JP2001113560A - Electric/electronic part - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electric/electronic part capable of being easily produced without requiring handling in an inert atmosphere, excellent in the adhesiveness of an internally mounted resin member and a polymer sealing the same, not generating the delamination between them and having the long life and high durability corresponding to high densification and high integration. SOLUTION: In an electric/electronic part, an internally mounted resin member is at least constituted of a cycloolefinic polymer and sealed with an olefinic polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a control component in which a printed circuit board is mounted in a storage container, a semiconductor module in which a silicon chip is mounted in a semiconductor module, and a member to be mounted in electric and electronic components such as a high voltage transformer in which a coil is mounted. And electric and electronic parts sealed with an olefin polymer using a specific resin member.

[0002]

2. Description of the Related Art As electric and electronic devices have become smaller and thinner, the components used have been increasing in density and integration, and the progress of semiconductor-related components in particular has been remarkable. These electric and electronic parts generally comprise a case material and components to be installed.

[0003] The constituent members include a printed wiring board and ICs, diodes, cables, connectors and the like connected to the wiring board as long as they are control parts. For high-voltage transformers such as an ignition coil and a flyback transformer, a bobbin material for winding the coil and a cushioning material for preventing collision between components to be installed are exemplified. These constituent members include inorganic materials such as metals and ceramics, and organic materials typified by polymer materials.

If a resin member is made of a polymer material among the constituent members, the resin member may be made of polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polycarbonate,
Thermosetting resins such as thermoplastic resins such as polytetrafluoroethylene, epoxy resins, phenol resins, urea resins, silicone resins, urethane resins, and polyester resins are used. Generally, in order to improve the durability and insulation of electrical and electronic components, epoxy resin, silicone resin, unsaturated polyester resin, urethane resin, etc. are cast-molded and sealed in the case and resin components. I have. Among these casting resins, epoxy resins are used as the most typical ones because of their excellent insulating properties, moisture resistance, thermal shock resistance, reflow crack resistance and adhesiveness to constituent members. However, with the demand for smaller and higher density electrical and electronic components, and the increasing demand for heat cycle resistance to adapt to harsher usage environments, it is not possible to improve crack resistance while maintaining insulation properties with epoxy resins. near. Further, silicone resin has a problem in adhesiveness, and urethane resin has a problem in insulating property.

On the other hand, cycloolefin resins obtained by metathesis polymerization of norbornene compounds are known to be excellent in mechanical properties, electrical properties, water resistance and the like. Production methods for sealing electric / electronic parts by reaction injection molding of a system compound have been proposed. In addition, Japanese Patent Application Laid-Open No. 9-183
No. 833 proposes a norbornene-based compound suitable for encapsulating electric and electronic components with a new metathesis polymerization catalyst. Furthermore, in JP-A-10-182922, the metathesis polymerizable cycloolefin-based compound (prepolymer) has a low viscosity even when a filler is added,
It is shown that it is suitable for sealing electric and electronic components. However, the polymers (cured products) of the cycloolefin-based compounds described therein have poor adhesiveness, so that the durability of electric / electronic parts cast with the resin is low.

The metathesis polymerization catalyst system described in Japanese Patent Publication No. 5-41088 is disclosed in JP-A-59-5191.
No. 1 discloses a combination of a catalyst component selected from an organic ammonium salt of tungsten and molybdenum and an activator selected from an alkoxyalkylaluminum halide and an aryloxyaluminum halide. There is also a problem that the molding must be performed in an inert atmosphere because it is easily deactivated.

[0007]

SUMMARY OF THE INVENTION The invention according to claims 1 to 7 can be easily manufactured without the need for handling in an inert atmosphere, and is characterized by the fact that an interior resin member and a polymer for sealing the resin member are sealed. An object of the present invention is to provide an electric / electronic component which has excellent adhesiveness, does not cause peeling therebetween, has a long life and high durability corresponding to high density and high integration.

[0008]

SUMMARY OF THE INVENTION The present invention relates to an electric / electronic component in which a resin member to be installed is made of at least a cycloolefin-based polymer, and the resin member is sealed with an olefin-based polymer. Further, the present invention relates to the above electric / electronic component, wherein the cycloolefin-based polymer is a norbornene-based resin. In addition, the present invention provides a method for producing an olefin polymer having a flexural modulus of 2
The present invention relates to the above-mentioned electric / electronic component having a pressure of 500 MPa or less at 3 ° C.

Further, the present invention provides an olefin polymer comprising:
The present invention relates to the above-mentioned electric / electronic component, which is a polymer obtained by subjecting a cycloolefin compound to metathesis polymerization. Further, the present invention relates to the electric / electronic component described above, wherein the olefin-based polymer contains a filler. Also,
The present invention provides a high-voltage transformer comprising a magnetic core, a primary coil, a secondary coil, and an external connection terminal.
It concerns electrical components. Further, the present invention relates to the electronic / electric component, which is an engine ignition coil.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The cycloolefin-based polymer constituting the resin member to be installed in the present invention is, for example, bicyclic norbornene such as norbornene, methylnorbornene, dimethylnorbornene, ethylnorbornene, ethylidene norbornene, butylnorbornene and dicyclic norbornene. Tricyclic norbornenes such as cyclopentadiene (a dimer of cyclopentadiene), dihydrodicyclopentadiene, methyldicyclopentadiene and dimethyldicyclopentadiene; tetracyclic dodecene, methyltetracyclododecene and dimethylcyclotetradodecene; 5- or more-ring norbornene, cyclobutene, cyclo, such as cyclic norbornene, tricyclopentadiene (trimer of cyclopentadiene), and tetracyclopentadiene (tetramer of cyclopentadiene) Pentene, cyclooctene, cyclododecene, tetrahydroindene, include polymers obtained by ring-opening polymerization or addition polymerization of cycloolefin compounds methyl tetrahydroindene.

Further, a compound having two or more norbornene groups, for example, a polyfunctional crosslinking agent such as tetracyclododecadiene or symmetric tricyclopentadiene or a norbornene derivative such as hymic acid, hymic anhydride or norbornadiene is copolymerized. It is also possible to denature.

From the viewpoint of adhesiveness, the cycloolefin-based polymer is preferably a norbornene-based resin having a norbornene structure in a polymer skeleton. Further, from the viewpoint of moldability of a resin member to be installed, a norbornene-based thermoplastic resin is preferably used. Is more preferable. Such a norbornene-based thermoplastic resin is a known resin disclosed in JP-A-3-122137 and the journal of the Chemical Society of Japan (No. 2, P81-88, 1998).

Examples of commercially available cycloolefin polymers include ZEONEX, ZEONOR (trade name, manufactured by Nippon Zeon Co., Ltd.) and ARTON (trade name, JSR
And Abel (trade name, manufactured by Mitsui Chemicals, Inc.).

The resin member composed of at least the cycloolefin polymer used in the present invention can be molded and manufactured by a known method. For example, when molding and manufacturing while producing a cycloolefin polymer using a thermosetting material, injection molding, impregnation molding, RTM molding, lamination molding, press molding, filament winding, centrifugal molding , A vacuum or pressure back method, a continuous molding method, a pultrusion molding method, and the like. Also,
When using a thermoplastic cycloolefin polymer, molding methods such as injection molding, press molding, extrusion molding, blow molding, rotational molding, and vacuum molding can be used, and the molding temperature is the melting temperature of the cycloolefin polymer used. But usually between 150 and 400 ° C.

The cycloolefin-based polymer used for the resin member may contain a conventional additive. As the additives, silica, calcium carbonate, carbon black, inorganic fillers such as titanium oxide and glass, aramid,
Reinforcing agents such as carbon, lubricants, pigments / dyes, antioxidants, fluidity improvers, flame retardants, antistatic agents, plasticizers, crosslinking agents, modifiers for engineering plastics such as elastomers and PPS And the like.

The shape of the resin member is not particularly limited. For example, if the member is a printed wiring board, it is plate-shaped, if it is a bobbin for a coil, it is cylindrical, if it is cable wiring for optical communication, it is linear, and if it is a connector or switch, it is rectangular. is there.

The olefin polymer used for sealing the resin member in the present invention includes, for example, hydrocarbon resins such as polyethylene, polypropylene, and polybutadiene. The reactive mixture before polymerization is obtained at room temperature. A polymer of a cycloolefin-based compound is preferable, and a cycloolefin compound capable of metathesis polymerization is more preferable because it is liquid and has excellent handleability at the time of casting.

Cycloolefin compounds capable of metathesis polymerization are roughly classified into norbornene-based cycloolefin compounds and non-norbornene-based cycloolefin compounds. As norbornene-based cycloolefin compounds,
For example, norbornene, methyl norbornene, dimethyl norbornene, ethyl norbornene, ethylidene norbornene, bicyclic norbornene such as butyl norbornene,
Tricyclic norbornenes such as dicyclopentadiene (a dimer of cyclopentadiene), dihydrodicyclopentadiene, methyldicyclopentadiene, and dimethyldicyclopentadiene; tetracyclododecene, methyltetracyclododecene, and dimethylcyclotetradodecene Examples include pentacyclic or higher norbornene such as tetracyclic norbornene, tricyclopentadiene (trimer of cyclopentadiene), and tetracyclopentadiene (tetramer of cyclopentadiene). Examples of the non-norbornene-based cycloolefin compound include cyclobutene, cyclopentene, cyclooctene, cyclododecene, tetrahydroindene, and methyltetrahydroindene.

Further, a compound having two or more norbornene groups, for example, tetracyclododecadiene, symmetric tricyclopentadiene or the like can be used as a polyfunctional crosslinking agent. Further, norbornene derivatives such as high acid, high acid anhydride and norbornadiene can be used. These metathesis polymerizable cycloolefin compounds can be used alone or in combination of two or more.

Of these, dicyclopentadiene, methyltetracyclododecene, ethylidene norbornene, tricyclopentadiene, cyclooctene, cyclooctadiene, cyclododecatriene and the like are preferred from the viewpoint of availability and economy.

Dicyclopentadiene is preliminarily subjected to heat treatment to convert a part of dicyclopentadiene into a cyclopentadiene oligomer such as tricyclopentadiene or tetracyclopentadiene, or to convert vinylnorbornene or methylvinylnorbornene as an impurity into tetrahydroindene. And methyltetrahydroindene. Heat treatment is usually 120 to 250
C. for about 0.5 to 10 hours.

Incidentally, these commercially available cycloolefin compounds may contain impurities. For example, dicyclopentadiene includes vinyl norbornene,
Contains tetrahydroindene, methylvinylnorbornene, methyltetrahydroindene, methyldicyclopentadiene, dimethyldicyclopentadiene, tricyclopentadiene, etc., and cyclooctadiene may contain unreacted butadiene and cyclooctane as impurities. is there. Various purity cycloolefin compounds are commercially available, but need not be particularly purified. These raw materials used in the electric / electronic parts of the present invention have a purity of usually 90% by weight or more, preferably 95% by weight or more, particularly preferably 98% by weight or more.

The olefin polymer has a flexural modulus of 500 at 23 ° C. from the viewpoint of resistance to thermal shock and adhesion.
It is preferably at most MPa.

Among the cycloolefin compounds, one having a molecular weight of 3
The elastic modulus of the resin can be controlled by using two or more cycloolefin compounds of less than 00 in combination. Resins obtained by polymerizing bicyclic or polycyclic compounds such as dicyclopentadiene and tricyclopentadiene are hard, and therefore monocyclic compounds such as cyclopentene, cyclooctene, cyclooctadiene, cyclododecatriene, and cyclooctatetraene are used. Can be used in combination to reduce the elastic modulus. These monocyclic cycloolefin compounds used for lowering the elastic modulus are preferably compounded in the range of 40 to 99 mol% based on the total number of moles of the polycyclic compound and the monocyclic compound. If the monocyclic body is less than 40 mol%, the elastic modulus tends to be too high. On the other hand, if it is used in an amount exceeding 99 mol%, the crosslink density is low, and the toughness of the resin tends to be low.

The metathesis polymerization catalyst used in the present invention may be a metal catalyst such as WCl ₆ , MoCl ₅ , RuCl ₃ alone, or a combination of the above catalyst component and an alkyl aluminum as disclosed in JP-A-59-51911. And a two-part metathesis catalyst system in combination with an activator such as In addition, Shrock type or Fischer type metal carbene catalysts, metal carbine catalysts, metallacyclobutane catalysts, and the like can also be used.

On the other hand, the general formula (1)

Embedded image (Wherein, M represents ruthenium or osmium;
And X ¹ each independently represent an anionic ligand;
And L ¹ each independently represent a neutral electron donating group;
Q and Q ¹ each independently represent a hydrogen atom, an alkyl group,
One-component metathesis polymerization catalysts such as those represented by alkenyl groups or aromatic groups) also metathesize (metathesis) metathesis-polymerizable cycloolefin compounds without easily losing their catalytic activity due to oxygen or moisture in the air. ) Since ring-opening polymerization can be carried out by the reaction, it can be suitably used.

In the above formula (1), the anion ligands represented by X and X ¹ are groups having a negative charge when the coordination to the central metal is removed. Examples of such a group include a hydrogen atom, a halogen atom, CF ₃ CO ₃ , C
H ₃ CO ₂ , CFH ₂ CO ₂ , (CH ₃ ) ₃ CO, (CF ₃ ) ₂ (C
H ₃ ) CO, (CF ₃ ) (CH ₃ ) ₂ CO, C 1-5 alkyl group, C 1-5 alkoxy group, phenyl group, phenoxy group, tosyl group, mesyl group, trifluoromethanesulfonate And X ¹ and X ¹ are both halogen atoms (particularly chlorine).

In the above formula (1), the neutral electron-donating groups represented by L and L ¹ are groups having a neutral charge when the coordination to the central metal is removed. Examples of such a group include, for example, PR ² R ³ R ⁴ (where R ² represents a secondary alkyl group or a cycloalkyl group, and R ³ and R ⁴ each independently represent an aryl group or a C 1 -C 1 group. -10, a primary alkyl group or a secondary alkyl group, and a cycloalkyl group), pyridine, p-fluoropyridine, imidazolylidene compounds, and the like. , L and L ^{1 are} both -P (C ₆ H ₁₁ ) ₃ , -P (C ₅ H ₉ ) ₃ , or -P (is
o-C ₃ H ₇ ) ₃ , wherein L and L ¹ may be different electron donating groups.

In the general formula (1), Q and Q ¹ are alkyl groups having 1 to 20 carbon atoms, and alkenyl groups are 2 to 20 carbon atoms.
And the aromatic group includes an aryl group, and the alkyl group, the alkenyl group, and the aromatic group each may have a substituent.

Specific examples of more preferred catalysts include the following formula (2) (Reference: Organometallics, No. 16)
Volume, No. 18, p. 3867 (1997)), the following formula (3) (Reference: Angew. Chem. Int. Ed., 37, 2490 (1998)), and the following formula (4) And carbene catalysts.

[0031]

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[0032]

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[0033]

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The amount of the metathesis polymerization catalyst to be added is 0.001 to 2 with respect to the cycloolefin compound.
It is preferably in the range of 0% by weight, and more preferably in the range of 0.01 to 5% by weight for reasons of economy and curing rate.

The mechanical properties of the polymer of the cycloolefin compound can be arbitrarily controlled by the type, combination and blending amount of the cycloolefin compound, and the addition of a modifier. When used for the purpose of improving the durability of a part, its mechanical properties are preferably in the range of 0.01 MPa to 10 GPa, and in the range of 0.1 MPa to 3 GPa, at a flexural modulus of elasticity of 23 ° C. Is more preferable, and it is particularly preferable to be in the range of 1 MPa to 2 GPa. If the flexural modulus is less than 0.01 MPa, there is a tendency that the strength for protection does not appear. On the other hand, when it exceeds 2 GPa, peeling or the like tends to occur easily at the interface with a different kind of material. For the purpose of considering the adhesiveness, it is preferable that the elasticity is low, less than 1 GPa.

The elastic modulus can be reduced, for example, by using a monocyclic compound in combination with a polycyclic compound in a cycloolefin compound. In consideration of the adhesiveness, the mixing ratio of the monocyclic compound in the cycloolefin compound is preferably 40 mol% to 99 mol based on the total mol number of the polycyclic compound and the monocyclic compound.
It is preferable to mix in a range of less than mol%. When the amount of the monocyclic ring is less than 40 mol%, the elastic modulus tends to be 1 GPa or more, and when it is 99 mol% or more, the cross-linking density of the polymer tends to be low, so that the strength tends not to be exhibited. .

In the present invention, generally, a predetermined amount of a metathesis polymerization catalyst is added to a cycloolefin compound which is liquid at room temperature, and a polymer (cured product or molded product) is obtained by a metathesis polymerization reaction. In this case, as a specific processing method,
For example, injection molding at atmospheric pressure, vacuum injection molding, pressure injection molding, impregnation molding, RTM molding, dipping,
Lamination molding methods such as hand lay-up and spray-up,
Press molding method, filament winding method, centrifugal molding method, vacuum or pressure back method, continuous molding method, pultrusion molding method, injection molding method, transfer molding and other generally known thermosetting or thermoplastic resin molding methods. .
Further, the processing method includes forming a film, a porous film, a sealing member, a packing, and the like in advance by the above processing method, and using the member for an electric / electronic component. Furthermore, it also includes use as an adhesive.

Although the above treatment can be left at room temperature, heating is generally performed. The temperature at which the metathesis polymerization catalyst is added to the cycloolefin-based compound is usually from 0 to 80 ° C, preferably from room temperature to 50 ° C. The heating operation for obtaining the cured product may be one-stage heating, two-stage heating, or multi-stage heating. In the case of one-stage 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 ° C. ° C, preferably 10 to 100 ° C, and the second stage temperature is usually 20 to 200 ° C, preferably 30 to 180 ° C.
It is. The polymerization time can be appropriately determined depending on the amount of the catalyst and the polymerization temperature, but is usually 1 minute to 50 hours.

In the present invention, the resin member to be installed is
Sealed with olefin polymer. The olefin polymer preferably contains a filler from the viewpoint of electrical characteristics. The olefin polymer can be produced by polymerizing the cycloolefin compound, and the filler can be included in the olefin polymer obtained by mixing the filler with the cycloolefin compound before or during the polymerization.

A filler can be added to the cycloolefin compound. For example, inorganic fillers such as fused silica, crystalline silica, silica sand, calcium carbonate, aluminum hydroxide, magnesium oxide, clay, expanded graphite and beads such as wood flour, polyester, silicone, polystyrene acrylonitrile-butadiene-styrene (ABS) Organic fillers. Further, a foamable organic filler (Expancel manufactured by Nippon Ferrite Co., Ltd.) in which isobutane gas is sealed in a core in a vinylidene chloride-polyacrylonitrile cell is also exemplified. In this,
Silica and aluminum hydroxide are preferred in terms of electrical properties and thermal conductivity. As this commercial product, CRT
-AA, CRT-D, RD-8 (trade name, manufactured by Tatsumori Co., Ltd.), COX-31 (trade name, manufactured by Micro Co., Ltd.), C-3
03H, C-315H, C-308 (Sumitomo Chemical Industries, Ltd.)
Trade name), SL-700 (trade name, manufactured by Takehara Chemical Industry Co., Ltd.) and the like.

The compounding amount of these inorganic and organic fillers is preferably 0 to 95% by weight, more preferably 10 to 95% by weight, more preferably 30 to 95% by weight, based on the cycloolefin compound. %, Particularly preferably 30 to 75% by weight. If the amount exceeds 95% by weight, the dielectric constant tends to exceed 3.0, and the electrical characteristics tend to decrease.

The particle size, shape, quality and the like of these inorganic and organic fillers can be appropriately determined depending on the use of electric / electronic parts, but the average particle size is preferably 0.1 to 100 μm. Those having a thickness of 1 to 50 μm are particularly preferred.
Further, by combining those having different average particle diameters, the fine packing property and the fluidity can be improved. Further, the shape of these inorganic and organic fillers is preferably spherical.

Also, milled glass, cut fiber,
Inorganic and organic fibrous fillers such as microfibers, microballoons, flaky glass powder, carbon fiber, and aramid fiber can also be used, and these can be used in combination. Further, the aspect ratio and shape can be appropriately selected according to the purpose. The amount of the fibrous filler is preferably 0 to 20 parts by weight, more preferably 0 to 10 parts by weight, based on 100 parts by weight of the cycloolefin compound.

The cycloolefin-based compound used in the electric / electronic component of the present invention may further include a modifier, a polymerization rate regulator, and
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.

Examples of the modifier used in the present invention include elastomers, natural rubbers, butadiene rubbers, styrene-butadiene copolymers (SBR), styrene-butadiene-styrene block copolymers (SBS), and styrene-maleic. Examples include acid copolymers, copolymers such as ethylene-vinyl acetate copolymers, and thermoplastic resins such as polymethyl methacrylate, polyvinyl acetate, and polystyrene. In addition, these copolymers and thermoplastic resins may be esterified, or a polar group may be grafted. Further, an epoxy resin, a urethane resin, a polyester resin, a silicone resin, a phenol resin, a polyimide resin, a polyamide resin, a polyamideimide resin, and derivatives thereof may be blended to improve physical properties.

Further, for example, a compound obtained by reacting an epoxy with norbornene monocarboxylic acid, a compound obtained by reacting an isocyanate compound with norbornene-ol, a hymic acid-modified polyester, a petroleum resin and the like can be mentioned. Examples of the petroleum resin include those produced using a known C5 or C9 fraction purified from an ethylene plant as a raw material. Examples thereof include Quinton (trade name of Nippon Zeon Co., Ltd.) and a thermoplastic polynorbornene resin Norsolex (Trade name, manufactured by Zeon Corporation). These petroleum resins have a number average molecular weight (measured by gel permeation chromatography and converted using a standard polystyrene calibration curve),
It is preferably 1,000 or more, and more preferably one having a functional group such as a hydroxyl group or an ester group in the resin skeleton.

Although the amount of these modifiers depends on the physical properties of the intended resin, it is generally preferable to use 0.2 to 50 parts by weight based on 100 parts by weight of the cycloolefin compound. More preferably, it is used in the range of 0.5 to 40 parts by weight. If the amount is less than 0.2 parts by weight, the effect of the modifier tends to be hardly exhibited, and if it is more than 50 parts by weight, the polymerizability tends to decrease.

Examples of the polymerization rate regulator used in the present invention include phosphates such as triisopropylphosphine, triphenylphosphine and tricyclohexylphosphine, 1-hexene and allyl compounds. These are cycloolefins. For 100 parts by weight of the system compound,
It is preferable to use 0.005 to 20 parts by weight. These polymerization rate regulators are used for the purpose of controlling the pot life for molding, and when the pot life may be short, the amount used is reduced, and when the pot life is desired to be increased, the amount is appropriately increased. , The amount can be adjusted.

Examples of the antifoaming agent include known antifoaming agents such as silicone oil, fluorine oil and polycarboxylic acid polymer. Usually, 0.001 to 5 parts by weight based on 100 parts by weight of cycloolefin compound. It is preferable to add parts by weight.

Examples of the foaming agent include low-boiling hydrocarbon compounds such as pentane, propane and hexane; generally known physical foaming agents such as carbon dioxide and steam; azobisisobutyronitrile; Examples include generally known chemical foaming agents such as azo compounds such as nitrosopentamethylenetetramine and compounds that generate nitrogen gas by decomposition such as nitroso compounds.

Examples of the coloring agent include inorganic pigments such as titanium dioxide, cobalt blue and cadmium yellow, and organic pigments such as carbon black, aniline black, β-naphthol, phthalocyanine, quinacridone, azo type, quinophthalone and indanthrene blue. And each can be blended according to the desired color tone. These may be used in combination of two or more. The amount of these pigments added is preferably 0.1 to 50 parts by weight based on 100 parts by weight of the cycloolefin compound.

The stabilizer used in the present invention includes an ultraviolet absorber, a light stabilizer and an antioxidant. Examples of the ultraviolet absorber include salicylic acid-based ultraviolet absorbers such as phenyl salicylate and para-t-butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4, Benzophenone-based ultraviolet absorbers such as 4'dimethoxybenzophenone,
(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole 2- (2'
-Hydroxy-3 ', 5'-di-t-amylphenyl)
Benzotriazole-based ultraviolet absorbers such as benzotriazole, 2-ethylhexyl-2-cyano-3,3'-
Diphenyl acrylate, ethyl-2-cyano-3,
Examples include cyanoacrylate-based ultraviolet absorbers such as 3'-diphenylacrylate. These can be used alone or 2
More than one kind may be used together. The addition amount of these ultraviolet absorbers is appropriately determined depending on the use environment of the electric / electronic parts, the presence / absence of the housing, and the required characteristics. You.

As a light stabilizer, bis (2,2)
2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, dimethyl succinate-1- (2
-Hydroxyethyl) -4-hydroxy-2,2,6
Hindered amine light stabilizers such as 6-tetramethylpiperidine polycondensate are exemplified. This light stabilizer is usually added to 100 parts by weight of the cycloolefin compound.
0.05 to 20 parts by weight can be added.

The antioxidants used in the present invention include quinones such as parabenzoquinone, tolquinone and naphthoquinone, and hydroquinones such as hydroquinone, para-t-butylcatechol and 2,5-di-t-butylhydroquinone. Phenols such as di-t-butyl-para-cresol hydroquinone monomethyl ether, pyrogallol, copper salts such as copper naphthenate and copper octenoate, and quaternary salts such as trimethylbenzylammonium chloride, trimethylbenzylammonium maleate and phenyltrimethylammonium chloride. Grade ammonium salts, oximes such as quinone dioxime and methyl ethyl ketoxime, amine hydrochlorides such as triethylamine hydrochloride and dibutylamine hydrochloride, and oils such as mineral oil, essential oil, and fatty oil. And the like. These antioxidants are
Depending on the conditions such as compatibility with the filler and the desired molding workability and resin storage stability, it can be added by changing the type and amount, usually, the addition amount is based on 100 parts by weight of the cycloolefin compound. 10 to 10,000 ppm.

Examples of the adhesion-imparting agent used in the present invention include silane coupling agents. As the silane coupling agent, (Y) _a -Si- (X) _4-a (wherein, Y represents a monovalent functional group bonded to Si, and X is
A monovalent group which has hydrolyzability and is bonded to Si;
Is an integer of 1 to 4). Examples of the functional group in Y include a vinyl group, an amino group, an epoxy group, a chloro group, a mercapto group, a methacryloxy group, a cyano group, a carbamate group, a pyridine group, a sulfonyl azide group, a urea, a styryl group, and chloromethyl. Groups, ammonium salts, alcohols and the like. X
Examples thereof include chlorine, a methoxy group, an ethoxy group, and a methoxyethoxy group.

As specific examples, for example, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycol Sidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N, N-dimethylaminophenyltriethoxysilane, mercaptoethyltriethoxysilane, methacryloxyethyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane hydrochloride and the like, and these can be used in combination. The silane coupling agent is usually used in an amount of 0.00 parts by weight based on 100 parts by weight of the cycloolefin compound.
Add 1 to 5 parts by weight.

As the flame retardant, for example, a halogen compound such as hexabromobenzene, tetrabromobisphenol A, decabromodiphenyl oxide, tribromophenol, dibromophenylglycidyl ether, perchloropentacyclodecane, or a hetic acid derivative is used alone or in combination. Two or more are used in combination. Further, a phosphate compound such as tris (dichloropropyl) phosphate and tris (dibromopropyl) phosphate, a boric acid compound and the like can also be used in combination. Further, examples of the auxiliary flame retardant include antimony trioxide, iron oxide, and aluminum hydride. When these are used in combination with the flame retardant, the flame retardant effect can be further enhanced. The halogen-based flame retardant is based on 100 parts by weight of the cycloolefin-based compound.
Usually, it is used in 1 to 50 parts by weight. The auxiliary flame retardant such as antimony trioxide is usually used in a range of 1 to 15 parts by weight based on 100 parts by weight of the cycloolefin compound. Hydrates such as commercially available aluminum hydroxide and magnesium hydroxide can also be used as fillers for flame retardancy as plastic fillers. These additives are added in an amount of 1 to 100 parts by weight of the cycloolefin compound.
It is preferably used in the range of 0 to 300 parts by weight.

In addition to these, in order to improve the wettability of the filler, for example, a coupling agent represented by a commercially available wetting agent such as BYK series manufactured by BYK-Chemie or a dispersing agent can be added. To improve workability, release agents such as silicone oil and zinc stearate, and inorganic ion exchangers (ion scavengers) that capture free ions such as chloride and sodium ions in polymers
If necessary, it can be added to the extent that the curing is not hindered.

Further, an organic peroxide can be added. Examples of the organic peroxide include cumene hydroperoxide, tertiary butyl peroxy-2-ethylhexanate, methyl ethyl ketone peroxide,
Known ones such as benzoyl peroxide, acetylacetone peroxide, bis-4-tert-butylcyclohexanedicarbonate, and 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexyne-3 are exemplified. Two or more kinds may be used in combination. The amount of these additives is usually 0.1 to 10 parts by weight based on 100 parts by weight of the cycloolefin compound.

The cycloolefin compound used in the present invention does not contain a solvent. This solvent is benzene,
It is a generally known non-reactive diluting solvent such as toluene, xylene, ethyl acetate, and methyl ethyl ketone. However,
Among the above additives, the solvents contained in the commercial products are neglected. However, even in this case, the amount of the solvent is preferably less than 2 parts by weight based on the cycloolefin-based compound in order to prevent swelling during curing.

In order to adjust the viscosity of the cycloolefin compound and the mechanical and electrical properties of the polymer, a low-viscosity reactive diluent such as an acrylic monomer, a methacrylic monomer, a vinyl monomer, or diallyl phthalate is used. These may be used alone or in combination of two or more.

In the production of the electric / electronic component of the present invention,
Sealing a resin member with an olefin-based polymer can be achieved by, for example, casting a reactive mixture containing a cycloolefin-based compound and a polymerization catalyst at atmospheric pressure, vacuum injection molding, pressure injection molding, impregnation molding. Method, RTM molding method, lamination molding method such as dipping, hand lay-up and spray-up, press molding method, filament winding method, centrifugal molding method, vacuum or pressure back method, continuous molding method, pultrusion molding method, injection molding method Molding by a transfer molding method or the like. When the metathesis polymerization catalysts represented by the general formulas (2) to (4) are used in the present invention, it is not necessary to form an inert atmosphere in these moldings.

In the electric / electronic component of the present invention, the storage container (case) is made of an inorganic material such as SUS, copper, iron, aluminum and ceramics, and a thermosetting resin, a thermoplastic resin, a biodegradable resin and a natural resin. From organic materials, purpose,
There is no limitation as it is selected depending on the application. Also, the shape and dimensions of the parts are arbitrarily designed according to the purpose. There may not be a case.

A high-voltage transformer, which is an example of the electric / electronic component of the present invention, means that a primary voltage of several volts to several hundreds of volts is changed to several thousand volts depending on the purpose by a mutual induction action between a primary coil and a secondary coil. It is an electrical part for extracting tens of thousands of volts from the secondary voltage. For example, a large transformer may include a transformer for power transformation in a power transmission facility, a small transformer may include a flyback transformer used for video equipment such as a television and a monitor, and an ignition coil for an automobile engine.

FIG. 1 schematically shows a cross-sectional structure of an example of the ignition coil. Here, the ignition coil is a core a,
It comprises a primary bobbin b, a primary coil c, a secondary bobbin d, a secondary coil e, a terminal f and the like. The primary coil is Φ
About 0.5 enameled wire about 200 times, the secondary coil,
A thin enamel wire having a diameter of about 0.05 is wound on the bobbin about 20,000 times. The primary coil is connected to the battery, and a direct current flows. The primary coil changes the magnetic flux by interrupting the current flowing through the ignition timing adjustment electronic circuit components and the power switch, and obtains a primary voltage by a self-induction action. This primary voltage is a high voltage of 20 to 40 KV due to the mutual induction between the primary coil and the secondary coil, and is an electric / electronic component that causes a spark discharge to a spark plug connected to a terminal.

[0066]

The present invention will be described below with reference to examples. In the examples, “parts” means “parts by weight” unless otherwise specified.

<Resin 1: Olefin Polymer> 50 parts by weight of high-purity dicyclopentadiene (manufactured by Maruzen Petrochemical Co., Ltd., purity: 99% by weight or more), cyclooctadiene (HULS)
(Purity: 98.5% by weight or more), 50 parts by weight, 0.1 part by weight of triphenylphosphine, and 1 part by weight of 2,5-di-tert-butylphenol were mixed. 0.1 part by weight of the resulting metathesis polymerization catalyst was added immediately before casting and tested. Curing condition is 38 ° C
× 2 hours + 100 ° C. × 1 hour + 125 ° C. × 1 hour.

<Resin 2: Olefin Polymer with Filler> 100 parts by weight of high-purity dicyclopentadiene and 0.1 part by weight of a silane coupling agent (FZ-3778, manufactured by Nippon Unicar Co., Ltd.) Mix while heating to about 35 ° C. Next, a predetermined amount of fused silica having an average particle size of 15 μm (Fuselex RD-8 manufactured by Tatsumori Co., Ltd.) was stirred and mixed to obtain a compound. Next, using the metathesis polymerization catalyst represented by the formula (2), the resin was cured in the same manner as the resin 1.

<Resin 3: Olefin Polymer> A 1-liter separable flask was charged with 500 parts by weight of high-purity dicyclopentadiene and 0.5 parts by weight of 2,5-di-tert-butylphenol, and was charged under a nitrogen atmosphere. 16
The mixture was heated and refluxed at 5 to 170 ° C. for 8 hours to obtain a heat-treated varnish. Solution A was added to this varnish by adding diethylaluminum chloride at a concentration of 40 mmol, n-propyl alcohol at a concentration of 52 mmol, and silicon tetrachloride at a concentration of 20 mmol in a dry box purged with nitrogen. Similarly to the solution A, tridecyl ammonium molybdate was added to the heat-treated varnish at a concentration of 10 mmol to prepare a solution B. The solution A and the solution B were mixed under a nitrogen atmosphere by 50 parts by weight and tested. Curing condition is 5
0 ° C. × 0.5 h + 125 ° C. × 1 h.

<Resin 4: Epoxy Resin> 100 parts by weight of bisphenol A type epoxy resin (YD- manufactured by Toto Kasei Co., Ltd.)
128) was mixed with 0.1 part by weight of a silane coupling agent (TSA-720, manufactured by Toshiba Silicone Co., Ltd.) to obtain a liquid A. On the other hand, as a curing agent, 87 parts by weight of methyltetrahydrophthalic anhydride (HN-2200 manufactured by Hitachi Chemical Co., Ltd.) was mixed with 2 parts of 2-ethyl-4-methylimidazole to prepare a liquid 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 fused silica having an average particle diameter of 15 μm (Fuselex RD-8 manufactured by Tatsumori Co., Ltd.)
And stirred well, while heating to 60 ° C.
Injected under (3 torr) vacuum. Curing condition is 100 ℃ x
1 h + 125 ° C. × 2 h + 140 ° C. × 3 h.

<Resin 5: Silicone Resin> A commercially available heat radiation type silicone resin (trade name K, manufactured by Shin-Etsu Silicone Co., Ltd.)
E-1223). Curing condition is 100 ℃ × 1h
And

Test Method <Output Characteristics Test> A 100-cycle heat cycle test was performed on the cast and sealed part models 1 and 3 with (-55 ° C. × 60 minutes + 150 ° C. × 60 minutes) as one cycle. It was tested whether an output of 20 KV or more was obtained as a secondary voltage when 12 V was applied as a primary voltage. Also,
The part after the test was cut, and the presence or absence of peeling was observed with an optical microscope.

<Control part continuity test> The part models 2 and 4 which were cast and sealed were subjected to a PCT treatment at 121 ° C. × 2 atm for 500 hours, and then subjected to a continuity test. The presence or absence of peeling was observed with an optical microscope. With respect to the part model 5, only the presence or absence of peeling was observed with an optical microscope.

<Parts Model 1> A polyphenylene sulfide (PPS) case material is provided with a magnetic core, an aluminum electrode, an ignition timing control circuit component (structure: ceramic substrate with IC / parts sealed with epoxy resin), cycloolefin-based polymer The test samples shown in Table 1 were cast into an ignition coil incorporating a primary coil and a secondary coil of a bobbin (Zeonor 1600R, manufactured by Zeon Corporation).

<Parts Model 2> A case material made of polybutylene terephthalate (PBT) is 150 × 150 × 2 mmt.
The test sample shown in Table 1 was cast into a control part having a printed circuit board circuit part made of a cycloolefin-based polymer (manufactured by JSR Corporation, trade name: Arton).

<Parts Model 3> A test sample shown in Table 1 was cast in the same manner as the parts model 1 except that the bobbin material was made of PPS to produce an ignition coil.

<Parts Model 4> Control samples were prepared by casting the test samples shown in Table 1 in the same manner as the parts model 2 except that the substrate of the printed wiring board was made of phenol resin.

<Parts Model 5> φ0.
Table 1 shows the electronic components equipped with a dicyclopentadiene-modified epoxy resin laminated board with a semiconductor element in which a 1-mm resin optical fiber (cycloolefin-based polymer, manufactured by JSR Corporation, trade name: Arton) was placed at a predetermined position. The test sample was cast.

Examples 1 to 3 and Comparative Examples 1 to 3 An output characteristic test and a control component continuity test were performed for each part model produced using the sealing polymer shown in Table 1, and the results are shown in Table 1. Was.

[0080]

[Table 1]

[0081]

The electric and electronic parts according to claims 1 to 7 are:
It can be easily manufactured without the need for handling in an inert atmosphere, and has excellent adhesion between the interior resin member and the polymer that seals it. It has long life and high durability corresponding to integration.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of an ignition coil as an example of an electric / electronic component of the present invention.

[Explanation of symbols]

 a core b primary bobbin c primary coil d secondary bobbin e secondary coil f terminal

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 23/31 H01F 31/00 501J // B29K 23:00 H01L 23/30 R B29L 31:34 (72) Inventor Masahiro Suzuki 4-3-1 Higashi-cho, Hitachi City, Ibaraki Prefecture Inside the Hitachi Chemical Co., Ltd.Yamazaki Office (72) Inventor Katsuhiko An 4-3-1-1, Higashi-cho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd.Yamazaki Business In-house F-term (reference) 4F206 AA12L AH16 AH33 JA07 JB12 JB17 JQ81 4M109 AA01 BA04 CA01 CA21 EA02 EA03 EB04 EB06 EB07 EB08 EB09 EB12 EB13 EB14 EB18 EB19 EC03 EC05 EC09 GA10 5E04A AC5 DA12E

Claims (7)

[Claims] 1. An electric / electronic component in which a resin member to be installed is made of at least a cycloolefin polymer, and the resin member is sealed with an olefin polymer. 2. The electric / electronic component according to claim 1, wherein the cycloolefin-based polymer is a norbornene-based resin. 3. The flexural modulus of the olefin polymer is 2
3. The electric / electronic component according to claim 1, which has a pressure of 500 MPa or less at 3 ° C. 4. The electric / electronic component according to claim 1, wherein the olefin-based polymer is a polymer obtained by metathesis polymerization of a cycloolefin-based compound. 5. The electric / electronic component according to claim 4, wherein the olefin-based polymer contains a filler. 6. The electronic / electric component according to claim 1, which is a high-voltage transformer comprising a magnetic core, a primary coil, a secondary coil, and an external connection terminal. 7. The electronic / electric component according to claim 6, which is an ignition coil for an engine.