KR100447711B1 - Electronic device - Google Patents

Abstract

In this invention, the electronic device provided with the sealing member whose bending elastic modulus in 500 degreeC or less at 23 degreeC obtained by superposing | polymerizing the polymerizable composition whose viscosity is less than 0.3 N * s * m <^-2> at 23 degreeC is included, and an olefin compound is included. The electronic device provided with the sealing member whose flexural modulus in 23 degreeC obtained by superposing | polymerizing the polymeric composition to make is 500 Mpa or less is provided.

Description

Electronic device {ELECTRONIC DEVICE}

As miniaturization and thinning of electric and electronic devices, high density and high integration of components used are progressing. In particular, the progress in semiconductor related parts called resin encapsulated semiconductor devices is surprising.

In these electrical and electronic components, gold, silver, copper, aluminium (aluminum bronze), brass, zinc, and silicon are generally used to improve the reliability of insulation, moisture resistance, thermal shock resistance, and reflow crack resistance. A member made of an inorganic material such as germanium, 42 alloy or stainless steel is sealed by a polymer material.

For example, in an IC component, an element (silicon chip) is normally sealed with an epoxy resin, and in an ignition coil part, a coil is sealed with an epoxy resin or a silicone resin. In addition, the electric / electronic parts in which the elements (IC, bare chip, etc.) are mounted on a support substrate made of ceramic, epoxy resin, or the like may be encapsulated with acrylic resin, silicone resin, urethane resin or epoxy resin depending on the environment used. It is.

As resin used for sealing in these electrical / electronic components, thermosetting resins, such as an epoxy resin, a silicone resin, a urethane resin, and a polyimide resin, and polyethylene, a polyethylene terephthalate, a polycarbonate, a modified polyphenylene oxide, a polyphenylene, for example Engineering plastics (thermoplastic resin), such as sulfide, are mentioned. Among these resins for sealing, epoxy resins are most frequently used in terms of excellent adhesion to inorganic materials.

The resin used for encapsulating these electrical and electronic parts should have a low linear expansion coefficient, that is, a linear expansion coefficient close to an inorganic member such as a silicon chip, an alumina electrode, or a copper wire in order to prevent peeling of the interface between the inorganic material and the polymer. Generally requested. In addition, it is common to increase the thermal conductivity in order to diffuse heat generated by electrical and electronic components such as joule heat generated during semiconductor operation or heat generation due to electrical resistance of copper wire coils, thereby improving durability and reliability of electrical and electronic components. Is requested. Therefore, in general, an inorganic filler such as silica or aluminum hydroxide is added to the encapsulating resin composition for low linear expansion coefficient and high thermal conductivity.

However, the addition of the filler makes the resin hard and brittle, so that cracks are likely to occur, thereby lowering the heat cycle resistance of the part. In general, when an inorganic filler is added, the polymerizable composition (aqueous support material before polymerization and curing) becomes solid at room temperature, or becomes a high viscosity of several to several tens of N · s · m ⁻² or more, resulting in insufficient fluidity. Therefore, the conventional polymeric composition could not be applied to the sealing of a high density integrated circuit, a microcircuit, etc., if filler was added. For example, Japanese Unexamined Patent Application Publication No. 10-219080 discloses a low viscosity epoxy resin prepolymer. In this prepolymer, for example, a low viscosity of 2.9 N · s · m ⁻² is realized. However, this level of viscosity still does not encapsulate high density integrated circuits or microcircuits. Moreover, since the glass transition temperature of the hardened | cured material (resin) is 110 degreeC, since it exhibits a mechanically hard and brittle property under actual use temperature, there exists a problem that a crack occurs easily in a heat-resistant test.

Therefore, a method of encapsulating using engineering plastics having excellent mechanical toughness has been considered. For example, Japanese Patent Laid-Open No. 10-292118 proposes a method of sealing electronic components such as IC chips by extrusion molding at a cylinder temperature of 300 ° C. using polyphenylene sulfide. However, engineering plastics are thermoplastic resins, and their molding generally requires high temperatures of 300 ° C. or higher, and furthermore, even at such high temperatures, they also exhibit high melt viscosity on the order of tens of N · s · m ⁻² . It is extremely difficult to fully impregnate the microcircuit using plastic.

On the other hand, low elastic modulus polymers, such as a silicone resin and a urethane resin, may be used as a sealing resin in order to prevent the reliability of electrical / electronic components from peeling and cracking of a sealing resin. However, prepolymers of silicone resins and urethane resins generally have high viscosity and have poor impregnation properties. In addition, the dielectric constant of these polymers is higher than that of the olefin resin, resulting in poor electrical characteristics. For this reason, in the technique described in Japanese Patent Laid-Open No. 8-316373, a method of optimizing the resin filling method during molding and a method of optimizing the structure of parts are proposed in Japanese Patent Laid-Open No. 10-233472. Improvements alone cannot yet sufficiently impregnate the microcircuit. In addition, Japanese Patent Application Laid-Open No. 5-287077 proposes a silicone resin having a lower viscosity of the prepolymer, but the viscosity is still 0.3 N · s · m ⁻² or more, so that it is still possible to sufficiently impregnate the microcircuit. I can't.

On the other hand, cycloolefin resins obtained by metathesis polymerization of norbornene-based compounds are known to be excellent in mechanical properties, electrical properties, and water resistance, and Japanese Patent Publication No. 5-41088 discloses reaction injection of norbornene-based compounds. The manufacturing method which seals an electrical / electronic component by shaping | molding is proposed. Japanese Unexamined Patent Publication No. Hei 9-183833 proposes a norbornene-based compound suitable for encapsulation of electrical and electronic components by a new metathesis polymerization catalyst. Furthermore, Japanese Patent Laid-Open No. 10-182922 discloses that the metathesis polymerizable cycloolefin-based compound (prepolymer) has a low viscosity even when a filler is added and is suitable for encapsulation of electrical and electronic parts. However, these are all made from the hardened | cured material of the prepolymer which combined the norbornene-type compound, such as dicyclopentadiene, and an inorganic filler, and since the hardened | cured material obtained has high glass transition temperature, it is lacking the adhesiveness to an inorganic member, Moreover, since elastic modulus is also high, there exists a problem that it will peel easily at the interface with an inorganic member.

In addition, the metathesis polymerization catalyst system described in Japanese Patent Application Laid-Open No. 5-41088 discloses an organoammonium salt of tungsten or molybdenum which is a catalyst component disclosed in Japanese Patent Application Laid-Open No. 59-51911, and an alkoxyalkylaluminum halide or aryl which is an activator. Since it is the same as the catalyst system which combined oxyaluminum halide, since it is easy to deactivate by oxygen, there also exists a problem that shaping | molding must be performed in inert gas atmosphere.

As described above, in hard resins having high modulus of elasticity such as epoxy resins, problems such as peeling and cracking are likely to occur, and there is a problem in reliability of electrical and electronic parts. In addition, a soft resin having a low elastic modulus such as a silicone resin or urethane resin has a high prepolymer viscosity, so that impregnation is poor, and there is a problem that a high density integrated circuit or a microcircuit cannot be sufficiently sealed. In addition, polymers obtained by using dicyclopentadiene as a cycloolefin-based resin and metathesis polymerization also have a problem of exfoliation because of high elastic modulus. Furthermore, there exists a problem that sealing with cycloolefin resin using a metathesis polymerization catalyst must be shape | molded completely in inert gas atmosphere.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates in particular to resin encapsulated electronic devices suitable for components including elements such as silicon chips, such as LSIs (large scale integrated circuits) and ICs (integrated circuits), transformers, coils, transistors, diodes, and power switches.

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

Disclosure of the Invention

In order to solve the problem mentioned above, in this invention, the sealing member obtained by superposing | polymerizing a polymeric composition is provided, The electronic device whose flexural modulus in 23 degreeC of the said sealing member is 500 Mpa or less is provided. However, flexural modulus is prescribed | regulated by JIS-K-7203. By using such a sealing member, good precision casting formation and reflow soldering resistance are obtained. Moreover, a polymeric composition is a polymeric liquid substance whose viscosity is less than 0.3 N * s * m <^-2> in 23 degreeC, or contains an olefin compound.

The electronic device of the present invention may be, for example, a part of another product such as a resin encapsulated semiconductor device or an ignition coil, or may be any of an electric part and an electronic part. Examples of the electronic device suitable for the present invention include an ignition coil having a center core made of a magnetic body, a primary coil and a secondary coil wound around the center core, and an outer core made of a magnetic body disposed outside the secondary coil. Can be mentioned.

It is preferable that the sealing member in this invention is at least one of following (1)-(4).

(1) Glass transition temperature is 80 ℃ or less.

(2) The coefficient of linear expansion is not less than 100 ppm at 23 ° C.

(3) Absorption rate is less than 0.1 weight% at 23 degreeC water immersion for 24 hours.

(4) Dielectric constant is 3.0 or less at 23 degreeC.

In addition, it is preferable that the polymeric composition which is a raw material of the sealing member does not contain a solvent, and may contain a filler, and is an additive (namely, a modifier, a polymerization rate regulator, a foaming agent, an antifoamer, a coloring agent, a stabilizer, adhesiveness). Imparting agent, flame retardant, coupling agent and / or organic peroxide). 1 type may be sufficient as an additive and may be used in combination of 2 or more type as needed. Moreover, you may use combining a filler and an additive.

It is preferable that a polymeric composition contains 1 or more types of metathesis polymerizable cycloolefin compounds, and it is more preferable that 2 or more types of compounds selected from the metathesis polymerizable cycloolefin compounds of molecular weight less than 300 are included.

When a polymerizable composition contains a metathesis polymerizable cycloolefin compound, it is preferable that a polymeric composition further contains a metathesis polymerization catalyst. As a metathesis polymerization catalyst which can be used, the compound represented by following General formula (1)-(3) is mentioned.

… (One)

… (2)

… (3)

In the general formulas (1) to (3), 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. And 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. R ¹ and R ² each independently represent 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, a carboxylate group having 1 to 18 carbon atoms, and a carbon group having 1 to 18 carbon atoms. Alkoxy group, C2-C18 alkenyloxy group, C2-C18 alkynyloxy group, C2-C18 aryloxy group, C2-C18 alkoxycarbonyl, C1-C18 alkylthio group, C1-C1 An alkylsulfonyl group of -18 or an alkylsulfinyl group of 1 to 18 carbon atoms is represented, and R ³ represents hydrogen, an aryl group or an alkyl group of 1 to 18 carbon atoms.

When these metathesis polymerization catalysts are used in the reaction for obtaining an olefin resin, since the influence of oxygen and moisture in air is hard to be affected, variation in molding can be reduced. Therefore, these catalysts are suitable for the present invention. In the electronic device of the present invention, a molded article in an atmosphere containing oxygen can be used as the sealing member.

Best Mode for Carrying Out the Invention

The electronic device of this invention is equipped with the sealing member which is a polymer of a polymeric composition. As for the sealing member, the flexural modulus in 23 degreeC prescribed | regulated to JIS-K-7203 is 500 Mpa or less. Hereinafter, in this specification, the resin composition which comprises a sealing member may be called low elasticity resin.

It is preferable that the said polymerizable composition is a polymerizable liquid substance which is liquid at 23 degreeC. It is preferable that the viscosity of a polymeric liquid substance is 0.005 N * s * m <^-2> -0.2N * s * m <^-2> . In the case of an electronic device such as a flyback transformer or an ignition coil, if the viscosity of the polymerizable liquid product exceeds 0.3 N · s · m ⁻² , impregnation inside the winding coil may be deteriorated, and an unfilled portion may be generated and the insulation may be deteriorated. have. Similarly, when a polymerizable liquid substance having a viscosity of more than 0.3 N · s · m ⁻² is used as an encapsulant of a semiconductor device in a semiconductor device represented by a dual inline package (DIP), a chip, a lead frame or a substrate ( The connection wiring between a polyimide film, a ceramic, etc.) can be cut | disconnected.

It is preferable that the flexural modulus of sealing resin used by this invention is 300 Mpa or less, and it is more preferable that it is 100 Mpa or less. When it exceeds 500 MPa, peeling or cracking tends to occur.

I. Bag member

The kind of resin for sealing used for the sealing member in this invention will not be restrict | limited especially if it is equipped with the above characteristic. For example, epoxy resins, urethane resins, silicone resins, acrylic resins, methacryl resins, polyester resins, phenol resins, olefin resins (that is, resins obtained by polymerizing olefin compounds) and the like can be used. Among these, acrylic resins, methacryl resins, polyester resins and olefin resins are preferable, and olefin resins are particularly preferable in terms of excellent electrical properties.

80 degrees C or less is preferable, as for the glass transition temperature of the sealing member used for the electronic device of this invention, 50 degrees C or less is more preferable, 25 degrees C or less is especially preferable. When the glass transition temperature exceeds 80 ° C., cracks are likely to occur inside the sealing member. For the same reason, the coefficient of linear expansion of the sealing member is preferably 100 ppm or more.

Further, the water absorption of the sealing member is preferably less than 0.1% by weight in water immersion at 23 ℃ 24 hours. If the water absorption is 0.1% by weight or more, the insulation property and the reflow soldering resistance tend to decrease.

In addition, with increasing density and high integration of the electronic device, the sealing member preferably has a dielectric constant of 2.0 to 3.0, and more preferably 2.0 to 2.9 so as not to interfere with electromagnetic waves.

II. Composition of Polymerizable Composition for Sealing

Hereinafter, the composition of the polymeric composition for sealing which is a raw material of the sealing member used for the electronic device of this invention is demonstrated concretely. It is preferable that the polymeric composition for sealing is a polymeric liquid substance whose viscosity is less than 0.3 N * s * m <^-2> at 23 degreeC, or contains an olefin compound as a resin raw material (monomer or oligomer).

A. Resin monomer oligomer

Although the kind of sealing resin used for the sealing member in this invention is not restrict | limited, An olefin resin is especially preferable.

As a raw material of the olefin resin suitable for the present invention, general publicly known general-purpose resins such as polyethylene, polypropylene, polybutadiene, etc. may be mentioned, but a cycloolefin compound is preferable, and a cycloolefin compound capable of metathesis polymerization is particularly preferable. to be.

Cycloolefin compounds which can be metathesis polymerized are roughly classified into norbornene-based cycloolefin compounds and non-norbornene-based cycloolefin compounds.

As norbornene-type cycloolefin compound, For example, substituted or unsubstituted,

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

Tricyclic norbornenes such as dicyclopentadiene (dimer of cyclopentadiene), dihydrodicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene,

Tetracyclic norbornenes such as tetracyclododecene, methyltetracyclododecene, dimethylcyclotetradodecene,

And five or more rings of norbornene such as tricyclopentadiene (trimer of cyclopentadiene) and tetracyclopentadiene (tetramer of cyclopentadiene).

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

Moreover, it is also possible to use the compound which has two or more norbornene groups, for example, tetracyclo dodecadiene, symmetric tricyclopentadiene, etc. as a polyfunctional crosslinking agent. Furthermore, norbornene derivatives, such as a high-mic acid, a high-hydric acid anhydride, norbornadiene, can also be used.

These metases polymerizable cycloolefin compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

Of these, dicyclopentadiene, methyltetracyclododecene, ethylidene norbornene, tricyclopentadiene, cyclooctene, cyclooctadiene, cyclododecatene, and the like are preferable in terms of availability and economical efficiency.

In addition, dicyclopentadiene is heat-processed beforehand, and a part of dicyclopentadiene is made into cyclopentadiene oligomers, such as a tricyclopentadiene and tetracyclopentadiene, or the vinyl norbornene and methyl vinyl norbornene which are impurities Isomerization with tetrahydroindene or methyltetrahydroindene can be carried out. This preheating process is normally performed at 120-250 degreeC for about 0.5 to 10 hours.

In addition, the commercially available commercial olefin resin raw materials may contain impurities, and various types of cycloolefin compounds are commercially available. For example, dicyclopentadiene includes vinylnorbornene, tetrahydroindene, methylvinylnorbornene, methyltetrahydroindene, methyldicyclopentadiene, dimethyldicyclopentadiene, tricyclopentadiene, and the like. Octadiene may contain unreacted butadiene, cyclooctane, or the like as impurities. However, these commercial items may be used without particular purification. In addition, when used for the electronic device of the present invention, as the water support material (monomer or oligomer), it is generally good to use 90% or more, and preferably 95% or more, particularly preferably 98% or more.

It is preferable to use these cycloolefin compounds in combination of 2 or more types of molecular weight less than 300. This is because the elastic modulus can be controlled.

For example, the resin obtained by polymerizing a bicyclic or polycyclic compound such as dicyclopentadiene or tricyclopentadiene is hard, but monocyclic compounds such as cyclopentene, cyclooctene, cyclooctadiene, cyclotodecatene and cyclooctatetraene By using a sieve together, elastic modulus can be reduced.

It is preferable to mix | blend these monocyclic cycloolefin compounds used in order to reduce an elasticity modulus in 40 mol% or more and less than 99 mol% with respect to the compounding total mole number of a polycyclic monomonomer. If the monocycle is less than 40 mol%, the elastic modulus will be 500 MPa or more. Moreover, when 99 mol% or more is used, since crosslinking density is low, the toughness of resin will fall.

B. Metathesis Polymerization Catalyst

It is preferable that the sealing resin suitable for this invention is what hardened | cured by metathesis polymerization. As the metathesis polymerization catalyst used for the metathesis polymerization, a known catalyst system can be used as the catalyst for the ring-opening metathesis polymerization of the cycloolefin-based compound, and examples thereof include a two-component catalyst and a one-component catalyst. There is no special limitation. However, since the stability is good in air, a one-component metal carbene type catalyst is preferable.

The amount of the metathesis catalyst added is usually 0.001 to 20% by weight based on the cycloolefin-based polymerizable composition, but is preferably in the range of 0.01 to 5% by weight for reasons of economic efficiency and curing rate.

The two-component metathesis polymerization catalyst is a catalyst system combining a catalyst component and an activator. As the two-component metathesis polymerization catalyst used in the present invention, a complex metal halide, a metal carbene or a Ziegler-Natta type including transition metals such as titanium, vanadium, molybdenum, tungsten, rhenium, iridium, ruthenium and osmium Coordination catalysts.

Specifically, tungsten compounds such as tungsten hexachloride, tungsten oxy tetrachloride, tungsten oxide and tridecyl ammonium tungstate, molybdenum pentachloride, molybdenum oxychloride, molybdenum oxide and tridecyl ammonium molybdate, and molybdenum pentachloride Tantalum compounds and the like [[cyclohexyl) ₃ P] ₂ RuCl ₂ , [(phenyl) ₃ P] ₃ RuCl ₂ , (cyclohexyl) ₃ P (p-cymene) RuCl ₂ , [(phenyl) ₃ P] ₃ (CO) and the like can be mentioned ruthenium compound of RuH ₂ and the like.

A well-known cocatalyst (activator) is used together in these bicomponent metathesis polymerization catalysts as needed. As the specific example, an alkyl aluminum halide, an alkoxy alkyl aluminum halide, an aryloxy alkyl aluminum halide, an organotin compound, etc. are mentioned.

Unlike the two-component catalyst system, the one-component metathesis polymerization catalyst is a ring-opening metathesis reaction of the cycloolefin-based compound by the metathesis reaction without losing the catalytic activity easily by moisture in the air or adsorption water on the solid surface. Cis polymerization can be carried out. As such a one-component metathesis polymerization catalyst, specifically, a metal carbene coordination stabilized with respect to water by taking a structure in which a metal carbene structure of ruthenium or osmium is the main skeleton and a ligand having a large steric hindrance is coordinated to the center metal. A catalyst is mentioned.

As a preferable example of these ruthenium or osmium metal carbene coordination catalyst, the compound represented by either of following General formula (1)-(3) is mentioned. Among these, the compound represented by General formula (3) is especially preferable from a viewpoint of catalyst activity, synthetic | combination yield, economy, etc.

… (One)

… (2)

… (3)

Here, M represents ruthenium or osmium.

X ¹ and X ² each represent an anionic ligand selected independently. Anionic ligand means an atom or group of atoms having a negative charge when the coordination to the central metal is removed. As such anionic ligands, for example, hydrogen, halogen, CF ₃ CO ₂ , CH ₃ CO ₂ , CFH ₂ CO ₂ , (CH ₃ ) ₃ CO, (CF ₃ ) ₂ (CH ₃ ) CO, (CF ₃ ) (CH ₃₎ a CO _2, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, a phenyl group, a phenoxy group, a tosyl group, mesyl group, trifluoromethanesulfonate group and the like. It is particularly preferable that both X ¹ and X ² are halogen (especially chlorine).

L ¹ and L ² each independently represent a neutral ligand. A neutral ligand means an atom or group of atoms having a neutral charge when the coordination to the central metal is removed. Such groups include, for example, PR ⁴ R ⁵ R ⁶ , wherein R ⁴ is a secondary alkyl group or a cycloalkyl group, and R ⁵ and R ⁶ are an aryl group, a C1-C10 primary alkyl group and a secondary alkyl group and a cycloalkyl group. Phosphine-based electron donors represented by each independently selected group). L ¹ and L ² are preferably both P (cyclohexyl) ₃ , P (cyclopentyl) ₃ or P (isopropyl) ₃ , and may be different from each other.

Furthermore, pyridine, p-fluoropyridine, imidazolylidene, etc. are mentioned as a ligand. As an imidazolylidene compound, the heterocyclic compound represented by following General formula (4) or (5) is preferable. Among these, it is particularly preferable to make the compound represented by Formula (5) as a ligand.

… (4)

… (5)

Here, R <^7> and R <^8> is a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a cycloalkyl group, an aryl group each independently selected. 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, and an aryl group. Furthermore, these groups may be halogen, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, It may be substituted with a phenyl group. In view of thermal stability, at least one of R ⁷ and R ⁸ is preferably a group represented by the following general formula (6).

… (3)

In this formula (6), R <^9> and R <^10> is hydrogen, a C1-C3 alkyl group or a C1-C3 alkoxyl group, respectively, R <^11> is hydrogen, a C1-C10 alkyl group, an aryl group, and a hydroxide Carboxyl group, thiol group, thioether group, ketone group, aldehyde group, ester group, ether group, amine group, imine group, amide group, nitro group, carboxylic acid group, disulfide group, carbonate group, isocyanate group, carbodiimide group, Carboalkoxy groups, carbamate groups, halogens and the like.

As a specific imidazolylidene compound which can be used as a ligand, the carbene represented by following structural formula (7) or (8) is mentioned. Among these, the imidazolylidene compound of the formula (7) is particularly preferable in terms of polymerization activity.

… (7)

… (8)

Q ¹ and Q ² each independently represent a 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 each independently selected 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, a carboxylate group having 1 to 18 carbon atoms, and 1 to C carbon atoms. 18 alkoxyl group, C2-C18 alkenyloxy group, C2-C18 alkynyloxy group, C2-C18 aryloxy group, C2-C18 alkoxycarbonyl group, C1-C18 alkylthio group, carbon number An alkylsulfonyl group having 1 to 18 or an alkylsulfinyl group having 1 to 18 carbon atoms is represented, and 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 those represented by the following structural formulas (9) to (11).

… (9)

… 10

… (11)

Moreover, the compound represented by following General formula (12) is also suitable for this invention.

… (12)

In General Formula (12), R ¹¹ is a phenyl group, isopropyl group or cyclohexyl group.

Such a metal carbene compound can be obtained by a well-known synthetic method. For example, a method using propargyl chloride disclosed in Organometallics Vol. 16, 18, p. 3867 (1997) is mentioned. The synthesis example of the compound represented by the said structural formula (9) is shown below (Ref .: Organometallics Vol. 16, No. 18, p. 3867 (1997)). In addition, cy represents a cyclohexyl group.

Synthesis Example

Into a 500 mL Fisher-Porter bottle, put 250 ml of cyclooctadiene ruthenium chloride (21 mmol), tricyclohexylphosphine (42 mmol), sodium hydroxide (7.2 g) and oxygen-free sec-butanol, Heated to 90 ° C. under hydrogen atmosphere. Pressurization is repeated several times until absorption of hydrogen is complete, and stirring is continued overnight. Cool to room temperature with hydrogen pressure to obtain a pale yellow precipitate. 30 ml of water is added, and the precipitate is filtered and dried in a hydrogen stream to obtain Ru (H) ₂ (H ₂ ) ₂ (P (cy) ₃ ) ₂ (yield about 80%). Next, this Ru (H) ₂ (H ₂ ) ₂ (P (cy) ₃ ) ₂ (1.5 mmol) was dissolved in 30 mL of dichloroethane, cooled to -30 ° C, and 3-chloro-3-methyl -1-butyne (1.5 mmol) is added. The solution turns red purple immediately. After reacting for 15 minutes as it is, the cooling bath is separated, and when degassed methanol (20 ml) is added, purple crystals precipitate. Washed with methanol and dried to give Ru carbene catalyst (Cl) ₂ (P (cy) ₃ ) ₂ Ru = CH-CH = C (CH ₃ ) ₂ (yield 95%).

C. Additives

The polymerizable composition for encapsulation (preferably polymerizable liquid) is a filler, a modifier, a polymerization rate regulator, a foaming agent, an antifoaming agent, a colorant, and a stabilization agent, if necessary, in consideration of the physical properties and appearance of the cured product, the moldability of the composition, and the like. An agent, an adhesion imparting agent, a flame retardant, a coupling agent, an organic peroxide, and the like can be optionally added.

(Filler)

Examples of the filler used in the present invention include inorganic fillers such as molten silica, crystalline silica, silica sand, calcium carbonate, aluminum hydroxide, magnesium oxide, clay and inorganic ion exchangers, and wood flour, polyester, silicone, polystyrene-acrylo Bead-like organic fillers such as nitrile-butadiene-styrene (ABS). Among these, silica and aluminum hydroxide are preferable in terms of electrical properties and thermal conductivity.

As a commercial item of the filler suitable for this invention, CRT-AA, CRT-D, RD-8 (above, brand names of leucine company), COX-31 (brand name of Micro Co., Ltd.), C-303H, C-315H, C-308 (above, brand names of Sumitomo Kagaku Kogyo Co., Ltd.), SL-700 (brand name of Takehara Kagaku Kogyo Co., Ltd.), etc. are mentioned.

The compounding quantity of these inorganic fillers is 0 to 95 weight% in resin, Preferably it is 10 to 95 weight%, More preferably, it is 30 to 95 weight%, It is especially preferable to set it as the compounding of 30 to 75 weight%. If the blending amount exceeds 95% by weight, the dielectric constant of the encapsulation member will exceed 3.0, resulting in deterioration of electrical characteristics.

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. It is preferable that it is between 0.1-100 micrometers, and, as for an average particle diameter, the thing of 1-50 micrometers is especially preferable. Combining these different average particle diameters can improve fine filling and fluidity.

Moreover, as a filler suitable for this invention, inorganic / organic fibrous fillers, such as a milled glass, a cut fiber, a microfiber, a microballoon, flaky glass powder, carbon fiber, and aramid fiber, are also mentioned. It is also possible to use these fibrous fillers together with a filler. Aspect ratios and shapes can be appropriately selected according to the purpose. The compounding quantity of these fibrous fillers is 0-20 weight part normally with respect to 100 weight part of sealing resin, Preferably it is 0-10 weight part.

(2) modifiers

As the modifier used in the present invention, for example, elastomer, natural rubber, butadiene rubber, copolymer (styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-maleic acid copolymer, ethylene- Vinyl acetate copolymers) and thermoplastic resins (methyl polymethacrylate, polyvinyl acetate, polystyrene and the like).

These copolymers and thermoplastic resins may be esterified and the polar group may be grafted. In addition, epoxy resins, urethane resins, polyester resins, silicone resins, phenol resins, polyimide resins, polyamide resins, polyamideimide resins and derivatives thereof may be blended to improve physical properties.

Further, for example, a compound obtained by reacting an epoxy compound with a norbornene monocarboxylic acid, a compound obtained by reacting an isocyanate compound with a norborneneol, a high-mic acid-modified polyester, a petroleum resin, etc. may also be mentioned as a modifier applicable to the present invention.

Further, petroleum resins may be those prepared by using known C5 or C9 fractions purified from ethylene plants as raw materials, for example, kynton (trademark of Nippon Zeon Co., Ltd.) or thermoplastic polynorbornene resin Nosorex (Nippon). Xeon Co., Ltd. brand name) etc. can be used. It is preferable that these petroleum resins have a number average molecular weight of 1000 or more, and it is more preferable to have functional groups, such as a hydroxyl group and ester group, in a resin skeleton.

Although the compounding quantity of these modifiers also depends on the physical property of resin made into the objective, it can be generally 0.2-50 weight part with respect to 100 weight part of polymerizable compositions. Preferably it is the range of 0.5-40 weight part. If it is less than 0.2 part by weight, the effect of the modifier is hardly expressed, and if it is 50 parts by weight or more, the polymerizability tends to be lowered.

(3) polymerization rate regulator

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

Moreover, when sealing resin is olefin resin, phosphate, such as triisopropyl phosphine, triphenyl phosphine, and tricyclohexyl phosphine, can be used as a polymerization rate regulator.

These polymerization rate regulators can be used 0.005-20 weight part with respect to 100 weight part of polymerizable compositions. The compounding quantity of these polymerization rate regulators is for the purpose of controlling the temporary service time for shaping | molding, and when the temporary service time may be short, the usage amount is reduced, and when it wants to lengthen, it increases.

(4) antifoaming agent

As the antifoaming agent, for example, known antifoaming agents such as silicone oil, fluorine oil and polycarboxylic acid polymer can be used. An antifoamer can be added 0.001-5 weight part with respect to 100 weight part of polymerizable compositions normally.

Examples of the blowing agent include low boiling point hydrocarbon compounds such as pentane, propane and hexane, physical foaming agents (carbonate gas, water vapor, etc.), chemical foaming agents (compounds that generate nitrogen gas by decomposition (azobisisobutylonitrile or N ', N-). Azo compounds such as dinitrosopentamethylenetetramine, nitroso compounds, and the like)).

(5) colorant

As a coloring agent suitable for this invention, inorganic pigments, such as titanium dioxide, cobalt blue, cadmium yellow, organic pigments, such as carbon black, aniline black, (beta) -naphthol, phthalocyanine, quinacridone, azo system, quinophthalone, and indanthrene blue These can be mentioned and can be mix | blended according to a desired hue. You may use these in combination of 2 or more type. Usually, 0.1-50 weight part of addition amounts of these pigment can be added with respect to 100 weight part of polymerizable compositions.

(6) stabilizer

As a stabilizer used for this invention, a ultraviolet absorber, a light stabilizer, and antioxidant are mentioned.

As a ultraviolet absorber, for example,

Salicylic acid type ultraviolet absorbers, such as phenyl salicylate and p-t- butylphenyl salicylate,

Benzophenone ultraviolet absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone,

2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- {2'-hydroxy-3 ', 5'-di (t-butyl) phenyl} benzotriazole, 2- {2' Benzotriazole ultraviolet absorbers such as -hydroxy-3 ', 5'-di (t-amyl) phenyl} benzotriazole,

And cyanoacrylate ultraviolet absorbers such as 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate. These may be used independently and may be used together 2 or more types.

Although the addition amount of these ultraviolet absorbers is suitably determined according to the use environment of an electronic device, the presence or absence of a housing, and a required characteristic, 0.05-20 weight part can be normally used with respect to 100 weight part of polymerizable compositions.

Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, Hindered amine light stabilizers, such as a succinate dimethyl 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6- tetramethyl piperidine polycondensate, are mentioned. These light stabilizers can generally be added in an amount of 0.05 to 20 parts by weight based on 100 parts by weight of the polymerization composition.

Furthermore, as antioxidant used by this invention,

Quinones such as parabenzoquinone, toluquinone and naphthoquinone,

Hydroquinones such as hydroquinone, para-t-butylcatechol, and 2,5-di (t-butyl) hydroquinone;

Phenols such as di (t-butyl) paracresol hydroquinone monomethyl ether and pyrogarol;

Copper salts such as copper naphthenate and copper octenate,

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

Oximes such as quinone dioxime and methyl ethyl ketooxime, amine hydrochlorides such as triethylamine hydrochloride and dibutylamine hydrochloride,

And oils such as mineral oil, essential oil and fatty oil. These antioxidants are added in varying types and amounts depending on conditions such as compatibility with the filler, desired molding workability, and resin storage stability. Usually, the addition amount can use 10-10,000 ppm with respect to 100 weight part of polymerizable compositions.

(7) adhesion imparting agent

As an adhesive imparting agent used by this invention, a silane coupling agent is mentioned. A silane coupling agent is represented by following General formula (13) normally.

Y _n -Si-X _4-n ... (13)

However, Y is a monovalent group which has a functional group, and couple | bonds with Si, X is a monovalent group which has hydrolyzability and couple | bonds with Si. n is an integer of 1-3.

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

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

Specific examples of such a silane coupling agent include vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, and γ-mercaptopropyltrimeth Oxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N, N-dimethylaminophenyltriethoxysilane, mercaptoethyltriethoxysilane, methacryloxyethyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, 3- (N-styrylmethyl-2-aminoethylamine) propyltrimethoxysilane hydrochloride, etc. are mentioned, These can also be mixed and used. A silane coupling agent can be added 0.001-5 weight part normally with respect to 100 weight part of polymerizable compositions.

(8) flame retardant

As the flame retardant, halogen-based compounds such as hexabrombenzene, tetrabrombisphenol A, decabrom diphenyloxide, tribromphenol, dibromophenyl glycidyl ether, perchloropentacyclodecane and fatty acid derivatives can be used. These may be used independently and may use 2 or more types together.

In addition, phosphoric acid compounds such as tris phosphate (dichloropropyl) and tris phosphate (dibromopropyl), boric acid compounds and the like can also be used in combination.

Further, as the flame retardant, antimony trioxide, iron oxide, alumina hydride and the like can be cited, and the flame retardant effect can be enhanced by using these together with the flame retardant.

Usually, a halogen flame retardant is 1-50 weight part with respect to 100 weight part of cycloolefin type compounds, and a flame retardant, such as antimony trioxide, is used in the range of 1-15 weight part.

Moreover, hydrates, such as aluminum hydroxide and magnesium hydroxide, which are commercially available as a filler for plastics, can also be used as a filler for the purpose of flame retardancy. It is preferable to use these addition amount in the range of 10-300 weight part with respect to 100 weight part of polymeric compositions.

(9) organic peroxides

Furthermore, organic peroxides can also be added. Examples of the organic peroxide include cumene hydroperoxide, tertiary butyl peroxy 2-ethylhexanate, methyl ethyl ketone peroxide, benzoyl peroxide, acetylacetone peroxide, bis-4- tertiary butyl cyclohexane dicarbonate, Known things, such as 2, 5- dimethyl- 2, 5-bis (tertiary butyl peroxy) hexyn-3, are mentioned, These may be used independently and may use 2 or more types together. It is preferable to use the addition amount 0.1-10 weight part with respect to 100 weight part of polymerizable compositions normally.

(10) reactive diluents

In the electronic device of the present invention, the polymerizable composition used for encapsulation includes an acrylic monomer, a methacryl monomer, a vinyl monomer, a diaryl phthalate, and the like in order to adjust the viscosity of the composition and the mechanical and electrical properties of the encapsulation member. Low viscosity reactive diluents may be used. These may be used individually by 1 type and may use 2 or more types together.

However, it is preferable that the polymeric composition used for sealing in the electronic device of this invention does not contain a solvent. The solvent here means a generally known non-reactive diluent such as benzene, toluene, xylene, ethyl acetate and methyl ethyl ketone.

Moreover, when using a commercial item as an additive, the solvent may be contained. The solvent contained in such a commercial item shall be ignored. However, also in this case, it is preferable that content of a solvent is less than 2 weight part with respect to a polymeric composition from the point of preventing swelling at the time of hardening.

(11) other

In the polymeric composition for sealing used by this invention, a red component can be added as needed other than the above component. For example, in order to improve the flowability of the filler, a coupling agent (represented by a commercially available wetting agent or a dispersing agent such as BYK series manufactured by Vikchem Co., Ltd.) may be added. Moreover, in order to improve workability, mold release agents, such as silicone oil and zinc stearate, can also be added.

D. Forming Method

As the molding method of the electronic device of the present invention, for example, vacuum injection molding, pressure injection molding, impregnation molding, RTM molding, dipping, lamination such as hand lay-up or spray-up, press molding, filament winding, centrifugal molding, vacuum or Pressurized bag method, continuous molding method, draw molding method, injection molding method, transfer molding and the like can be used. When using the metathesis polymerization catalyst represented by the general formulas (1) to (3), it is not necessary to perform these moldings in an inert gas atmosphere.

When using a cycloolefin type polymerizable composition, superposition | polymerization can be performed by adding and dissolving a metathesis polymerization catalyst to a composition, and heating.

The temperature at the time of adding and melting the metathesis polymerization catalyst to the polymerizable composition is usually 0 to 80 ° C, preferably room temperature to 50 ° C.

The heating operation for obtaining a polymer may be one step heating, or two or more multistep heating. In the case of one-step heating, the temperature is usually 0 to 250 ° C, preferably 20 to 200 ° C. In the case of two-stage heating, the temperature of the first stage is usually 0 to 150 캜, preferably 10 to 100 캜, and the temperature of the second stage is usually 20 to 200 캜, preferably 30 to 180. It is set to ° C.

Moreover, although polymerization time can be suitably determined according to the quantity of a catalyst and polymerization temperature, it is 1 minute-50 hours normally.

III. housing

Although the electronic device of this invention is equipped with the sealing member which is the hardened | cured material of the polymeric composition mentioned above, this may be covered by the housing again. In this case, the sealing member and the housing may be integrally formed. Furthermore, you may enclose the board | substrate which mounted an element in the housing, and resin-sealed.

The material of the housing is selected from inorganic materials such as SUS, copper, iron, aluminium, ceramics, and organic materials such as thermosetting resins, thermoplastic resins, biodegradable resins, and natural resins according to the purpose and use. none. The shape and dimensions of the housing and electronic device can also be arbitrarily designed according to the purpose and the like.

Hereinafter, an Example demonstrates this invention. In addition, "part" in a following example and a comparison means a "weight part" unless there is particular limitation.

I. Preparation of resin

<Resin 1: Olefin-Low Modulus Resin>

50 parts by weight of high-purity dicyclopentadiene (manufactured by Marsen Seki Yuka Chemical Co., Ltd., purity of 99% or more), 50 parts by weight of cyclooctadiene (manufactured by HULS, purity of 98.5% or more), and a silane coupling agent (Nippon Unica Co., Ltd.) ), FZ-3778) 0.1 parts by weight was mixed. Subsequently, the molten silica (Ryushin Co., Ltd., Hughex RD-8) of 15 micrometers of average particle diameters, or aluminum hydroxide (C-308 Sumitomo Chemical Co., Ltd. make, C-308) of 8 micrometers of average particle diameters was shown in Table 1. Quantification was added to obtain a compound. 0.2 parts by weight of the metathesis polymerization catalyst represented by Structural Formula (9) was added to the compound immediately before the mold, and was used for the test. Unless otherwise specified, curing conditions were made into 38 degreeC 2 hours + 100 degreeC 1 hour + 125 degreeC 1 hour.

<Resin 2: Acrylic Low Elastic Modulus Resin>

10 parts of polypropylene glycol dimethacrylates (manufactured by Kyo-Eshaka Gaku Co., Ltd., NK ester 9PG) are mixed with 90 parts of lauryl methacrylate (manufactured by Kyo-Eshaka Gaku Co., Ltd., light ester L), and further, a silane is added. 0.1 weight part of coupling agents (made by Nippon Unicar Co., Ltd., FZ-3778) were mixed. Subsequently, a predetermined amount of molten silica (manufactured by Ryushin Co., Ltd., Hughex RD-8) having an average particle diameter of 15 µm was added to the compound, thereby obtaining a compound. To this compound, 0.5 part of t-butylperoxy-2-ethylhexanoate as a polymerization catalyst was added immediately before the mold to provide a test. Unless otherwise specified, curing conditions were made into 40 degreeC 1 hour + 60 degreeC 3 hours + 80 degreeC 1 hour + 100 degreeC 1 hour.

<Resin 3: Polyester-based low modulus resin>

463 parts of diethylene glycol, 454 parts of neopentyl glycol, 927 parts of adipic acid and 156 parts of maleic anhydride were added to a two-liter four-necked flask equipped with a stirrer, a condenser, a nitrogen gas introduction tube, and a thermometer. While flowing slowly, it heated up at 150 degreeC over 1 hour using a mantle heater, it warmed for 1 hour, and it heated up at 220 degreeC over 5 hours. It was kept at that temperature for 6 hours to obtain an unsaturated polyester having an acid value of 30.

Here, the styrene monomer dissolved in 0.01% of hydroquinone is added to dissolve the unsaturated polyester component so as to be 70% by weight, and the unsaturated polyester having a viscosity at 25 ° C. of 0.19 Pa · s (0.19 N · s / m 2) is obtained. It was made into a resin solution.

0.15 parts of bis (4-t-butylcyclohexyl) peroxydicarbonate, 0.45 part of cumene hydroperoxide, and 0.8 part of benzoyl peroxide were added as an organic peroxide to this resin liquid. Curing conditions were 80 degreeC 3 hours + 125 degreeC 3 hours, unless there is particular notice.

<Resin 4: Dicyclopentadiene Resin 1>

100 parts by weight of the same high-purity dicyclopentadiene as in Resin 1 and 0.1 parts by weight of a silane coupling agent (manufactured by Nippon Unica Co., Ltd., FZ-3778) were mixed. Subsequently, a predetermined amount shown in Table 2 was added to a molten silica (manufactured by Ryushin Co., Ltd., Hughex RD-8) having an average particle diameter of 15 µm, followed by stirring and mixing to obtain a compound. Curing was carried out in the same manner as in Resin 1 using a metathesis polymerization catalyst represented by Structural Formula (9).

<Resin 5: Dicyclopentadiene resin 2>

To dicyclopentadiene used in Resin 1, 40 mmol of diethyl aluminum chloride, 52 mmol of n-propyl alcohol, and 20 mmol of silicon tetrachloride were added to a dry box purged with nitrogen, respectively, to prepare a solution A.

In addition, 10 mmol mol of tridecyl ammonium molybdenate was added to dicyclopentadiene in the same manner as solution A to prepare solution B.

50 parts by weight of the solution A and solution B were mixed, and 100 parts by weight of molten silica (Ryushin Co., Ltd., Hughex RD-8) having an average particle diameter of 15 µm was quickly mixed in equal amounts under a nitrogen atmosphere to provide a test. Curing conditions were 50 degreeC 0.5 hour + 125 degreeC 3 hours, unless otherwise specified.

<Resin 6: Epoxy Resin>

0.1 weight part of silane coupling agents (Toshiba Silicone Co., Ltd. make, TSA-720) were mixed with 100 weight part of bisphenol-A epoxy resins (made by Totokasei Co., Ltd., YD-128), and it was set as A liquid.

On the other hand, 2 parts of 2-ethyl-4-methylimidazole was mix | blended with 87 weight part of methyl tetrahydro phthalic anhydrides (made by Hitachi Chemical Co., Ltd., HN-2200) as a hardening | curing agent, and it was set as B liquid.

50 parts by weight of this solution A and 45 parts by weight of solution B were mixed, and 100 parts by weight of molten silica (manufactured by Ryushin Co., Ltd., Hughex RD-8) having an average particle diameter of 15 µm was further mixed and sufficiently stirred to be used for the test. Unless otherwise specified, curing conditions were 100 degreeC 1 hour, 125 degreeC 2 hours, and 140 degreeC 3 hours.

<Resin 7: Silicone Resin>

A commercial heat radiation type silicone resin (manufactured by Shin-Etsu Silicone Co., Ltd., KE-1223) was provided for the test. Curing conditions were 100 degreeC 1 hour, unless there is particular notice.

<Resin 8: Urethane Resin>

0.1 weight part of a silane coupling agent (Nipponical Co., Ltd. product, AZ-6171) is mixed and stirred by 100 weight part of commercially available urethane resins (made by Hitachi Chemical Co., Ltd., KU-707), and affixed by heating. 100 parts by weight of molten silica (Hugh Rex RD-8 manufactured by Ryushin Co., Ltd.) having an average particle diameter of 15 µm from which water was removed was mixed again. Curing conditions were 50 degreeC 3 hours + 100 degreeC 2 hours unless there is particular notice.

<Resin 9: Olefin-based low modulus resin>

25 parts by weight of high-purity dicyclopentadiene, 75 parts by weight of cyclooctadiene, and 0.1 parts by weight of a silane coupling agent (Nippon Chemical, FZ-3778) were blended. Subsequently, a predetermined amount of high-purity synthetic silica (Ryushin Co., Ltd. product, Adomappa SO-25H) having an average particle diameter of 0.5 µm was added to the compound, thereby obtaining a compound. 0.01 parts by weight of the metathesis polymerization catalyst represented by the general formula (10) was added to the compound immediately before the mold and used for the test. Curing conditions were made into 25 degreeC 1 hour + 100 degreeC 1 hour, unless there is particular notice.

<Resin 10: Olefin-based low modulus resin>

After mixing 25 parts by weight of high-purity dicyclopentadiene, 37.5 parts by weight of cyclooctadiene, and 37.5 parts by weight of cyclooctene (manufactured by HULS, 97% purity), 0.01 part by weight of the metathesis polymerization catalyst represented by the general formula (10) It was added immediately before and provided to the test. Curing conditions were made into 25 degreeC 1 hour + 100 degreeC 1 hour, unless there is particular notice.

II. Test Methods

<Viscosity>

Using a Brookfield viscometer, the rotor No. 23 ℃. At 3, the viscosity was measured under the condition of 60 rpm.

<Flexural Modulus>

About said resin 1-10, the casting plate of thickness 3mm was produced, respectively, and it measured based on JIS-K-7203. The shape of the test piece was 25 × 80 × 3 mm, the test span was 48 mm, and the test speed was 100 mm / minute.

<Model Impregnation Test>

A polypropylene test tube of 15 mm in diameter was filled with vibrating glass beads (average particle diameter: 80 μm) dried at 100 ° C. for 1 hour while vibrating to a height of about 60 mm, and then weighed and weighed by weight W ₀ (g ) Was measured.

Subsequently, the polymerizable composition was injected into a polypropylene test tube after the completion of glass bead filling so that the liquid surface had a height of about 60 mm, and the resultant was allowed to stand at a pressure of 1.3 kPa for 10 minutes, followed by thermosetting under prescribed conditions.

Thereafter, glass beads separated from the cured product without impregnation were collected, and the weight W ₁ (g) was measured, and the model impregnation rate was calculated by the following equation.

Model Impregnation Rate (%) = {(W ₀ -W ₁ ) / W ₀ } × 100

<Output Characteristics>

Heat cycle test using (-40 ° C 30 minutes + 125 ° C 30 minutes) as 1 cycle was performed for the device models 1 to 3, and when 12 V was applied as the primary voltage after the test, 20 kV was used as the secondary voltage. It was tested whether the above output was obtained. Moreover, the component after a test was cut | disconnected and the presence or absence of peeling was observed with the optical microscope.

<Moldability>

About the apparatus model 4, the cutting state of the gold wire was confirmed by soft X-ray, and it evaluated by the presence or absence of the disconnection.

<Reflow Soldering Resistance>

Using apparatus models 4 and 5, the mixture was allowed to stand in an atmosphere of 85 ° C./85% RH for 168 hours, and then heated at 240 ° C. for 10 seconds three times to observe cracking and conduct electricity tests.

<Manufacturing method of device model>

(1) Device Model 1: Ignition Coil

As shown in FIG. 1, the ignition coil manufactured in the present embodiment has a central core 11, an outer core 12, a primary bobbin 13, a primary coil 14, and a secondary bobbin 15 of a magnetic material. ), 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 encapsulating the IC ceramic substrate 19 with an epoxy resin 22. In addition, in FIG. 1, hatching except a part was abbreviate | omitted in order to make drawing easy to see.

The primary coil 14 is wound about 200 times of enameled wire about 0.5 mm in diameter, and the secondary coil 16 is wound around 20,000 times of enameled thin wire about 0.05 mm in diameter, respectively, on bobbins 13 and 15, respectively. . The primary coil 14 is connected to a battery and a direct current flows. The primary coil 14 interrupts the current flowing by the ignition timing control electronic circuit component 18 and the power switch to change the magnetic flux, thereby obtaining a primary voltage by magnetic dielectric action. It is supposed to be. The ignition coil generates a high voltage of 20 kV to 40 kV by the mutual induction of the primary coil 14 and the secondary coil 16, causing spark discharge to the spark plug connected to the terminal.

The device model 1 includes a magnetic core (11, 12), an aluminum electrode, an ignition timing control circuit part (18), and a modified-polyphenylene oxide (PPO) bobbin in a case 21 made of polyphenylene sulfide (PPS). 13, 15, the test samples (1 0.67 kPa) shown in Table 1 and Table 2 as a polymerizable composition for encapsulation in the assembly which incorporated the primary coil 14, the secondary coil 16, etc. which were wound up. And then degassed for a minute), and cured under a curing condition of 30 ° C 1 hour + 50 ° C 1 hour + 80 ° C 1 hour + 120 ° C 1 hour to form a sealing member 23 to obtain an ignition coil.

(2) Device Model 2: Ignition Coil

The test samples shown in Table 1 as polymerizable compositions for encapsulation in the assembly having the same configuration as that of the device model 1, except that the bare chip IC ceramic substrate (unpacked parts) was used as the ignition timing control circuit component 18 (0.67 kPa 1). And then degassed for a minute), cured under the curing conditions of 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, and the electronic circuit parts and the coil were collectively A sealed ignition coil was obtained.

(3) Device Model 3: Caseless Ignition Coil

Primary coils 14 wound around magnetic cores 11 and 12, brass electrodes, ignition timing control circuit components 18 (bare chip IC ceramic boards (unpacked parts)) and modified PPO bobbins 13 and 15 And after the necessary wiring of the secondary coil 16 is placed at a predetermined position in the center of the mold, the test sample (defoamed at 0.67 kPa for 1 minute) shown in Table 1 is cast as a polymerizable composition for sealing, and 30 It cured under the hardening conditions of 1 degreeC + 50 degreeC 1 hour + 80 degreeC 1 hour + 120 degreeC 1 hour, and formed the sealing member 23, and it took out from the metal mold | die, and obtained the batch sealing caseless ignition coil.

(4) Device Model 4: IC Components

In the center of the modified PPO 凹 -shaped case 21 having a length of 25 mm, a width of 25 mm, and a thickness of 5 mm, an epoxy resin encapsulation 16-pin DIP type IC substrate ceramic substrate of 15 mm in width and width was placed, and the test sample degassed in advance was placed. It poured, the sealing member was formed and the semiconductor device for resin sealing was obtained.

(5) Device Model 5: DIP IC Package

Using a test device (with a silicon wiring installed on a silicon chip having an oxide film having a vertical thickness of 5 mm), a 42-alloy lead frame which was partially silver plated was connected with an epoxy-based silver paste and a thermosonic wire Using a bonder, the bonding pat and the inner lead of the element were connected at 200 ° C. with a gold wire of 10 μm. Thereafter, the test sample degassed in advance was potted and cured to form a sealing member to obtain a resin-encapsulated 16-pin type DIP semiconductor package.

<Glass Transition Temperature (Tg)>

It measured using TMA8310 made from Lig Corporation.

<Coefficient of linear expansion>

It measured to -100 degreeC-200 degreeC using TMA8310 made from Lig Corporation.

<Permittivity>

It measured at 1 MHz using Ando Denki Co., Ltd. TR-10C type dielectric hand measuring instrument.

<Absorption rate>

It measured based on JIS-K-7114.

III. Test result

The results of the examples and the comparative examples are shown in Table 1 and Table 2. The electronic device of each embodiment has better output characteristics, moldability, and reflow soldering resistance than the epoxy resin and dicyclopentadiene-based resin having high modulus of elasticity, and the comparative examples which are encapsulated with a low modulus of silicone resin and urethane resin. Had This result shows that the electronic device of the present invention has excellent reliability.

As described above, the electronic device of the present invention is excellent in water resistance, reflow crack resistance, and the like, and has high reliability. For this reason, when the electronic device of the present invention is used, it is possible to provide a long life and high durability electric and electronic devices that are compatible with high density and high integration.

Claims (50)

It is provided with the sealing member obtained by superposing | polymerizing a polymeric composition, The said polymeric composition is a polymeric liquid substance whose viscosity is less than 0.3 N * s * m <^{-2> in 23} degreeC, The sealing member is an electronic device having a flexural modulus of 500 MPa or less at 23 ° C. It is provided with the sealing member obtained by superposing | polymerizing the polymerizable composition containing an olefin compound, The sealing member is an electronic device having a flexural modulus of 500 MPa or less at 23 ° C. The method of claim 2, The said polymerizable composition contains resin which is a polymeric liquid substance whose viscosity is less than 0.3 N * s * m <^-2> in 23 degreeC. The method according to claim 1 or 2, The sealing member is an electronic device, characterized in that the glass transition temperature is 80 ℃ or less. The method according to claim 1 or 2, The encapsulation member is an electronic device, characterized in that the linear expansion coefficient of 100ppm or more at 23 ℃. The method according to claim 1 or 2, The sealing member is an electronic device, characterized in that the water absorption is less than 0.1% by weight in water immersion at 23 ℃ 24 hours. The method according to claim 1 or 2, The encapsulation member is an electronic device, characterized in that the dielectric constant is 23 or less at 23 ℃. The method according to claim 1 or 2, Electronic device characterized in that the polymerizable composition comprises a filler. The method according to claim 1 or 2, And wherein said polymerizable composition comprises at least one additive of a modifier, a polymerization rate modifier, a foaming agent, an antifoaming agent, a coloring agent, a stabilizer, an adhesion imparting agent, a flame retardant, a coupling agent and an organic peroxide. The method according to claim 1 or 2, Electronic device characterized in that the polymerizable composition does not contain a solvent. The method of claim 1, Wherein said polymerizable composition comprises at least one metathesis polymerizable cycloolefin compound. The method of claim 11, And said polymerizable composition comprises two or more compounds selected from metathesis polymerizable cycloolefin compounds having a molecular weight of less than 300 as said metathesis polymerizable cycloolefin compounds. The method of claim 11, The polymerizable composition comprises a metathesis polymerization catalyst. delete delete delete delete delete The method of claim 12, The polymerizable composition comprises a metathesis polymerization catalyst. The method of claim 2, Wherein said polymerizable composition comprises at least one metathesis polymerizable cycloolefin compound. The method of claim 20, And said polymerizable composition comprises two or more compounds selected from metathesis polymerizable cycloolefin compounds having a molecular weight of less than 300 as said metathesis polymerizable cycloolefin compounds. The method of claim 20, And wherein the polymerizable compound comprises a metathesis polymerization catalyst. The method of claim 21, The polymerizable composition comprises a metathesis polymerization catalyst. The method according to any one of claims 13, 19, 22 and 23, The electronic device, characterized in that the metathesis polymerization catalyst is a compound represented by the following general formula (1). … (One) Where M represents ruthenium or osmium, X ¹ and X ² each independently represent an anionic ligand, L ¹ and L ² each independently represent a neutral ligand, and 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.) The method according to any one of claims 13, 19, 22 and 23, The electronic device, characterized in that the metathesis polymerization catalyst is a compound represented by the following general formula (2). … (2) Where M represents ruthenium or osmium, X ¹ and X ² each independently represent an anionic ligand, L ¹ and L ² each independently represent a neutral ligand, and 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.) The method according to any one of claims 13, 19, 22 and 23, The electronic device, characterized in that the metathesis polymerization catalyst is a compound represented by the following general formula (3). … (3) (Wherein M represents ruthenium or osmium, X ¹ and X ² each independently represent an anionic ligand, L ¹ and L ² each independently represent a neutral ligand, and R ¹ and R ² each independently C1-C18 alkyl group, C2-C18 alkenyl group, C2-C18 alkynyl group, aryl group, C1-C18 carboxylate group, C1-C18 alkoxyl group, C2-C18 alkene C1-C18 alkynyloxy group, C2-C18 aryloxy group, C2-C18 alkoxycarbonyl group, C1-C18 alkylthio group, C1-C18 alkylsulfonyl group, or C1-C18 An alkylsulfinyl group of 18, and R ³ represents hydrogen, an aryl group, or an alkyl group having 1 to 18 carbon atoms.) The method according to claim 1 or 2, And the encapsulation member is molded in an atmosphere containing oxygen. The method according to claim 1 or 2, The electronic device is an ignition coil having a center core made of a magnetic material, a primary coil and a secondary coil wound around the center core, and an outer core made of a magnetic material disposed outside the secondary coil. Electronics. As a polymerizable composition for superposing | polymerizing and obtaining the sealing member for electronic devices, The polymerizable composition is a liquid polymerizable liquid substance having a viscosity of less than 0.3 N · s · m ⁻² at 23 ° C., The said sealing member is a polymeric composition whose flexural modulus in 23 degreeC is 500 Mpa or less. As a polymerizable composition for superposing | polymerizing and obtaining the sealing member for electronic devices, The polymerizable composition includes an olefin compound, The said sealing member is a polymeric composition whose flexural modulus in 23 degreeC is 500 Mpa or less. The method of claim 30, A polymerizable composition comprising a resin which is a polymerizable liquid substance having a viscosity of less than 0.3 N · s · m ⁻² at 23 ° C. The method of claim 29 or 30, The sealing member, the glass transition temperature is 80 ℃ or less, the polymerizable composition, characterized in that. The method of claim 29 or 30, The sealing member is a polymerizable composition, characterized in that the linear expansion coefficient of 100ppm or more at 23 ℃. The method of claim 29 or 30, The sealing member has a water absorptivity of less than 0.1% by weight when immersed at 23 ° C for 24 hours. The method of claim 29 or 30, The sealing member has a dielectric constant of 23 or less at 23 ° C., the polymerizable composition. The method of claim 29 or 30, A polymerizable composition comprising a filler. The method of claim 29 or 30, An electronic device comprising at least one of a modifier, a polymerization rate regulator, a blowing agent, an antifoaming agent, a coloring agent, a stabilizer, an adhesion imparting agent, a flame retardant, a coupling agent, and an organic peroxide. The method of claim 29 or 30, It does not contain a solvent, The polymeric composition characterized by the above-mentioned. The method of claim 29, A polymerizable composition comprising at least one metathesis polymerizable cycloolefin compound. The method of claim 39, A polymerizable composition comprising two or more compounds selected from metathesis polymerizable cycloolefin compounds having a molecular weight of less than 300 as the metathesis polymerizable cycloolefin compounds. The method of claim 39, A polymerizable composition comprising a metathesis polymerization catalyst. The method of claim 40, A polymerizable composition comprising a metathesis polymerization catalyst. The method of claim 30, A polymerizable composition comprising at least one metathesis polymerizable cycloolefin compound. The method of claim 43, A polymerizable composition comprising two or more compounds selected from metathesis polymerizable cycloolefin compounds having a molecular weight of less than 300 as the metathesis polymerizable cycloolefin compounds. The method of claim 43, A polymerizable composition comprising a metathesis polymerization catalyst. The method of claim 44, A polymerizable composition comprising a metathesis polymerization catalyst. The method according to any one of claims 39, 40, 43 and 44, The said metathesis polymerization catalyst is a compound represented by following General formula (1), The polymeric composition characterized by the above-mentioned. … (One) Where M represents ruthenium or osmium, X ¹ and X ² each independently represent an anionic ligand, L ¹ and L ² each independently represent a neutral ligand, and 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.) The method according to any one of claims 39, 40, 43 and 44, The said metathesis polymerization catalyst is a compound represented by following General formula (2), The polymeric composition characterized by the above-mentioned. … (2) Where M represents ruthenium or osmium, X ¹ and X ² each independently represent an anionic ligand, L ¹ and L ² each independently represent a neutral ligand, and 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.) The method according to any one of claims 39, 40, 43 and 44, The said metathesis polymerization catalyst is a compound represented by following General formula (3), The polymeric composition characterized by the above-mentioned. … (3) (Wherein M represents ruthenium or osmium, X ¹ and X ² each independently represent an anionic ligand, L ¹ and L ² each independently represent a neutral ligand, and R ¹ and R ² each independently C1-C18 alkyl group, C2-C18 alkenyl group, C2-C18 alkynyl group, aryl group, C1-C18 carboxylate group, C1-C18 alkoxyl group, C2-C18 alkene C1-C18 alkynyloxy group, C2-C18 aryloxy group, C2-C18 alkoxycarbonyl group, C1-C18 alkylthio group, C1-C18 alkylsulfonyl group, or C1-C18 An alkylsulfinyl group of 18, and R ³ represents hydrogen, an aryl group, or an alkyl group having 1 to 18 carbon atoms.) The method of claim 29 or 30, A polymerizable composition, which can be molded in an atmosphere containing oxygen in a sealing member having a flexural modulus at 23 ° C. of 500 MPa or less.