WO2000051178A1 - Electronic device - Google Patents

Abstract

An electronic device including a sealing member produced by polymerizing a polymerizable comoposition having a viscosity of less than 0.3 N.s.m-2 at 23 °C and a modulus of elasticity of less than 500 MPa at 23 °C. Another electronic device including a sealing member produced by polymerizing a polymerizable composition containing an olefin compound and having a modulus of elasticity of less than 500 MPa at 23 °C.

Description

 Specification

TECHNICAL FIELD The present invention relates to components including elements such as silicon chips such as LSIs (large-scale integrated circuits) and ICs (integrated circuits), transformers, coils, transistor diodes, and power switches. The present invention relates to a resin-sealed electronic device suitable for:

BACKGROUND ART With the miniaturization and thinning of electric and electronic devices, the density and integration of components used have been increasing. In particular, the progress in semiconductor-related components such as resin-encapsulated semiconductor devices has been remarkable.

 These electrical and electronic components are generally used to improve reliability such as insulation, moisture resistance, thermal shock resistance, and reflow crack resistance. Gold, silver, copper, aluminum, brass, zinc, silicon Materials made of inorganic materials such as iron, germanium, 42 alloy, and stainless steel are sealed with a polymer material.

For example, in an IC component, the element (silicon chip) is usually sealed with epoxy resin, and the ignition coil component is used. The coil is sealed with epoxy resin or silicone resin. In addition, electrical and electronic components in which elements (Ic, bare chips, etc.) are mounted on a support substrate made of ceramic, epoxy resin, etc., are made of acrylic resin, silicone, etc., depending on the environment in which they will be used. The element is sealed with resin, urethane resin, epoxy resin, etc.o

 Examples of resins used for encapsulation in these electric and electronic components include thermosetting resins such as epoxy resin, silicone resin, urethane resin, and polyimide resin, and polyethylene, Examples include engineering plastics (thermoplastic resins) such as polyethylene terephthalate, polycarbonate, modified polyphenylene oxide, and polyphenylene sulfide. Among these sealing resins, epoxy resins are most frequently used because they have the best adhesion to inorganic materials.

 The resin used to seal these electrical and electronic components must have a low coefficient of linear expansion in order to prevent separation at the interface between the inorganic member and the polymer. It is generally required that the material be close to inorganic materials such as copper wire. It also diffuses the heat generated by electrical and electronic components, such as Joule heat generated during semiconductor operation and heat generated by the electrical resistance of the copper wire coil, to improve the durability and reliability of electrical and electronic components. Increasing the rate is generally required. Therefore, generally, an inorganic filler such as silica or aluminum hydroxide is added to the encapsulating resin composition in order to reduce the coefficient of linear expansion and increase the thermal conductivity.

However, the addition of fillers makes the resin hard and brittle. This can lead to cracks and reduce the heat cycle resistance of the part. In general, the addition of inorganic filler, the polymerizable composition (resin raw material before polymerization curing), or become solid at room temperature, or, several to several tens of N - s' nT ² or more high viscosity It becomes less fluid. Therefore, the conventional polymerizable composition cannot be applied to encapsulation of a high-density integrated circuit or a fine circuit when a filler is added. For example, Japanese Patent Application Laid-Open No. H10-210800 proposes a low-viscosity epoxy resin prepolymer. This Prevost Rimmer, for example, 2. 9 N ■ s · π 2 and low viscosity would have is realized. However, at this level of viscosity, high-density integrated circuits and microcircuits still cannot be sufficiently sealed. In addition, the cured product (resin) has a glass transition temperature of 110 ° C, and is mechanically hard and brittle at the actual operating temperature. There is a problem that it is easy to occur.

Therefore, a method of sealing using engineering plastics having excellent mechanical toughness has been studied. For example, in Japanese Patent Application Laid-Open No. H10-292921, a polystyrene sulfide is used to extrude an electronic device such as an IC chip by extrusion at a cylinder temperature of 300 ° C. Methods for sealing components have been proposed. However, engineering plastics are thermoplastics, and their molding generally requires high temperatures of 300 ° C or more, and even at such high temperatures, dozens of N's 'to indicate high melt viscosity of about ² nT, it is very difficult to sufficiently impregnate the fine circuit using such plastics.

On the other hand, in order to prevent the reliability of electrical and electronic parts from deteriorating due to peeling of the sealing resin and cracking, low resin such as silicone resin and resin resin is used. In some cases, a polymer having an elastic modulus is used as a sealing resin. However, prepolymers such as silicone resin and urethane resin generally have high viscosity and poor impregnation. In addition, the dielectric constant of these polymers is higher than that of the olefin-based resin, and is inferior in electric characteristics. For this reason, the technique described in Japanese Patent Application Laid-Open Publication No. Hei 8 — 3 16 3 7.3 optimizes the resin filling method at the time of molding, and the technique described in Japanese Patent Laid-Open Publication No. Hei 10 — 233 472 optimizes the structure of parts. Although methods have been proposed, these improved methods alone cannot sufficiently impregnate fine circuits. Further, JP-5 -. Although 2 8 7 0 7 7 No. Shi Li co one down resin having a reduced viscosity of Purebori Ma one in publication have been proposed, but the viscosity 0 3 N 's' nT ² or Ah However, it has not yet reached a level where microcircuits can be sufficiently impregnated. On the other hand, cycloolefin resins obtained by polymerizing norbornene compounds are known to have excellent mechanical properties, electrical properties, water resistance, and the like. No. 8 proposes a production method for sealing electric and electronic parts by reaction injection molding of a norbornene-based compound. In addition, Japanese Patent Application Laid-Open No. Hei 9-183383 proposes a norbornene-based compound suitable for encapsulating electric and electronic components with a new metathesis polymerization catalyst. Further, in Japanese Patent Application Laid-Open No. H10-182922, the viscosity of the polymerizable cycloolefin compound (prepolymer) is low even when a filler is added, and the viscosity is low. · It is shown to be suitable for sealing electronic components. However, all of these use a prepolymer cured product obtained by combining a norbornene-based compound such as dicyclopentene and an inorganic filler as a sealing material, and the obtained cured product has a high glass transition temperature. On the other hand, since it has poor adhesion to inorganic members and has a high elastic modulus, it easily peels off at the interface with inorganic members. There is a problem of leaving them apart.

 In addition, the metathesis polymerization catalyst system described in the above-mentioned Japanese Patent Publication No. 5-41088 is a catalyst component, which is a catalyst component disclosed in Japanese Patent Publication No. 59-51911. It is similar to a catalyst system in which an organic ammonium salt of tungsten or molybdenum is combined with an activator, an alkoxyalkylaluminum halide or aryloxyaluminum halide. There is also a problem that molding must be performed in an inert gas atmosphere because it is active.

 As described above, a hard resin having a high elastic modulus such as an epoxy resin is likely to cause problems such as peeling and cracking, and has a problem in reliability of electric and electronic components. In addition, soft resins with low elastic modulus, such as silicone resin and urethane resin, have high impregnation properties due to the high viscosity of prepolymers, making it impossible to seal high-density integrated circuits and microcircuits sufficiently. There is. Further, a polymer obtained by using dicyclopentene resin as a cycloolefin resin and subjecting it to polymerizing the polymer also has a problem of peeling due to its high elastic modulus. In addition, sealing with a cycloolefin-based resin using a polymerization catalyst has a problem that the molding must be performed completely in an inert gas atmosphere.

DISCLOSURE OF THE INVENTION In order to solve the above-described problems, the present invention includes a sealing member obtained by polymerizing a polymerizable composition, and the sealing member is heated at 23 ° C. An electronic device having a bending elastic modulus of 500 MPa or less is provided. However, the flexural modulus is specified in JIS-K-7203. If such a sealing member is used, good precision cast moldability and solder reflow resistance can be obtained. The polymerization composition, 0. 3 N · s · π 2 below a is polymerizable liquid material or out in viscosity 2 3 ° C, or, including Orefu fin compounds.

 The electronic device of the present invention may be a component of another product such as a resin-sealed semiconductor device or an ignition coil, and may be any of an electric component and an electronic component. An electronic device suitable for the present invention includes, for example, a core made of a magnetic material, a primary coil and a secondary coil wound around the outer periphery of the center core, and an electronic device arranged outside the secondary coil. An ignition coil having an external core made of a magnetic material is provided.

 In the present invention, the sealing member is desirably at least one of the following (1) to (4).

 (1) The glass transition temperature is 80 ° C or less.

 (2) The coefficient of linear expansion is 100 ppm or more at 23 ° C. (3) Water absorption is less than 0.1% by weight when immersed in water at 23 ° C for 24 hours.

 (4) The dielectric constant is not more than 3.0 at 23 ° C.

The polymerizable composition, which is a raw material of the sealing member, desirably does not contain a solvent, and may contain a filler, and may contain an additive (ie, a modifier, a polymerization rate). (A regulator, a foaming agent, an antifoaming agent, a coloring agent, a stabilizing agent, an adhesion-imparting agent, a flame retardant, a capping agent and / or an organic peroxide). One type of additive may be used, or two or more types may be used in combination as needed. Also, A filler and an additive may be used in combination.

 The polymerizable composition desirably contains one or more metathesis polymerizable cycloolefin compounds, and is selected from a monomeric polymerizable cycloolefin compound having a molecular weight of less than 300 2 It is even more desirable to include more than one compound.

 When the polymerizable composition contains a metathesis polymerization cycloolefin compound, it is desirable to further include a metathesis polymerization catalyst. Examples of the metathesis polymerization catalyst that can be used include: Examples include compounds represented by the following general formulas (1) to (3).

X 1 ¹ L τ 1 Q ¹

M = C (1)

X 2 ^Δ τ L 2 Q

X 1 ¹ τ L 1 Q

Μ = C = C (2)

X 2 'τ L 2

 Q

X ¹ LR

Μ = C

 (3)

X 2 ^L L τ 2 C = C

H In the general formulas (1) to (3), M represents ruthenium or osmium, and X ¹ and X ^{2 each} independently represent anionic properties. L ¹ and L ^{2 each} independently represent a neutral ligand; Q ¹ and Q ^{2 each} independently represent hydrogen, an alkyl group, an alkyl group having a substituent, an alkenyl group Represents an alkenyl group having a substituent, an aromatic group, or an aromatic group having a substituent. R ¹ and R ² are each independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group, and a carbon atom having 1 to 18 carbon atoms. A carboxylate group, an alkoxyl group having 1 to 18 carbon atoms, an alkenyloxy group having 2 to 18 carbon atoms, an alkynyloxy group having 2 to 18 carbon atoms, an aryloxy group having 2 to 18 carbon atoms R ³ represents an alkoxycarbonyl group having 2 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, an alkylsulfonyl group having 1 to 18 carbon atoms, or an alkylsulfinyl group having 1 to 18 carbon atoms; It represents hydrogen, aryl group or alkyl group having 1 to 18 carbon atoms. If these polymerization catalysts are used in the reaction for obtaining the olefin-based resin, the variation in molding can be reduced because they are less susceptible to oxygen and moisture in the air. Therefore, these catalysts are suitable for the present invention. In the electronic device of the present invention, a sealing member molded in an atmosphere containing oxygen can be used.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a cross-sectional view showing an example of a structure of an ignition coil.

BEST MODE FOR CARRYING OUT THE INVENTION The electronic device of the present invention includes a sealing member that is a polymer of a polymerizable composition. The sealing member has a flexural modulus at 23 ° C specified in JIS-K-720 of 500 MPa or less. Hereinafter, in this specification, the resin composition forming the sealing member may be referred to as a low elastic modulus resin.

The polymerizable composition is desirably a polymerizable liquid that is liquid at 23 ° C. The viscosity of the polymerizable liquid material is preferably 0.05 N's'nT ² to 0.2 N.s'nT ² . For Furaino brute preparative La Nsuyai grayed Nisshiyo Nkoiru electronic devices, such as, viscosity of the polymerizable liquid material is 0. 3 Ν · 3 · ηΓ 2 a Ri of poor impregnation into inside卷線coil exceeds, Not Filling may occur and the insulation may decrease. The viscosity similar to zero. 3 Ν · 3 · ηΓ ² more than the polymerizable liquid material, when used as a sealing material of a semiconductor element in the semiconductor device typified by a DIP (Dual Inline Package), nitride The connection wiring between the lead frame and the lead frame or substrate (such as a polyimide film or ceramic) may be cut.

 The bending elastic modulus of the sealing resin used in the present invention is preferably at most 300 MPa, more preferably at most 100 MPa. If it exceeds 500 MPa, peeling and cracking are likely to occur.

 I. Sealing member

The type of sealing resin used for the sealing member in the present invention is not particularly limited as long as it has the above characteristics. For example, epoxy resin, urethane resin, silicone resin, acrylic resin, methacrylic resin, polyester resin, phenol resin, or olefin resin In-based resins (that is, resins obtained by polymerizing an olefin compound) and the like can be used. Of these, acrylic resins, methyl resins, polyester resins and olefinic resins are preferred, and olefinic resins are particularly preferred because of their excellent electrical properties.

 The glass transition temperature of the sealing member used in the electronic device of the present invention,

80 ° C or less is preferred, 50 ° C or less is more preferred, and 25 ° C or less is particularly preferred. When the glass transition temperature exceeds 80 ° C, cracks are easily generated inside the sealing member. For the same reason, the linear expansion coefficient of the sealing member is preferably 10 O ppm or more.

 Further, the water absorption of the sealing member is preferably less than 0.1% by weight when immersed in water at 23 ° C. for 24 hours. If the water absorption is 0.1% by weight or more, the insulation ゃ solder reflow resistance tends to decrease.

 Also, with the increase in density and integration of electronic devices, the sealing member preferably has a dielectric constant of 2.0 to 3.0 to prevent mutual interference of electromagnetic waves. More preferably it is 2.9. II. Composition of polymerizable composition for sealing

Hereinafter, the composition of the polymerizable composition for sealing which is a raw material of the sealing member used in the electronic device of the present invention will be specifically described. Incidentally, the sealing polymerizable composition, or a 0. 3 Ν · 3 · π 2 polymerizable liquid material is less than the viscosity of 2 3 ° C, or, tree fat feedstock Orefu fin compounds ( It is desirable to include them as monomers or oranges.

 A. Resin monomer 'Origoma

 The type of the sealing resin used for the sealing member in the present invention is not particularly limited, but an olefin resin is particularly preferred.

As a raw material of the olefin resin suitable for the present invention, Commonly known general-purpose resins such as ren, polypropylene, and polybutadiene are also exemplified. Cycloolefin-based compounds are preferred, and particularly preferred are cycloolefins which can be polymerized by polymerization. It is a compound.

 Cycloolefin compounds capable of metathesis polymerization can be broadly classified into norbornene-based cycloolefin compounds and non-norbornene-based cycloolefin compounds.

 Examples of the norbornene-based cycloolefin compound include, for example, substituted and unsubstituted

 Bicyclic norbornenes such as norbornene, methyl norbornene, dimethyl norbornene, ethyl norbornene, ethylidene norbornene, and butyl norbornene;

 Trinorbornene, tetracyclododecene, methyltetracyclododecene, methyltetracyclododecene, and dimethylcyclopentadiene Tetracyclic norbornenes such as tradodecene,

 More than five rings of norbornene, such as tricyclopencil (trimer of tetracycline) and tetracycline (trimer of tetracycline)

 And the like.

 Examples of the non-norbornene cycloolefin compound include cyclobutene, cyclopentene, cyclooctene, cyclododecene, tetrahydroindene, methyltetrahydroindene, and the like.

Compounds having two or more norbornene groups, for example, Tricyclododecadiene, symmetric tricyclopentene, and the like can also be used as the polyfunctional crosslinking agent. Furthermore, norbornene derivatives such as hymic acid, hymic anhydride, norbornadiene can also be used.

 One of these monomeric polymerizable cycloolefin compounds may be used alone, or two or more thereof may be used in combination.

 Of these, dicyclopentene, methyltetracyclododecene, ethylidene nornorbornene, tricyclopenide, cyclooctene, cyclohexene, and cyclohexene are considered to be readily available and economical. Roddeca Trien is preferred.

 The dicyclopentene is heated in advance to convert a part of the dicyclopentene into cyclopentane, such as tricyclopentene, or tetracyclopentene, or to remove impurities with impurities. Certain vinyl norbornene-methylvinylnorbornene can be isomerized to tetrahydroidone-den-methyltetrahydroidene-dene. This preliminary heat treatment is usually performed for 120 to 250 ° (for about 0.5 to 10 hours).

Note that ordinary commercially available olefin resin raw materials may contain impurities, and cycloolefin compounds having various purities are commercially available. For example, dicyclopentane includes vinyl norbornene, tetrahydroindene, methylvinylnorbornene, methyltetrahydrodenden, methyldicycloben, dimethyldicycloben, tricyclopentane, and the like. In some cases, cyclohexene may contain unreacted nitrogen and cyclooctane as impurities. However, using these commercial products without particular purification Is also good. When used in the electronic device of the present invention, as the resin raw material (monomer or orange), a resin material of 90% or more is usually used, preferably 95% or more, and particularly preferably. Use at least 98% purity.

 It is desirable to use two or more of these cycloolefin compounds having a molecular weight of less than 300 in combination. This is because the elastic modulus can be controlled in this way.

 For example, a resin obtained by polymerizing a bicyclic or polycyclic compound such as dicyclopentene tricyclopentene is hard, but cyclopentene, cyclooctene, cyclooctene, cyclodextrin, cyclodextrin, By using a simple substance such as cyclotetraethylene, the elastic modulus can be reduced.

 These monocyclic cycloolefin compounds used for lowering the elastic modulus are compounded in a range of 40 mol% or more and less than 99 mol% based on the total mol number of the polycyclic and monocyclic compounds. It is preferable to do so. If the amount of the monocyclic ring is less than 40 mol%, the elastic modulus becomes 500 MPa or more. If it is used in an amount of 99 mol% or more, the crosslink density is low, and the toughness of the resin is reduced.

 B. Polymerization catalyst

It is desirable that the sealing resin suitable for the present invention be a resin cured by methathesis polymerization. As the polymerization polymerization catalyst used in the polymerization, a known catalyst system can be used as a catalyst for the ring-opening polymerization of cycloolefin compounds. Type catalysts and one-component type catalysts, but there is no particular limitation. However, a one-component metal carbene catalyst is preferred because of its good stability in air. The amount of the catalyst added is usually 0.01 to 20% by weight based on the cycloolefin-based polymerizable composition, but is preferably 0.01 to 20% by weight for reasons of economy and curing speed. A range of 5% by weight is preferred.

 The two-component metathesis polymerization catalyst is a catalyst system that combines a catalyst component and an activator. Examples of the two-component metathesis polymerization catalyst used in the present invention include transition metals such as titanium, vanadium, molybdenum, tungsten, rhenium, iridium, ruthenium, and osmium. Including, complex metal halides, metal catalysts such as Ruben or Ziegler-Nautsun type coordination catalysts.

Specifically, tungsten compounds such as tungsten hexachloride, tungsten tetrachloride tungsten, tungsten oxide, tridecyl ammonium hydroxide, molybdenum pentachloride, molybdenum trioxychloride, and the like. oxidized Mo Li Buden, molybdenum compounds such as Application Benefits decyl ammonium Niu Mumo Li Bude DOO, five data down barrel compounds such as chlorides tantalum, and [(hexyl consequent _{b) 3 P] 2 Ru Cl 2} , [( full et two Le) ₃ P] ₃ RuCl doctor (cyclohexyl) ₃ P (p - staking down) RuCl _2, and the like [(full d _{sulfonyl) 3 P] 3 (CO)} RuH 2 ruthenium compound such as .

 A known cocatalyst (activator) is used in combination with these two-component metathesis polymerization catalyst systems as necessary. Specific examples thereof include an alkylaluminum nitride, an alkoxyalkylaluminum nitride, an aryloxyalkylaluminum nitride, and an organotin compound.

The one-component polymerization catalyst is different from the two-component catalyst system in that the cycloolefin compound is easily converted into a catalyst without losing catalytic activity due to moisture in the air or water adsorbed on the solid surface. Ring-opening polymerization can be carried out by a thesis reaction. Such a one-component type Specifically, the metathesis polymerization catalyst has a structure in which a metal carbene structure of ruthenium or osmium is used as a central skeleton and a ligand having large steric hindrance is coordinated to the central metal. And metal carbene-type coordination catalysts stabilized against moisture.

 Preferred examples of the ruthenium or osmium metal carbene-type coordination catalyst include compounds represented by any of the following general formulas (1) to (3). Of these, the compound represented by the general formula (3) is particularly preferable in terms of high catalytic activity, high synthesis yield, and economic efficiency.

X 1 "L τ 1 Q ¹

M = C (1)

X 2 ^L τ L 2 Q

X ¹ LQ

M = C = C (2)

X 2 τ L 2 Q

X 1 ¹ τ L 1 R

M = C R

 (3)

X ² LC = C

H R Here, M represents ruthenium or osmium.

X ¹ and X ² represent independently selected anionic ligands Show. An anionic ligand is an atom or atomic group that has a negative charge when decoordinated to the central metal. It is in this Anio emissions ligands, for example, hydrogen, _{halogen, CF 3 C0 2, CH 3} C0 2, CFH 2 CO 2, (CH 3) 3 CO, (CF 3) 2 (CH 3) CO ,

(CF ₃ ) (CH ₃ ) ₂ CO, alkyl group having 1 to 5 carbon atoms, alkoxyl group having 1 to 5 carbon atoms, phenyl group, phenoxyl group, tosyl group, mesyl group, trifluoromethane sulfonate Group. It is particularly preferred that both X ¹ and X ² are both halogen (especially chlorine).

L ¹ and L ^{2 each} represent a neutral ligand independently selected. The neutral ligand is an atom or an atomic group having a neutral charge when the coordination to the central metal is removed. Examples of such a group include PR ⁴ R ⁵ R ⁶ (where R ⁴ is a secondary alkyl group or a cycloalkyl group, and ¹⁵ and ¹⁶ are an aryl group and a carbon number of 1 to Phosphine-based electron donors represented by the following formulas: a primary alkyl group and a secondary alkyl group, and a cycloalkyl group. L ¹ and L ^2, both both P (cyclohexyl consequent b) _3, P (consequent Ropenchiru) _3, or P (i Sopuro pill) ₃ in which the this is rather preferred, may be different from one each other .

Further, examples of the ligand include pyridine, p-fluorovinylidine, imidazolylidene, and the like. As the imidazolylidene compound, a heterocyclic compound represented by the following general formula (4) or (5) is preferable. Of these, it is particularly preferable to use the compound represented by the formula (5) as the ligand. ( Four )

( Five )

Here, R ⁷ and R ⁸ are each independently selected from an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and a cycloalkyl group. , A reel group. R ⁷ and R ⁸ may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, or an aryl group. It may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, or a phenyl group. From the viewpoint of thermal stability, arbitrarily favored and this person least for Tomohen of R ⁷ and R ⁸ is a group represented by the following general formula (6).

… (6)

R

In the formula (6), R ⁹ and R ¹⁰ are each hydrogen, an alkyl group having 1 to 3 carbon atoms or an alkoxyl group having 1 to 3 carbon atoms, and R ¹¹ is hydrogen and ¹ to 3 carbon atoms. 10 alkyl groups, aryl groups, hydroxyyl groups, thiol groups, thioether groups, ketone groups, aldehyde groups, ester groups, ether groups, amine groups, imine groups, amide groups Nitro group, carboxylic acid group, disulfide group, carbonate group, isocyanate group, carbodiimide group, carbalkoxy group, olebamate group, halogen and the like. As a specific imidazolylidene compound that can be used as a ligand, a carbene represented by the following structural formula (7) or (8) can be given. Of these, imidazolylidene compounds of structural formula (7) are particularly preferred from the viewpoint of polymerization activity.

Q ¹ and Q ^{2 each} independently represent hydrogen, an alkyl group, an alkenyl group or an aromatic group, and the alkyl group, alkenyl group or aromatic group may have a substituent.

R ¹ and R ² are independently selected from an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group, and a carbon atom having 1 carbon atom. ~ 18 carboxylate group, 1 ~ 18 carbon atom alkoxyl group, 2 ~ 18 carbon atom alkenyloxy group, 2 ~ 18 carbon atom alkynyloxy group, 2 ~ 18 carbon atom Riloxy group, alkoxy group having 2 to 18 carbon atoms, alkoxyl group, alkylthio group having 1 to 18 carbon atoms, alkylsulfonyl group having 1 to 18 carbon atoms, or alkylsulfinyl group having 1 to 18 carbon atoms R ³ represents hydrogen, an aryl group or an alkyl group having 1 to 18 carbon atoms.

Specific examples of the catalyst suitable for the present invention include the following structural formula (9) (1 1)

)

Further, a compound represented by the following general formula (12) is also suitable for the present invention. CIP (R ^{1 1} ) 3

M = C = C H C (C H 3) (1 2)

C 1 P (R 1 1

3 In the general formula (12), R ¹¹ is a phenyl group, an isobutyl group or a cyclohexyl group.

 Such a metal carbene compound can be obtained by a known synthesis method. For example, a method using propargyl chloride shown in Organometallics Vol. 16, No. 18, p. 3687 (1991) can be mentioned. An example of the synthesis of the compound represented by the above structural formula (9) is shown below (Reference: Organometallics Vol. 16, No. 18, p. 3867 (19997)). Here, cy represents a cyclohexyl group.

 <Synthesis example>

In a 500 ra1 Fisher-Porter bottle, add cyclohexane gentilium dichloride (21 mmol), tricyclohexyl phosphine (42 mmol), and sodium hydroxide ( 7.2) Add 250 ml of sec-butanol to which oxygen has been removed, and heat at 90 ° C under a hydrogen atmosphere of 200 kPa. Pressurize several times until hydrogen absorption is completed, and continue stirring overnight. Cool to room temperature while applying hydrogen pressure to obtain a pale yellow precipitate. 30 ml of water was added, and the precipitate was filtered and dried in a stream of hydrogen to obtain Ru (H) ₂ (H ₂ ) ₂ (P (cy) ₃ ) ₂ (yield: about 80%). Next, the Ru (H) ₉ (H ₂ ) 2 (P (cy) ₃ ) ₂ (1-5 mmo 1) Dissolve in 0 ml and cool to 130 ° C. 3-Black mouth 3-Methyl 1 1 Putin (1.5 mm 01) is added. The solution immediately turns reddish purple, and after reacting as it is for 15 minutes, the cooling bath is removed and degassed methanol (20 ml) is added, and purple crystals precipitate. After washing with methanol and drying, Ru carbene catalyst (Cl) ₂ (P (cy) ₃ ) ₂ Ru = CH—CH = C (CH ₃ ) ₂ is obtained (yield: 95%).

 C. Additive

 For the polymerizable composition for sealing (preferably a polymerizable liquid material), a filler, a modifying agent, and a polymerization rate are used as necessary in consideration of the physical properties and appearance of the cured product, the moldability of the composition, and the like. A regulator, a foaming agent, an antifoaming agent, a coloring agent, a stabilizer, an adhesion-imparting agent, a flame retardant, a coupling agent, an organic peroxide, and the like can be optionally added.

 (1) Filler

 The filler used in the present invention includes, for example, inorganic fillers such as molten silica, crystalline silica, silica sand, calcium carbonate, aluminum hydroxide, magnesium oxide, clay, and inorganic ion exchangers. And bead-like organic fillers such as wood flour, polyester, silicone, polystyrene acrylonitrile-butadiene-styrene (ABS). Of these, silica and aluminum hydroxide are preferred in terms of electrical properties and thermal conductivity.

 Commercially available fillers suitable for the present invention include CRT-AA, CRT-D, D-8 (trade names, manufactured by Tatsumori Co., Ltd.), and COX-31 (Micro Co., Ltd.) C-303H, C-315H, C-308 (or more, Sumitomo Chemical Co., Ltd. product name), SL-700 (Takehara Chemical Industry Co., Ltd.) Product name).

The amount of these inorganic fillers is 0 to 95% by weight in the resin. It is preferably from 10 to 95% by weight, and more preferably from 30 to 95% by weight. It is particularly preferred that the amount be 30 to 75% by weight. If the compounding amount exceeds 95% by weight, the dielectric constant of the sealing member exceeds 3.0, so that the electrical characteristics are reduced.

 The particle size, shape, quality and the like of the filler can be appropriately determined according to the use of the electronic device to be manufactured, but the shape of the inorganic filler is preferably spherical. The average particle size is preferably between 0.1 and 100 zm, and more preferably between 1 and 50111. By combining those having different average particle sizes, the fine packing property and the fluidity can be improved.

 Examples of the filler suitable for the present invention include milled glass, cut fin, micro fin, mono chloro to lane, flaky glass powder, carbon fiber, and aramide fiber. Inorganic / organic fibrous fillers such as these can also be used, and these fibrous fillers can be used in combination with the above-mentioned fillers. The aspect ratio and shape can be appropriately selected according to the purpose. The compounding amount of these fibrous fillers is usually 0 to 20 parts by weight, preferably 0 to L: 0 parts by weight, based on 100 parts by weight of the sealing resin.

 (2) Modifier

Examples of the modifier used in the present invention include elastomers, natural rubbers, butadiene rubbers, copolymers (styrene copolymers (SBR), styrene-butadiene-styrene copolymers). Polymer (SBS), styrene-maleic acid copolymer, ethylene-vinyl acetate copolymer, etc., and thermoplastic resin (polymethyl methacrylate, vinyl polyacetate, polystyrene, etc.) Are listed. These copolymers and thermoplastic resins may be esterified, and the polar groups may be grafted. In addition, epoxy resins, urethane resins, polyester resins, silicone resins, phenolic resins, polyimide resins, polyamide resins, polyamide imide resins and their derivatives are blended for physical properties. Can also be improved.

 Furthermore, for example, a compound obtained by reacting an epoxy compound with norbornene monocarboxylic acid, a compound obtained by reacting an isopropylate compound with norbornene-ol, a high-acid-modified polyester, a petroleum resin, etc. Can also be mentioned as a modifying agent applicable to the present invention.

 Examples of the petroleum resin include those produced using a known C5 or C9 fraction purified from ethylene plant as a raw material. For example, Quinton (a product manufactured by Nippon Zeon Co., Ltd.) Name) or thermoplastic polynorbornene resin Norsolex (trade name, manufactured by Nippon Zeon Co., Ltd.). These petroleum resins preferably have a number average molecular weight of 100 or more, and more preferably have a functional group such as a hydroxyl group or an ester group in the resin skeleton. .

 The amount of these modifiers depends on the physical properties of the target resin, but can be generally from 0.2 to 50 parts by weight per 100 parts by weight of the polymerizable composition. Preferably it is in the range of 0.5 to 40 parts by weight. When the amount is less than 0.2 part by weight, the effect of the modifier is hardly exhibited, and when the amount is more than 50 parts by weight, the polymerizability tends to decrease.

 (3) Polymerization rate regulator

When the encapsulating resin is a radical polymerizable resin such as an acrylic resin or a polyester resin, methyl styrene is used as a polymerization rate regulator. A chain transfer agent such as a dimer can be used.

 In addition, when the sealing resin is an olefin-based resin, a phosphoric acid such as triphosphine, phosphin fin, triphenyl phosphine, tricyclohexyl phosphine, etc. Salts can be used as polymerization rate regulators.

 These polymerization rate regulators can be used in an amount of 0.05 to 20 parts by weight based on 100 parts by weight of the polymerizable composition. The amount of these polymerization rate regulators is for the purpose of controlling the pot life for molding.If the pot life can be shortened, the amount used should be reduced and the pot length should be increased. Do more.

 (4) Antifoaming agent and foaming agent

 As the defoaming agent, for example, known defoaming agents such as silicone oil, fluorine oil, and polycarboxylic acid polymer can be used. The defoaming agent can be added in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the polymerizable composition.

 Examples of the blowing agent include low-boiling hydrocarbon compounds such as pentane, propane, and hexane; physical blowing agents (such as carbon dioxide and water vapor); and chemical blowing agents (which generate nitrogen gas by decomposition). Compounds (azo compounds such as azobisisobutyronitrile and N ', N-dinitrothopenthyl methylentramine, and ditoros compounds), and the like.

 (5) Colorant

Examples of the coloring agent suitable for the present invention include inorganic pigments such as titanium dioxide, cobalt and cadmium, carbon black, aniline black,? -Naphthol, and phthalol. Evening cyanine, quinacridone, azo, quinophthalone, and indian blue Organic pigments can be used, and can be blended according to a desired color tone. These may be used in combination of two or more. Usually, the addition amount of these pigments can be 0.1 to 50 parts by weight based on 100 parts by weight of the polymerizable composition.

 (6) Stabilizer

 Examples of the stabilizer used in the present invention include an ultraviolet absorber, a light stabilizer and an antioxidant.

 As an ultraviolet absorber, for example,

 Salicylic acid-based UV absorbers such as phenylsali silicate and p-t-butylphenylsali silicate;

2, 4 Jihi Dorokishibenzofu perilla down, 2 - heat Dorokishi one 4 - Main Tokishibenzofu perilla emissions, 2, 2 'Jihi Dorokishi 4, 4 ⁵ - dimethyl Tokishibenzofu We Bruno Benzofu We Bruno emissions based ultraviolet ray absorbing agents such as down,

 2 — (2,1-Hydroxy-1,5-methylphenyl) benzotriazole, 2— {2,1-Hydroxy-1,3,, 5,1-di (t-butyl) phenyl} benzotri Azotriol, 2— {2, hydroxyl 3 ', 5, di (t-amino) phenyl) benzotriazole-based ultraviolet absorber such as benzotriazole,

 2 —Ethylhexyl 2 —Cyano 3,3 ′ diphenyl acrylate, ethyl 1 2 —cyano 3,3,1-diphenyl acrylate, etc.

 Is mentioned. These may be used alone or in combination of two or more.

The amount of the ultraviolet absorber to be added is appropriately determined depending on the use environment of the electronic device, the presence or absence of housing, and the required characteristics. Usually, the amount of the ultraviolet absorber is 0.05 to 20 parts by weight based on 100 parts by weight of the polymerizable composition. Use parts by weight Can be.

 Bis (2,2,6,6—tetramethyl-14-piperidyl) sebacate and bis (1,2,2,6,6—pentymethyl 4-biperidinyl) as light stabilizers Sebacate, dimethyl conodate '11-(2-hydroxylexetyl) 1-4-hydroxy-2,2,6,6-Hindered amine photo stabilizer such as tetramethylbiperidine polycondensate Can be This light stabilizer can be added in an amount of 0.05 to 20 parts by weight based on 100 parts by weight of the polymerizable composition.

 Further, as the antioxidant used in the present invention,

 Quinones such as norabenzoquinone, tonolequinone, and naphtoquinone;

 Hydroquinones, such as rho-, hydroquinone, normal t-butyl catechol, 2,5-di- (t-butyl) hydroquinone,

 Di- (t-butyl) ■ phenols such as norlac resole nodroquinone monomethyl ether, pyrogallol,

 Copper salts such as copper naphthenate and copper octenoate;

 Quaternary ammonium salts such as trimethylbenzylammonium chloride, trimethylbenzylammonium maleate, and phenyltrimethylammonium chloride;

 Oximes such as quinondioxime / methylethylketoxime, and amic acids such as triethylamine hydrochloride and dibutylamine hydrochloride;

 Oils such as mineral oil, essential oil, and fatty oil

And the like. These antioxidants are added in different types and amounts depending on conditions such as compatibility with the filler, intended molding workability and resin storage stability. Usually, the amount added is 100% by weight of the polymerizable composition. 10 to:: 0,000 ppm can be used for each part.

 (7) Adhesion imparting agent

 Examples of the adhesion-imparting agent used in the present invention include a silane-based coupling agent. The silane coupling agent is generally represented by the following general formula (13).

Y _n -S i-X ₄ _ _n- (1 3) where Y is a monovalent group having a functional group and binding to S i, and X is hydrolyzable and binding to S i. It is a group of. n is an integer of 1 to 3.

 Examples of the functional group in Y include vinyl, amino, epoxy, black, mercapto, methacryloxy, cyano, carbamate, pyridine, sulfonyl azide, urea, styryl, chloromethyl, ammonium salt, and the like. There are groups such as alcohol.

 Examples of X include chlor, methoxy, ethoxy, methoxyethoxy, and the like.

Specific examples of such silane coupling agents include vinyl trimethoxy silane, vinyl tris (2-methoxetoxy) silane, and α- (2-aminoethyl) aminoprobitrime. Toxicilane, α-mercaptopropyl trimethoxysilane, α-glycidoxypropyl trimethoxysilane, α-glycoloxypropyl trimethoxysilane, N, N-Dimethylaminophenyl trier Toxicylane, mercaptoethyl triethoxysilane, methyl oxo-oxyl dimethyl (3-trimethoxysilyl propyl) ammonium chloride, 3- (N-styrylmethyl 1-2-aminoaminoethylamino ) Provir trimethoxysilane hydrochloride and the like. This both allowed to Noh. The silane coupling agent can be added usually in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the polymerizable composition. (8) Flame retardant

 Hexabromobenzene, tetrabromobisphenol A, and decabromidine: flame retardants: phenyl oxide, tribromophenol, dibromophenylglycidyl ether, park mouth pen Even halogen-based compounds such as cyclodecane and a phosphoric acid derivative can be used. These may be used alone or in combination of two or more.

 In addition, phosphoric acid compounds such as trisphosphate (dichloropropane) and trisphosphate (dibromopropyl), and boric acid compounds can also be used.

 Further, examples of the auxiliary flame retardant include antimony trioxide, iron oxide, aluminum hydride, and the like. When these are used in combination with the flame retardant, the flame retardant effect is enhanced.

 Usually, the halogen-based flame retardant is used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the cycloolefin compound, and the auxiliary flame retardant such as antimony trioxide is used in an amount of 1 to 15 parts by weight.

 In addition, commercially available hydrates such as aluminum hydroxide and magnesium hydroxide can also be used as fillers for plastics as flame retardants. It is preferable to use these additives in the range of 100 to 300 parts by weight based on 100 parts by weight of the polymerizable composition.

 (9) Organic peroxide

Further, an organic peroxide can be added. Organic peroxides include, for example, Kumenheim-dropperoxide and Yusha Polybutyloxy 2 —ethylhexanate, methylethyl ketone peroxyside, benzoyl peroxyside, acetyl acetate propoxyside, bis-1 4 — Yushiichi Sharpylcyclohexane xandicarbonate, 2,5 —Dimethyl 2,5—Bis (Ethyl-butylbutyloxy) hexine—3 and the like, and these may be used alone or in combination of two or more. Usually, it is preferable to use 0.1 to 10 parts by weight based on 100 parts by weight of the polymerizable composition.

 (10) Reactive diluent

 The polymerizable composition used for sealing in the electronic device of the present invention may be an acrylic monomer or a methacrylic monomer in order to adjust the viscosity of the composition and the mechanical and electrical properties of the sealing member. First, a low-viscosity reactive diluent such as a vinyl monomer or diaryl phthalate may be used. One of these may be used alone, or two or more may be used in combination.

 However, the polymerizable composition used for sealing in the electronic device of the present invention preferably does not contain a solvent. Here, the solvent is a generally known non-reactive diluting solvent such as benzene, toluene, xylene, ethyl acetate, and methyl ethyl ketone.

 When a commercial product is used as an additive, a solvent may be contained. Solvents contained in such commercial products shall be ignored. However, even in this case, the content of the solvent is preferably less than 2 parts by weight based on the polymerizable composition in order to prevent swelling during curing.

 (1 1) Other

In the polymerizable composition for sealing used in the present invention, the above In addition to the components, components can be appropriately added as needed. For example, to improve the wettability of the filler, a capping agent (for example, a commercially available wetting agent or dispersant such as BYK series manufactured by BYK-Chemie Co., Ltd.) can be added. In addition, a mold release agent such as silicone oil / zinc stearate can be added to improve workability.

 D. Molding method

 Examples of the molding method of the electronic device of the present invention include a vacuum injection molding method, a pressure injection molding method, an impregnation molding method, an RTM molding method, a diving, a hand lay-up spray-up, and the like. Laminate molding method, press molding method, filament winding method, centrifugal molding method, vacuum or pressure back method, continuous molding method, pultrusion molding method, injection molding method, transformer molding, etc. Can be used. When using the polymerization catalysts represented by the above general formulas (1) to (3), it is not necessary to carry out these moldings in an inert gas atmosphere.

 When a cycloolefin-based polymerizable composition is used, the polymerization can be carried out by adding a female sis polymerization catalyst to the composition, dissolving the composition, and then heating the composition.

 The temperature at the time of adding and dissolving the polymerizable composition to the polymerizable composition is usually 0 to 80 ° (: preferably room temperature to 50 ° C).

The heating operation for obtaining the polymer may be one-stage heating or two or more-stage heating. In the case of one-step heating, the temperature is usually 0 to 250 ° C; preferably 20 to 200 ° C. C. In the case of two-stage heating, the temperature of the first stage is usually 0 to 150 ° C, preferably 10 to 100 ° C, and the temperature of the second stage is usually 20 ° C. Up to 200 ° C, preferably 30 to 180 ° C. The polymerization time can be appropriately determined according to the amount of the catalyst and the polymerization temperature, and is usually from 1 minute to 50 hours.

III. Knowing

 The electronic device of the present invention includes a sealing member, which is a cured product of the above-described polymerizable composition, and may further be covered by a housing. In this case, the sealing member and the housing may be integrally formed. Further, the substrate on which the element is mounted may be put in a housing and sealed with a resin.

 The housing material can be selected from inorganic materials such as sus, copper, iron, aluminum, and ceramics, and organic materials such as thermosetting resin, thermoplastic resin, biodegradable resin, and natural resin. It is selected depending on the application, and there is no particular limitation. Also, the shape and dimensions of the housing and the electronic device are arbitrarily designed according to the purpose and the like.

Examples Hereinafter, the present invention will be described with reference to Examples. In the following Examples and Comparative Examples, “parts” means “parts by weight” unless otherwise specified.

 I. Preparation of resin

 <Resin 1: Olefin low elastic modulus resin>

 High-purity dicyclopentene (Maruzen Petrochemical Co., Ltd., purity

50 parts by weight, Cyclone Gen (purity 98.5% or more, manufactured by HULS) 50 parts by weight, and silane coupling agent (FZ manufactured by Nippon Tunicer Co., Ltd.-37778) 0.1 part by weight was mixed. Next, a fused silica with an average particle size of 15 m (Fuselex RD-8 manufactured by Tatsumori Co., Ltd.) or an aluminum hydroxide with an average particle size of 8 μm (C-13 manufactured by Jitomo Chemical Co., Ltd.) 08) was added in the amounts shown in Table 1 to obtain a compound. To this compound, 0.2 part by weight of the polymerization catalyst represented by the above structural formula (9) was added immediately before casting, and a test was conducted. The curing conditions were 38 ° C for 2 hours + 100 ° C for 1 hour + 125 ° C for 1 hour unless otherwise stated.

<Resin 2: Acrylic low modulus resin>

 Laurylmethacrylate 90 parts (Kyoeisha Chemical Co., Ltd. Light Ester L) and Polypropylene Glycomethacrylate (Kyoeisha Chemical Co., Ltd. NK Ester 9 PG) 10 parts by weight, and 0.1 part by weight of a silane coupling agent (FZ-37878, manufactured by Nippon Rikiichi Co., Ltd.) was further mixed. Next, a predetermined amount of a molten silica (Fuselex RD-8, manufactured by Tatsumori Co., Ltd.) having an average particle size of 15 μm as shown in Table 1 was added to obtain a compound. To this compound, 0.5 part of t-butylpropyl-2-ethylhexanoate as a polymerization catalyst was added just before casting to give a test. The curing conditions were 40 ° C. for 1 hour + 60 ° C. for 3 hours + 80 ° C. for 1 hour + 100 ° C. for 1 hour unless otherwise stated.

 <Resin 3: Polyester low modulus resin>

In a 2-liter 4-necked flask equipped with a stirrer, capacitor, nitrogen gas inlet tube and thermometer, diethyl glycol 463, neobentyl glycol 454, adipic acid 927 parts Then, with the addition of 156 parts of maleic anhydride, the temperature was raised to 150 ° C over 1 hour using a mantle heater while gently flowing nitrogen gas. After keeping the temperature for 2 hours, the temperature was raised to 220 ° C over 5 hours. The mixture was kept at that temperature for 6 hours to obtain an unsaturated polyester having an acid value of 30.

To this, a styrene monomer dissolved in 0.01% of hydrydroquinone was added and dissolved so that the unsaturated polyester content was 70% by weight, and the viscosity at 25 ° C was 0.19 Pa · S (0.19Ν · s / m ² ) was used as the unsaturated polyester resin liquid.

 In 100 parts of this resin solution, 0.15 parts of bis (4.1t-butylcyclohexyl) peroxide carbonate and 0.45 parts of cumene hydroperoxide were added as organic peroxides. Penzoyl oxide 8 parts was added. Curing conditions were 80 ° C for 3 hours + 125 ° C for 3 hours unless otherwise noted.

<Resin 4: Dicyclopentene resin 1>

 100 parts by weight of high-purity dicyclopentene similar to Resin 1 and 0.1 part by weight of a silane coupling agent (FZ-37778, manufactured by Nippon Rikiichi Co., Ltd.) were mixed. Next, a predetermined amount of a molten silica having an average particle size of 15 μm (Fuselex RD-8, manufactured by Tatsumori Co., Ltd.) as shown in Table 2 was added, followed by stirring and mixing to obtain a compound. Curing was carried out in the same manner as for Resin 1 using a female polymerization catalyst represented by the structural formula (9).

 <Resin 5: dicyclopentadiene resin 2>

 In the dicyclopentene used for Resin 1, 40 millimoles of getyl aluminum dimethyl chloride, 52 millimoles of n-propyl alcohol, and 20 millimoles of silicon tetrachloride, Each was added in a nitrogen-purged dry box to obtain solution A.

In addition, tridecyl was added to dicyclopropene as well as solution A. Ammonium molybdate was added at a concentration of 10 millimolar to prepare solution B.

 50 parts by weight of the liquids A and B are mixed together, and 100 parts by weight of molten silica having an average particle diameter of 15 μm (Fuselex RD-8, manufactured by Tatsumori Co., Ltd.) are immediately added to a nitrogen atmosphere. The samples were mixed under equal amounts below. The curing conditions were 0.5 hours at 0.5 ° C. + 3 hours at 125 ° C. unless otherwise stated.

<Resin 6: epoxy resin>

 Bisphenol A-type epoxy resin 100 parts by weight (YD-128, manufactured by Toto Kasei Co., Ltd.) and 0.1 part by weight of a silane coupling agent (TSA-72, manufactured by Toshiba Silicone Corp.) 0) was mixed to obtain solution A.

 On the other hand, 2 parts of 2-ethyl-4-methylimidazole are mixed with 87 parts by weight of methyl tetrahydrofluoric anhydride (HN-200, manufactured by Hitachi Chemical Co., Ltd.) as a curing agent. The solution was designated as solution B.

 50 parts by weight of the liquid A and 45 parts by weight of the liquid B are mixed, and 100 parts by weight of a molten silica having an average particle size of 15 m (Hyuzulex RD manufactured by Tatsumori Corporation) — 8) was mixed and thoroughly stirred for the test. The curing conditions were 100 ° C. for 1 hour, 125 ° C. for 2 hours, and 140 ° C. for 3 hours unless otherwise specified.

<Resin 7: Silicone resin>

 A commercially available heat-dissipating type silicone resin (KE-122, manufactured by Shin-Etsu Silicone Co., Ltd.) was tested. The curing conditions were 100 ° C. for 1 hour unless otherwise specified.

 <Resin 8: urethane resin>

Commercially available urethane resin for casting (KU-7, manufactured by Hitachi Chemical Co., Ltd.) 0 7) 0.1 parts by weight of 100 parts by weight of a silane coupling agent (AZ-61 1 1 manufactured by Nippon Tunicer Co., Ltd.) was mixed and stirred. m molten silica (Fusex RD-8, manufactured by Tatsumori Co., Ltd.) 100 parts by weight was further mixed. Curing conditions were 50 ° C for 3 hours + 100 ° C for 2 hours unless otherwise specified.

Resin 9: resin low elastic modulus resin>

 Twenty-five parts by weight of high-purity dicyclopentene, 75 parts by weight of cyclone, and 0.1 part by weight of a silane power coating agent (FZ-37778 manufactured by Nippon Tunica) were blended. Next, a high-purity synthetic silica having an average particle size of 0.5 m (Adumafin SO—25H manufactured by Tatsumori Co., Ltd.) was added in a predetermined amount shown in Table 1 to obtain a compound. To this compound, 0.01 part by weight of a metathesis polymerization catalyst represented by the general formula (10) was added immediately before casting and tested. The curing conditions were 25 ° C for 1 hour + 100 ° C for 1 hour unless otherwise noted.

<Resin 10: olefin-based low modulus resin>

 After mixing 25 parts by weight of high-purity dicyclopentagen, 37.5 parts by weight of cyclooctane, and 37.5 parts by weight of cyclooctene (97% pure by HULS), the formula (1) 0) 1 part by weight of the polymerization catalyst represented by the following formula (1) was added immediately before casting and tested. The curing conditions were 25 ° C. for 1 hour + 100 ° C. for 1 hour unless otherwise stated.

 II. Test method

 Viscosity>

Using a B-type viscometer, the viscosity was measured at 23 ° C. and at a mouth speed of No. 3 at 60 rpm. Bending elastic modulus>

 For each of the resins 1 to 10 described above, cast plates having a thickness of 3 mm were prepared and measured in accordance with JIS-K-172. The test piece shape was 25 x 80 x 3 mm, the test span was 48 mm, and the test speed was 100 mm / min.

<Model impregnation test>

 Glass beads (average particle size: 80 μm) dried at 100 ° C for 1 hour in a polypropylene polypropylene test tube with a diameter of 15 mm to a height of approximately 60 mm After filling while shaking, weigh and weigh glass beads. (G) was measured.

 Next, the polymerizable composition was poured into a polypropylene test tube filled with glass beads so that the liquid level was about 60 mm, and the pressure was reduced to 1.3 cPa for 10 minutes. After standing, it was thermally cured under the specified conditions.

 Thereafter, the glass beads separated from the cured product without being impregnated were collected and their weight W i (g) was measured. The model impregnation rate was calculated from the following equation.

 Model impregnation rate (%) = {(W. one / W J X 100

<Output characteristics>

 For equipment models 1 to 3, a heat cycle test was performed with a cycle of (140 ° C for 30 minutes + 125 ° C for 30 minutes) as one cycle, and the primary voltage after the test was performed. It was tested whether an output of 20 KV or more could be obtained as a secondary voltage when 12 V was applied. After the test, the parts were cut and the presence or absence of peeling was observed using an optical microscope. Moldability>

For equipment model 4, the cutting state of the gold wire was changed to soft X-ray. Was checked and evaluated based on the presence or absence of disconnection.

<Solder reflow resistance>

 Using device models 4 and 5, after leaving in an atmosphere of 85 ° C / 85% RH for 16 hours, heating at 240 ° C for 10 seconds was performed three times, and observation of crack generation and An energization test was performed.

Method of manufacturing the equipment model>

 (1) Device model 1: ignition coil

 As shown in FIG. 1, the ignition coil manufactured in the present embodiment has a magnetic core 11, an outer core 12, a primary bobbin 13, a primary coil 14, a secondary bobbin 15, a secondary bobbin 15, and a secondary bobbin 15. It is provided with a secondary coil 16, a terminal 17, an ignition timing control circuit component 18, a primary terminal 20, a housing (case) 21, and a sealing member 23 made of a sealing resin. The ignition timing control circuit component 18 is obtained by sealing a ceramic substrate 19 with IC with epoxy resin 22. In Fig. 1, hatching is omitted except for some parts to make the figure easier to read.

The primary coil 14 has an enamel wire with a diameter of about 0.5 mm about 200 times, the secondary coil 16 has an enamel wire with a diameter of about 0.05 mm about 2000 times, and the bobbin 1 It is wound in 3,15. Although the primary coil 14 is connected to the battery and direct current flows, the current flowing by the ignition timing adjustment electronic circuit components 18 and the power switch is intermittently changed to change the magnetic flux, and the self-induction operation is performed. It is designed to obtain more primary voltage. The ignition coil generates a high voltage of 20 to 40 KV by the mutual induction of the primary coil 14 and the secondary coil 16 by applying this primary voltage to the terminal. What causes spark discharge to the connected spark plug It is.

 The device model 1 is composed of a case 21 made of polyolefin sulfide (PPS), a magnetic core 11 and 12, an aluminum electrode, an ignition control circuit component 18, and a modified polyolefin. As an assembly incorporating the primary coil 14 and the secondary coil 16 wound around the bobbins 13 and 15 made of ethylene oxide (PP0), the polymerizable composition for sealing is listed as The test samples shown in Table 1 and Table 2 (degassed at 0.67 kPa for 1 minute) were cast, and 30 ° 01 hours + 50.封 止 The composition was cured under the curing condition of 1 hour + 800 1 hour + 1.degree. C. for 1 hour to form a sealing member 23, and an ignition coil was obtained.

(2) Device model 2: Other than using a ceramic board with bare chip IC (parts unsealed) as the enclosed ignition coil ignition timing control circuit part 18 Injects the test sample (defoamed at 0.67 kPa for 1 minute) shown in Table 1 as an encapsulating polymerizable composition into an assembly having the same configuration as device model 1. 30 ° C for 1 hour + 50 ° C for 1 hour + 80 ° C for 1 hour + 120 ° C for 1 hour to form the sealing member 23, An ignition coil in which the coil and the coil were sealed was obtained. (3) Device model 3: Case-less ignition coil Magnetic cores 11 and 12, brass electrodes, ignition timing control circuit parts 18 (Ceramic board with bare chip IC (parts unsealed The primary coil 14 and the secondary coil 16 wound on the bobbins 13 and 15 made of PP0 and modified PP0 are placed in the specified position in the center of the mold after the necessary wiring is performed, and the package is sealed. The test sample shown in Table 1 (defoamed at 0.67 kPa for 1 minute) was cast as a shutdown polymerizable composition, and then 30 ° C for 1 hour + 50 ° C for 1 hour + 80 ° C for 1 hour + 120 ° C for 1 hour After curing under the above curing conditions to form the sealing member 23, the sealing member 23 was removed from the mold to obtain a batch sealing case-less ignition coil. (4) Equipment model 4: IC parts

 Modified PP0 concave case 21 mm in length, 25 mm in width, 25 mm in width, and 5 mm in thickness. The sealing material was formed by pouring the deaerated test sample in advance to obtain a resin-sealed semiconductor device.

 (5) Device model 5: DIP type IC package

 A test element (a silicon chip with an oxide film of 5 mm in length and width and aluminum wiring applied to it) was used, and this was applied to a 42-alloy lead frame with a partial silver plating and an epoxy-based element. Using a silver paste, a thermosonic wire bonder was used to connect the bonding pad of the element to the inner lead at 200 ° C with a 10-µm gold wire. Thereafter, the test sample which had been defoamed in advance was potted and cured to form a sealing member, thereby obtaining a resin-sealed 16-bin type DIP type semiconductor package.

<Glass transition temperature (Tg)>

 The measurement was performed using TMA8310 manufactured by Rigaku Corporation.

 Glow linear expansion coefficient>

 One hundred and ninety using TMA8310 manufactured by Rigaku Corporation. It was measured from C to 200 ° C.

 <Dielectric constant>

 It was measured at 1 MHz using a TR-10 C type dielectric loss measuring instrument manufactured by Ando Electric Co., Ltd.

<Water absorption> It was measured according to JIS K7114.

III. Test results

Tables 1 and 2 show the results of the examples and comparative examples. The electronic device of each embodiment is different from the device of each comparative example sealed with an epoxy resin and a dicyclopentadiene resin having a high elastic modulus and a silicone resin and a urethane resin having a low elastic modulus. It also had excellent output characteristics, moldability, and resistance to solder reflow. This result indicates that the electronic device of the present invention has excellent reliability.

table 1

Table 2

Industrial applicability

As described above, the electronic device of the present invention is water-resistant and reflow-resistant. It has excellent reliability and high reliability. Therefore, by using the electronic device of the present invention, it is possible to widely provide a long-life, high-durability electric / electronic device corresponding to high density and high integration.

Claims

The scope of the claims

1. A sealing member obtained by polymerizing the polymerizable composition is provided, and the polymerizable composition is a polymerizable liquid material having a viscosity of less than 0.3 N's'm- ^{2 at} 23 ° C. And

 The electronic device, wherein the sealing member has a flexural modulus at 23 ° C of 500 MPa or less.

2. A sealing member obtained by polymerizing a polymerizable composition containing an olefin compound,

 The sealing member,

 An electronic device having a flexural modulus at 23 ° C of 500 MPa or less.

3. The electronic device according to claim 2, wherein the polymerizable composition contains a resin that is a polymerizable liquid having a viscosity of less than 0.3Νπ · ^{2 at} 23 ° C.

4. The above sealing member,

 The electronic device according to any one of claims 1 to 3, wherein the glass transition temperature is 80 ° C or less.

5. The sealing member is

 The electronic device according to any one of claims 1 to 4, wherein a linear expansion coefficient is 10 Oppm or more at 23 ° C.

6. The sealing member is The electronic device according to claim 1, wherein a water absorption is less than 0.1% by weight when immersed in water at 23 ° C. for 24 hours.

7. The sealing member is

 The electronic device according to any one of claims 1 to 6, wherein a dielectric constant at 3.0 ° C is 3.0 or less.

8. The polymerizable composition is

 8. The electronic device according to claim 1, further comprising a filler.

9. The polymerizable composition is

 At least one of modifiers, polymerization rate regulators, foaming agents, defoamers, coloring agents, stabilizers, adhesion promoters, flame retardants, coupling agents, and organic peroxides The electronic device according to claim 1, further comprising an additive.

10. The electronic device according to any one of claims 1 to 10, wherein the polymerizable composition does not contain a solvent.

1 1. The polymerizable composition is

 The electronic device according to any one of claims 1 to 10, further comprising at least one kind of polymerizable cycloolefin compound.

1 2. The polymerizable composition,

12. The electron according to claim 11, comprising two or more compounds selected from the group consisting of polymerizable cycloolefin compounds having a molecular weight of less than 300.

1 3. The polymerizable composition,

 13. The electronic device according to claim 11, which comprises a polymerization catalyst.

1 4. The above-mentioned polymerization catalyst

 14. The electronic device according to claim 13, which is a compound represented by the following general formula (1).

X ¹ L ¹ Q ¹

 \ I /

 M = C (1)

/ I \

X ² L ² Q ²

(Where M represents ruthenium or osmium, X ¹ and X ^{2 each} independently represent an anionic ligand, and L ¹ and L ^{2 each} independently represent a neutral ligand. , Q ¹ and Q ^{2 each} independently represent hydrogen, an alkyl group, an alkyl group having a substituent, an alkenyl group, an alkenyl group having a substituent, an aromatic group or an aromatic group having a substituent.)

1 5. The above-mentioned polymerization catalyst

 14. The electronic device according to claim 13, which is a compound represented by the following general formula (2).

X ¹ L ¹ Q ¹

 \ I /

 M = C = C (2)

/ I \

X ² L ² Q ² (Where M represents ruthenium or osmium, X ¹ and X ^{2 each} independently represent an anionic ligand, and L ¹ and L ^{2 each} independently represent a neutral ligand. , Q ¹ and Q ^{2 each} independently represent hydrogen, an alkyl group, an alkyl group having a substituent, an alkenyl group, an alkenyl group having a substituent, an aromatic group or an aromatic group having a substituent.)

1 6. The above metathesis polymerization catalyst

 The compound according to claim 13, which is a compound represented by the following general formula (3):

X ¹ LR

M = C

 (3)

X 2 ^Δ τ L 2 C = C

H ²

(Where Μ represents ruthenium or osmium, X ¹ and X ^{2 each} independently represent an anionic ligand, and L ¹ and L ^{2 each} independently represent a neutral ligand. R ¹ and R ² are each independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group, and a carbon atom having 1 carbon atom. ~ 18 carboxylate group, 1 ~ 18 carbon atom alkoxyl group, 2 ~ 18 carbon atom alkenyloxy group, 2 ~ 18 carbon atom alkynyloxy group, 2 ~ 18 carbon atom Lyoxy group, carbon number 2 ~

Represents an alkoxycarbonyl having 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, an alkylsulfonyl group having 1 to 18 carbon atoms or an alkylsulfinyl group having 1 to 18 carbon atoms, and R ³ represents hydrogen or aryl group. Or an alkyl group having 1 to 18 carbon atoms. )

1 7. The sealing member is

 The electronic device according to any one of claims 1 to 16, wherein the electronic device is formed in an atmosphere containing oxygen.

1 8. The above electronic device

 An ignition coil including a central core made of a magnetic material, a primary coil and a secondary coil wound around the outer periphery of the central core, and an external core made of a magnetic material provided outside the secondary coil. An electronic device according to any one of claims 1 to 17.