the epoxy resin composition before curing is significantly increased, which adversely affects the wetting on the metal surface, lowering the bonding strength and insufficient wetting at the bonding interface. This causes a problem that corrosion is easily generated.

For this reason, the present inventor has proposed an epoxy resin which is liquid at room temperature, conductive particles such as carbon black and metal particles, piezoelectric particles, and an acrylic powder resin which is wettable to the epoxy resin. An adhesive as an essential component has been proposed (Japanese Patent Application No. 5-01468). This adhesive swells when the acrylic powdery resin absorbs the epoxy resin,
As a result, conductive particles and piezoelectric particles are gathered around the swollen acrylic powdery resin to form a layer having a function of converting vibration energy into heat energy, thereby improving the wetting characteristics and T peel strength. Demonstrate damping without lowering.

[0008] However, the adhesive proposed above uses carbon black as the conductive particles,
Since the carbon black itself does not have high conductivity, there is a disadvantage that the conductivity of the resin composition after thermosetting is unstable and the reliability of the desired vibration damping property is low. Further, when metal particles are filled as conductive particles, the metal particles are easily dispersed and hardly aggregated in the epoxy resin, so it is necessary to add a large amount to the epoxy resin, and the fatigue strength is significantly reduced. There was a disadvantage.

Accordingly, an object of the present invention is to provide an adhesive resin composition having excellent vibration damping properties without deteriorating the wettability and adhesion to an adherend as an epoxy resin composition. is there.

[0010]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that a liquid epoxy resin composition at room temperature, a heat-activated curing agent, and a metal film on the surface. When an acrylic resin, which has extremely high swelling properties with respect to powdery resin and liquid epoxy resin, and piezoelectric particles are mixed as essential components, wetting and adhesion to the adherend as an epoxy resin composition It has been found that an adhesive resin composition having excellent vibration damping properties can be obtained without lowering the viscosity, and the present invention has been achieved.

An object of the present invention is to provide a liquid epoxy resin (A) having at least one epoxy group in a molecule, which is liquid at room temperature (A), and a heat-activated curing agent (B).
And a powdered resin (C) 1 having a metallization ratio in the range of 5 to 70% and a metal film formed in the range of 5 to 100 μm in particle diameter.
As essential components, 5 parts by weight, 80 to 250 parts by weight of piezoelectric particles (D), and 5 to 40 parts by weight of an acrylic powdery resin (E) having a swelling property with respect to a liquid epoxy resin. This has been achieved by an adhesive resin composition characterized in that:

Hereinafter, the present invention will be described in more detail. The adhesive resin composition of the present invention is obtained by heating the powdery resin at 90 to 150 ° C. so that the swellable powdery particulate resin absorbs the epoxy resin, and as a result, the surface of the swellable particulate resin becomes a metal film around the swellable particulate resin. This has an important feature in forming a layer having a function of converting vibration energy into heat energy by gathering together piezoelectric particles. In other words, the formed layer composed of powdered resin, piezoelectric particles, and epoxy resin, whose surface has a vibration-damping property, is effectively distributed in the epoxy matrix, so that the damping property and the adhesive strength are reduced without lowering the adhesive strength. It is possible to exhibit vibration.

The epoxy resin used in the present invention can be appropriately selected from known epoxy resins as long as it is a liquid resin having at least one epoxy group in one molecule. Resins can be used by dissolving them in a liquid epoxy resin. Specific examples thereof include diglycidyl ethers, aliphatic diglycidyl ethers, such as condensates of ordinary bisphenol A and epichlorohydrin and condensates of bisphenol F and epichlorohydrin, alicyclic epoxides, phthalic acid derivatives and epichlorohydrin. Diglycidyl esters, hydantoin-based epoxy resins, novolak-type epoxy resins, glycidylamine-type epoxy resins, and the like. These resins can be used alone or as a mixture of two or more.

The heat-activated curing agent can be a usual curing agent which exerts a curing effect by heating, and examples thereof include dicyandiamide, 4,4'-diaminodiphenylsulfone and 2-n-pentadiethylimidazole. Imidazole derivatives, isophthalic acid dihydrazide, N,
N'-dialkyl urea derivatives, N, N'-dialkyl thiourea derivatives, alkylaminophenol derivatives, melamine, guanamine and the like. These curing agents are appropriately added to the composition at an arbitrary weight ratio depending on the epoxy resin equivalent and curing conditions to be used, but it is usually preferably 1 to 15 parts by weight based on 100 parts by weight of the epoxy resin.

[0015] Imidazole derivatives, N, N'-dialkylurea derivatives and alkylaminophenol derivatives can also be used as accelerators. The necessary and sufficient amount of the curing agent and the accelerator for curing can be easily determined by conducting a test in advance.

The acrylic powdery resin used in the present invention is a spherical powdery polymer obtained by emulsion polymerization and suspension polymerization, and absorbs an epoxy resin and oil on a steel plate to be bonded by heating. Have the property of As this polymer, there is a polymer containing halogen such as polyvinyl chloride (PVC). However, in the case of a powdery resin containing halogen, chlorine gas is generated at the time of high heat treatment and the corrosion of metal is promoted. Therefore, it is necessary to use a halogen-free powder resin.

Examples of the acrylic powder resin include a fine powder (meth) acrylate polymer. (Meta)
The monomer constituting the acrylate-based polymer is not particularly limited, and any monomer can be used as long as a powdery polymer can be obtained. For example, methyl methacrylate,
Alkyl methacrylates such as ethyl methacrylate and stearyl methacrylate, alkyl acrylates such as methyl acrylate and butyl acrylate,
Alkoxy (meth) acrylates such as butoxyethyl (meth) acrylate, hydroxyl-containing (meth) acrylates such as glycidyl methacrylate, allyl glycidyl ether, and hydroxylpropyl methacrylate; amino-containing (meth) acrylates such as dimethylaminoethyl methacrylate; and acrylonitrile and N
-Methylol acrylamide and the like. Among these, epoxy group-containing (meth) acrylates such as glycidyl methacrylate and allyl glycidyl ether can be preferably used.

These (meth) acrylate monomers can be used as a polymer composed of one component, or as a copolymer using two or more monomers, and a powder resin can be obtained by graft polymerization. it can. Further, by mixing polymers obtained from different monomers, it can be used as a powdery resin. The grain system of this powder is 10-50
It is preferably in the range of μm. When the particle size exceeds 50 μm, the powdery resin is less likely to be thermally cured, and the conductivity is poor. Conversely, if the thickness is less than 10 μm, the powder properties deteriorate, which hinders production and mixing.

The acrylic powder resin used in the present invention has a gel fraction of 50% or less. The term "gel fraction" as used herein means a value of an extraction residue when the acrylic powder is dissolved in methyl ethyl ketone at room temperature. If the gel fraction is more than 50%, the swelling ability of the powdered resin is low, and the desired vibration damping properties cannot be obtained after thermosetting, and the properties of the entire composition become brittle, which adversely affects the peel strength. The preferred gel fraction of the acrylic powder resin used in the present invention is from 0 to 50%, but from the viewpoint of economic efficiency, a gel fraction of from 5 to 50% is advantageous.

The piezoelectric particles used in the present invention are not particularly limited, and any type may be used as long as the piezoelectric effect is remarkable and practical. Typical examples of the piezoelectric particles include quartz, lithium niobate, barium titanate, lead titanate, lead zirconate titanate, lead metaniobate, polyvinylidene fluoride, and the like. It is preferable to use a solid solution in which lanthanum is added to lead zirconate titanate or lead zirconate titanate.

When carbon black is used as conductive particles in place of the metal-coated powdery resin used in the present invention, the carbon black itself does not have high conductivity. The composition lacks conductivity,
It is difficult to develop desired damping properties. Further, when the metal particles are filled, the metal particles are easily dispersed and hardly aggregated in the epoxy resin. Therefore, it is necessary to add the metal particles in an amount of 50 parts by weight or more based on 100 parts by weight of the epoxy resin. Is significantly reduced. For this reason, a metal-coated powdery resin which has excellent conductivity and exhibits desired vibration damping properties at a low weight ratio is optimal.

The powdery resin coated with a metal film according to the present invention is not particularly limited as long as it is in the form of fine powder. Fluororesin, epoxy resin, nylon resin, acrylic resin,
Cross-linked acrylic resin, polystyrene, cross-linked polystyrene,
Polyethylene, phenolic resin, guanamine resin, silicone resin and the like can be used, but it is particularly preferable to use crosslinked acrylic resin and crosslinked polystyrene having a heat resistance temperature of 180 ° C. or higher. 180 temperature
If the temperature is lower than ℃, the powdery resin is thermally deformed at the time of baking the coating film, so that a desired electrical conductivity cannot be obtained in the resin composition after thermosetting. The particle size of the powdery resin used in the present invention is 5 to 5.
It is preferably in the range of 100 μm, especially 10 to 5 μm.
It is preferably in the range of 0 μm. If the particle size is less than 5 μm, the powder property becomes poor, which hinders the production and mixing. Conversely, if the particle size exceeds 100 μm, the curability of the adhesive composition becomes poor, so the cured product Not only shows brittleness but also adversely affects conductivity.

The method of applying a metal film to the metal-coated powdery resin used in the present invention may be any method as long as an appropriate metal film can be formed on the surface of the powdered resin. It is preferable to use the following dropping method. First, an organic film-forming treatment is performed using γ-aminopropyltriethoxysilane, and then a catalyst is applied in an aqueous palladium solution to be subjected to plating.

The nickel film is formed on the powdery resin by a dropping method. 300 mL of a plating stock solution containing 4 to 6 g / L of nickel ions is put into a reaction tank, adjusted to a pH range of 6.5 to 7.0, heated to 65 ° C., charged with a powdery resin into the solution, and then added with sulfuric acid. Using a plating solution composed of nickel hexahydrate, disodium hydrogen phosphate monohydrate, malic acid and succinic acid as a stock solution (composition ratio is shown in Table 3), and different concentrations obtained by mixing with distilled water. The plating solution is added dropwise over 1 hour while stirring to reduce and deposit films having different amounts of nickel on the surface of the powder resin.

The deposited film is a nickel-phosphorus alloy film, and the amount of nickel-phosphorus deposited on the powdery resin is expressed as a percentage of nickel-phosphorus relative to the total weight after plating, washing with water, drying with hot air, and plating. This is defined as the metallization ratio. The metallization ratio is preferably in the range of 5 to 70%. If the amount of nickel-phosphorus is less than 5%, the conductivity after curing of the adhesive becomes insufficient. Conversely, if it exceeds 70%, the affinity between the epoxy resin and the powdered resin having a metal film is reduced, which causes the physical properties to be reduced.

Next, the composition ratio of the vibration damping resin composition of the present invention will be described. The composition of the vibration-damping resin composition of the present invention comprises 100 parts by weight of a room-temperature liquid epoxy resin (A) having at least one epoxy group in a molecule, a heat-activated curing agent (B), Metallization ratio in the range of 5 to 70% Metallized powdery resin (C) in the range of 5 to 100 μm in particle size of 5 to 100 μm and acrylic having swelling property with respect to liquid epoxy resin Based resin (D) 5
It is characterized by containing 40 parts by weight and 80 to 250 parts by weight of piezoelectric particles (E) as essential components.

When the amount of the powdered resin (C) formed into a metal film is less than 1 part by weight with respect to 100 parts by weight of the epoxy resin,
The desired conductivity cannot be obtained. Conversely, if it exceeds 5 parts by weight, the whole composition becomes brittle, so that the peel strength decreases. When the amount of the acrylic powder resin having swelling property with respect to the epoxy resin is less than 5 parts by weight, the desired vibration damping property is hardly obtained because the particulate resin itself has a particle size distribution. vice versa,
If the amount of the swellable powdery resin exceeds 40 parts by weight, the intended peel strength cannot be obtained due to the filling effect of the powdery resin.

When the amount of the piezoelectric particles is less than 80 parts by weight,
The desired damping effect cannot be obtained. Conversely, if the amount exceeds 250 parts by weight, the viscosity of the epoxy resin composition in a paste state before curing is significantly increased, so that the wettability is reduced and corrosion is easily generated.

In the present invention, the main component epoxy resin (A)
Instead, a flexible epoxy resin such as a rubber-modified epoxy resin or a urethane-modified epoxy resin may be used as necessary. In addition, the above (A), (B), (C),
In addition to the components (D) and (E), fillers such as talc, calcium carbonate, and silica powder, and additives such as elastomers may be appropriately added.

[0030]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 Epicoat 828 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.) as the (A) component epoxy resin, dicyandiamide as the (B) component, and a metal film of (C) component Powder resin obtained by forming a metal film on Fine Pearl PB-3000 (trade name, manufactured by Sumitomo Chemical Co., Ltd.) which is a crosslinked polystyrene having an average particle size of 40 μm and a heat resistance temperature of 200 ° C. ,
PZT-5A (trade name, manufactured by Fuji Ceramics Co., Ltd.) as the piezoelectric particles of the component (D), and an acrylic powdery resin of the component (E) obtained by suspension polymerization having a molecular weight of about 800,000 and a particle size of 30 μm. Methyl methacrylate (MMA) and glycidyl methacrylate (GMA) copolymer (MM
A / GMA = 90/10, gel fraction = 10%), using Hiker CTBN1300 × 13 (trade name, manufactured by Ube Industries, Ltd.) as a liquid rubber and using three rolls in the amounts shown in Table 1. The mixture was kneaded for 30 minutes to obtain an adhesive resin composition.

Example 2 The component (C) in Example 1 was applied to Fine Pearl PB-3002 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), a crosslinked polystyrene having an average particle size of 30 μm and a heat resistance temperature of 200 ° C. To the resin subjected to the same metallization treatment as in Example 1, the component (E) was added with methyl methacrylate (MM) obtained by suspension polymerization using a crosslinking agent having a molecular weight of about 400,000 and a particle size of 30 μm.
An adhesive resin composition was obtained in exactly the same manner as in Example 1, except that the copolymer of A) and glycidyl methacrylate (GMA) was used (MMA / GMA = 95/15, gel fraction 35%). .

Example 3 The component (A) in Example 1 was replaced with R1309 (trade number manufactured by AC R Co., Ltd.), and the fraction of the component (E) was changed to 2
An adhesive resin composition was obtained in exactly the same manner as in Example 1 except that the amount was changed to 8 parts by weight.

Example 4 An adhesive resin composition was obtained in the same manner as in Example 1 except that the fraction of the component (D) was changed to 38 parts by weight.

Example 5 The component (D) in Example 1 was replaced with PZT-8 (trade name of Fuji Ceramics Co., Ltd.), and the fraction was 45.
An adhesive resin composition was obtained in exactly the same manner as in Example 1 except that the amount was changed to parts by weight.

COMPARATIVE EXAMPLE 1 The procedure of Example 1 was repeated except that the resin (P) × 568 (trade name of Mitsui Petrochemical Co., Ltd.) was used as the non-swellable powdery resin in place of the component (E) in Example 1. In the same manner as in Example 1, an adhesive resin composition was obtained.

Comparative Example 2 An adhesive resin composition was prepared in the same manner as in Example 1 except that the amount of the component (D) was changed as shown in Table 1 and the component (E) was not added. I got something.

Comparative Examples 3 and 4 An adhesive resin composition was obtained in the same manner as in Example 1 except that the amount of the component (E) was changed as shown in Table 1.

Comparative Examples 5, 6, 7 An adhesive resin composition was obtained in the same manner as in Example 1 except that the amount of the component (D) was changed as shown in Table 1.

Comparative Examples 8, 9, 10 An adhesive resin composition was obtained in the same manner as in Example 1 except that the amount of the component (C) was changed as shown in Table 1.

Next, the acrylic powdery resin gel fraction,
The particle size and the metallization ratio of the metal-coated powdery resin will be described (Tables 2, 3, and 4).

Example 6 In Example 1, the component (E) was replaced with a molecular weight of about 700,000 and a particle size of 4
A copolymer of methyl methacrylate (MMA) and glycidyl methacrylate (GMA) obtained using suspension polymerization with a cross-linking agent of 0 μm (MMA / GMA = 95/5,
An adhesive resin composition was obtained in exactly the same manner as in Example 1, except that the gel fraction was changed to 45%.

Example 7 In Example 1, the component (E) was replaced with a molecular weight of about 750,000 and a particle size of 4
Methyl methacrylate (MMA) and glycidyl methacrylate (GMA) copolymer (MMA / GMA = 80/2) obtained by suspension polymerization using a 0 μm crosslinking agent
(0, gel fraction 38%), except that the adhesive resin composition was obtained in the same manner as in Example 1.

Comparative Example 11 In Example 1, the component (E) was changed to a molecular weight of about 550,000 and a particle size of 4
Methyl methacrylate (MMA) and glycidyl methacrylate (GMA) copolymer (MMA / GMA = 75/2) obtained by suspension polymerization using a 0 μm crosslinking agent
5, the gel fraction was 55%), and an adhesive resin composition was obtained in exactly the same manner as in Example 1.

Comparative Example 12 In Example 1, the component (E) was changed to a molecular weight of about 650,000 and a particle size of 4
Methyl methacrylate (MMA) and glycidyl methacrylate (GMA) copolymer (MMA / GMA = 75/2) obtained using suspension polymerization with a 5 μm crosslinker
5, the gel fraction was 85%), and an adhesive resin composition was obtained in exactly the same manner as in Example 1.

Example 8 The component (C) in Example 1 was subjected to the same metallization treatment as in Example 1 on Fine Pearl 3000F (trade name of Sekisui Chemical Co., Ltd.) having an average particle diameter of 6 μm and a heat resistance temperature of 200 ° C. MMA having a gel fraction of 10% obtained by suspension polymerization of a resin having a molecular weight of about 700,000 and a particle size of 40 μm.
Of styrene and GMA (MMA / GMA = 80/20)
The adhesive resin composition was obtained in exactly the same manner as in Example 1 except that each was replaced by The proportions of the components C and D were the same as in Example 1 and Example 1. This is constant throughout Example 9 and Comparative Examples 13, 14 and 15 below.

Example 9 The same metallization treatment as in Example 1 was carried out by applying (C) component in Example 1 to Fine Pearl PB-3005 (trade name, manufactured by Sekisui Chemical Co., Ltd.) with an average particle size of 50 μm and a heat resistance of 200 ° C. And the component (E) having a molecular weight of about 70
10% gel fraction obtained by suspension polymerization with a particle size of 40 μm
Copolymer of MMA and GMA (MMA / GMA = 60)
/ 40) was obtained in the same manner as in Example 1 except that the adhesive resin composition was replaced.

Comparative Example 13 In Example 1, the component (C) was replaced with a powdery resin obtained by forming a metal film on Techpolymer SBP (trade name of Sekisui Chemical Co., Ltd.) having an average particle size of 3 μm and a heat resistance temperature of 200 ° C. Except for this, the adhesive resin composition was obtained in the same manner as in Example 8.

Comparative Example 14 In Example 1, the component (C) was used as a powder resin obtained by forming a metal film on Fine Pearl PB-3012 (trade name of Sekisui Chemical Co., Ltd.) having an average particle size of 200 μm and a heat resistance temperature of 200 ° C. Except having changed, the adhesive resin composition was obtained exactly like Example 8.

Comparative Example 15 In Example 1, the component (C) was used as a powdery resin obtained by forming a metal film on Fine Pearl PB-3013 (trade name of Sekisui Chemical Co., Ltd.) having an average particle size of 400 μm and a heat resistance temperature of 200 ° C. Except having changed, the adhesive resin composition was obtained exactly like Example 8.

Examples 10 and 11 and Comparative Examples 16 and 17 An adhesive resin was prepared in the same manner as in Example 2 except that the metallization ratio of the component (C) in Example 2 was changed as shown in Table 4. A composition was obtained.

Tables 1 to 4 show the results of Examples 1 to 11 and Comparative Examples 1 to 17.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

[0056]

[Table 4]

In Examples and Comparative Examples, peel strength and impact strength were measured according to JIS K 6854 and JIS, respectively.
K6855. The vibration damping property is obtained by molding the epoxy resin composition into a film shape, measuring the spectrum of viscoelasticity at a temperature range of −150 ° C. to 250 ° C. with DMTA (trade name of Polymer Lab Co., Ltd.), and measuring the tan δ at room temperature. The value was used as an index. Finally, to evaluate the wettability of the uncured epoxy resin composition, the epoxy resin composition was applied in a bead form on a cold-rolled steel sheet, left in an oven at 140 ° C. for 15 minutes, and then the contact angle was measured. At this time, the case of 50 ° or more is indicated by ×, 50
The case of ° to 40 ° and the case of less than Δ40 ° were evaluated as ○. Here, when producing a film and an adhesive joint using the adhesive obtained in the above example, the curing condition was 170 ° C.2
Hold for 0 minutes.

[0058]

According to the present invention, an epoxy resin composition which is liquid at room temperature, a heat-active type curing agent, a powdery resin having a metalized surface and a liquid epoxy resin have extremely high swelling properties. Adhesive resin with excellent vibration damping properties without lowering wettability and adhesion to adherend as epoxy resin composition by mixing acrylic resin and piezoelectric particles as essential components A composition.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C09J 163/00 C09J 163/00 F16F 15/02 F16F 15/02 Q (56) References JP-A-63-150366 (JP, A JP-A-1-113476 (JP, A) JP-A-1-201384 (JP, A) JP-A-4-189815 (JP, A) JP-A-5-240298 (JP, A) JP-A-5-205 240299 (JP, A) JP-A-6-116540 (JP, A) JP-A-7-157740 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 63/00-63 / 10 C08L 33/00-33/26 C08L 101/00 C08K 3/34 C08K 3/24 C09J 163/00-163/10 F16F 15/02

Claims (1)

(57) [Claims] 1. A room temperature liquid epoxy resin (A) having at least one epoxy group in a molecule, 100 parts by weight, a heat-activated curing agent (B), and a metallization ratio of 5 to 70.
% Of powdered resin (C) having a particle diameter of 5 to 100 μm and 80 to 250 parts by weight of piezoelectric particles (D), and a liquid epoxy resin. On the other hand, swellable acrylic powdery resin (E) 5
An adhesive resin composition comprising 40 parts by weight as an essential component.