JP2001342328A - Metathesis polymerizable composition and electric/ electronic part therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metathesis polymerizable composition giving a resin with oxidative deterioration resistance and excellent heat resistance, and to provide a highly densified and highly integrated electric/electronic part where with with a long life and high durability. SOLUTION: This metathesis polymerizable composition contains a metathesis polymerization catalyst (A), at least a metathesis polymerizable cycloolefin compound (B), and a fluorine surfactant (C), and this electric/electronic part are prepared therewith.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is useful as a metathesis polymerization catalyst, a sealing material containing a cycloolefin-based compound such as dicyclopentadiene or tricyclopentadiene and a fluorine-based surfactant, a chemical material such as an insulating material or a coating material. The present invention relates to a novel metathesis polymerizable resin composition and an electric / electronic component using the same.

[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 components generally comprise a case material and components to be installed. Examples of the constituent members include a printed wiring board and a resin-sealed IC or a diode mounted on the wiring board as long as it is a control component.
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 the resin member is made of a polymer material among the constituent members, the resin member may be 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, an epoxy resin is used as the most representative resin because of its 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. Further, generally soft type resins such as silicone resin and urethane resin have poor durability against external impact. About these measures,
JP-A-5-220767 and JP-A-6-16446
As disclosed in Japanese Patent Application Publication No. 5 (1993) -105, there is known a method of molding another resin on the surface.

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. Also, Japanese Patent Application Laid-Open No. 9-18383
No. 3 discloses electricity and electricity using a new metathesis polymerization catalyst.
Norbornene-based compounds suitable for sealing electronic components have been proposed. Further, JP-A-10-182922 discloses that a metathesis-polymerizable cycloolefin-based compound (prepolymer) has a low viscosity even when a filler is added, and is suitable for sealing electric / electronic parts. I have. However, the cycloolefin-based compounds and other olefin-based compounds described in these publications also have a problem in that when they are thermally degraded in the presence of oxygen, they are oxidatively degraded and their mechanical and electrical properties are reduced.

As described above, a hard resin having a high modulus of elasticity such as an epoxy resin is liable to cause problems such as peeling and cracking, and has a problem in reliability of electric and electronic parts. In addition, the silicone resin has a problem in adhesiveness, and the urethane resin has a problem in insulation, and there is a problem that a high-density integrated circuit or a fine circuit cannot be sufficiently sealed. In addition, polymers obtained by metathesis polymerization of dicyclopentadiene as an olefin resin and other olefin compounds generally change their properties due to oxidative deterioration when thermally degraded in the presence of oxygen. There are problems such as peeling off at the interface of the resin and cracking of the resin.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a metathesis polymerizable resin composition which suppresses oxidative deterioration and has excellent heat resistance.

Another object of the present invention is to provide a high-density, long-life, high-durability electric / electronic component using the above-mentioned metathesis polymerizable resin composition, which has a high density and is compatible with high integration. .

[0007]

Means for Solving the Problems The present inventors have found that the above-mentioned olefinic compound has a problem in that it undergoes thermal degradation due to oxygen.
As a result of earnestly examining the problem that the reliability of electronic components is impaired, by sealing electric and electronic components with a metathesis polymerizable resin composition containing a fluorine-based surfactant,
The inventors have found that oxidative deterioration of a polymer obtained by curing a resin composition made of an olefin-based polymer covering a component can be suppressed, and that the reliability of electric / electronic components can be improved. Based on this finding, the present invention has been completed.

That is, the present invention relates to a metathesis polymerizable resin composition containing a metathesis polymerization catalyst (A), one or more metathesis polymerizable cycloolefin-based compounds (B) and a fluorine-based surfactant (C). .

[0009] The present invention also relates to a metathesis polymerizable resin composition wherein the fluorine-containing surfactant (C) is a fluorine-containing nonionic surfactant.

[0010] The present invention also relates to the above metathesis polymerizable resin composition containing 1 to 500 parts by weight of a filler with respect to 100 parts by weight of the cycloolefin compound (B).

The present invention further relates to at least one additive selected from the group consisting of a modifier, a polymerization rate regulator, a foaming agent, an antifoaming agent, a colorant, a stabilizer, an adhesion promoter and a flame retardant. The present invention relates to the above metathesis polymerizable resin composition.

Further, the present invention relates to an electric / electronic part using the above-mentioned metathesis polymerizable resin composition.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The metathesis polymerization catalyst (A) used in the present invention includes WCl ₆ , MoCl ₅ , RuCl
₃ alone or in the case of a metal catalyst such as disclosed in JP-A-59-5191.
No. 1 publication, the two-component metathesis catalyst system comprising a combination of the catalyst component and an activator such as alkylaluminum, a Shock-type or Fischer-type metal carbene catalyst, a metal carbine catalyst, a metallacyclobutane type Catalysts, oxyhalide-based catalysts and the like are also included.

On the other hand, the one-component metathesis polymerization catalysts represented by the general formulas (1), (2) and (3) also convert cycloolefin compounds without easily losing catalytic activity due to oxygen or moisture in the air. Since ring-opening polymerization can be performed by metathesis (metathesis) reaction, it can be suitably used.

[0015]

Embedded image (M represents ruthenium or osmium, X and X1 each independently represent an anionic ligand, L and L1 each independently represent a neutral electron donating group or a nucleophilic carbene, and Q and Q1 each independently Represents a hydrogen, an alkyl group, an alkenyl group or an aromatic group, and the alkyl group, the alkenyl group or the aromatic group may have a substituent.)

[0016]

Embedded image (M represents ruthenium or osmium, X and X1 each independently represent an anionic ligand, L and L1 each independently represent a neutral electron donating group or a nucleophilic carbene, and Q and Q1 each independently Represents a hydrogen, an alkyl group, an alkenyl group or an aromatic group, and the alkyl group, the alkenyl group or the aromatic group may have a substituent.)

[0017]

Embedded image (M represents ruthenium or osmium, X and X1 each independently represent an anionic ligand, L and L1 each independently represent a neutral electron donating group or a nucleophilic carbene, and R ¹ and R ² represent Each independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms,
8 alkynyl group, aryl group, carboxylate group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, alkenyloxy group having 2 to 18 carbon atoms, alkynyloxy group having 2 to 18 carbon atoms, 2 carbon atoms -18 allyloxy groups,
Alkoxycarbonyl having 2 to 18 carbon atoms, 1 to 1 carbon atoms
8 represents an alkylthio group, an alkylsulfonyl group having 1 to 18 carbon atoms or an alkylsulfinyl group having 1 to 18 carbon atoms, and R ³ represents hydrogen, an aryl group or an alkyl group having 1 to 18 carbon atoms. ) Among such one-component metathesis polymerization catalysts,
The metathesis polymerization catalyst represented by the general formula (1) is particularly preferred.

[0018]

Embedded image In the general formula (1), M represents ruthenium or osmium. X and X1 each independently represent an anionic ligand. An anionic ligand is a group that has a negative charge when decoordinated to the central metal. Such groups include, for example, hydrogen, halogen, CF ₃ CO ₃ , CH ₃ C
O ₂ , CFH ₂ CO ₂ , (CH ₃ ) ₃ CO, (CF ₃ ) ₂ (C
_{H 3) CO, (CF 3} ) (CH 3) 2 CO, alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group, a phenoxy group, a tosyl group, mesyl group, trifluoromethane sulfonate There are groups and the like, and particularly preferred are halogen (particularly, chlorine) for both.

Q and Q1 each independently represent hydrogen, an alkyl group, an alkenyl group or an aromatic group. The alkyl group includes an alkyl group having 1 to 20 carbon atoms, the alkenyl group includes an alkenyl group having 2 to 20 carbon atoms, and the aromatic group includes an aryl group, for example, an aryl group having 6 to 20 carbon atoms. , An alkenyl group or an aromatic group may have a substituent.

L and L1 each independently represent a neutral electron donating group or a nucleophilic carbene. These are groups that have a neutral charge when decoordinated to the central metal. Such groups include, for example, PR ² R ³ R ⁴ (here, R ²
Is a secondary alkyl or cycloalkyl group, R ³ and R ⁴
Each independently represents an aryl group, a primary or secondary alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group. ), Pyridine, p-fluoropyridine, imidazolylidene compounds, and the like. Preferred L is -P (cyclohexyl)
₃ , -P (cyclopentyl) ₃ , -P (isopropyl) ₃
Similarly, L1 is preferably an imidazolylidene compound, -P (cyclohexyl) ₃ , -P (cyclopentyl) ₃ , or -P (isopropyl) ₃ . As the imidazolylidene compound exemplified as the nucleophilic carbene, a heterocyclic compound represented by the general formula (4) or (5) is preferable, and a heterocyclic compound represented by the general formula (5) is more preferable.

[0021]

Embedded image

[0022]

Embedded image Here, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms,
Examples thereof include an alkynyl group, a cycloalkyl group, and an aryl group having 2 to 20 carbon atoms. R ⁴ and R ⁵ have 1 to 1 carbon atoms
It may be substituted by an alkyl group having up to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group. Further, these groups may be halogen, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. Or a phenyl group. From the viewpoint of thermal stability, at least one of R ⁴ and R ⁵ is preferably a group represented by the general formula (6).

[0023]

Embedded image Here, R ⁶ and R ⁷ are each hydrogen, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and R ⁸ is hydrogen, an alkyl group having 1 to 10 carbon atoms, and aryl. Group or hydroxyl 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 , A carboalkoxy group, a carbamate group, a halogen and the like.

Specific examples of the imidazolylidene compound include the formulas (7) and (8). Particularly preferably,
It is an imidazolylidene compound of the formula (8) from the viewpoint of polymerization activity.

[0025]

Embedded image

[0026]

Embedded image Specific examples of such a catalyst preferably include formulas (9) to (11).

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image Hereinafter, a synthesis example of the catalyst represented by the formula (9) will be described.

<Synthesis Example> 500 ml of Fisher-P
Cyclooctadiene ruthenium dichloride (21 mmol), tricyclohexylphosphine (42 mmol), sodium hydroxide (7.2 g), sec-butanol 25 from which oxygen was removed was placed in an alter bottle.
Add 0 ml and heat at 90 ° C. under 2 atmospheres of hydrogen. Pressurization is repeated several times until the absorption of hydrogen is completed, and stirring is continued overnight. Cool to room temperature while applying hydrogen pressure to obtain a pale yellow precipitate. 30 ml of water was added and the precipitate was filtered, dried in a stream of hydrogen and dried over Ru (H) ₂ (H ₂ ) ₂ (P
cy ₃ ) ₂ [cy: cyclohexyl group] is obtained (yield: about 8).
0%). Next, this Ru (H) ₂ (H ₂ ) ₂ (Pcy ₃ ) ₂
(1.5 mmol) is dissolved in 30 ml of dichloroethane solution and cooled to -30 ° C. 3-chloro-3-methyl-
Add 1-butyne (1.5 mmol). The solution immediately turns reddish purple and is allowed to react for 15 minutes. The cooling bath was removed and degassed methanol (20 ml) was added to precipitate purple crystals. Wash with methanol and dry to obtain the desired catalyst (95% yield). (Reference: Org
nanometallics, Vol. 16, No. 18, 38
67 (1997)) The amount of these catalysts to be added is preferably 0.0005 to 0.05 based on the metathesis polymerizable cycloolefin compound (B).
Although it is 20% by weight, it is more preferably in the range of 0.001 to 5% by weight for reasons of economy and curing rate.

The raw material metathesis polymerizable cycloolefin compound used in the present invention may be any compound that is useful in metathesis polymerization. Among them, substituted or unsubstituted norbornene, dicyclopentadiene,
Norbornene monomers such as dihydrodicyclopentadiene are preferably used. Examples of the norbornene-based monomer include bicyclic norbornenes such as norbornene, methyl norbornene, dimethyl norbornene, ethyl norbornene, ethylidene norbornene, and butyl norbornene, dicyclopentadiene (a dimer of cyclopentadiene), dihydrodicyclopentadiene, and methyldicyclopentadiene. , Dimethyldicyclopentadiene, etc., tricyclic norbornene, tetracyclododecene, methyltetracyclododecene, tetracyclic norbornene such as dimethylcyclotetradodecene, tricyclopentadiene (trimer of cyclopentadiene), tetracyclopentadiene ( Norbornene having five or more rings, such as a tetramer of cyclopentadiene). Further, a compound having two or more norbornene groups, for example, norbornadiene, tetracyclododecadiene, symmetric tricyclopentadiene, or the like can be used as the polyfunctional crosslinking agent.

Among them, dicyclopentadiene, methyltetracyclododecene, ethylidene norbornene, tricyclopentadiene and tetracyclopentadiene are preferred, and dicyclopentadiene is particularly preferred, in terms of availability and economy. In addition, normal commercially available dicyclopentadiene is vinylnorbornene, tetrahydroindene, methylvinylnorbornene, methyltetrahydroindene, methyldicyclopentadiene,
Dicyclopentadiene, tricyclopentadiene, and the like may be contained as impurities in some cases, and dicyclopentadiene of various purity is commercially available. The dicyclopentadiene used in the present invention is usually 90% or more in purity, preferably 95% or more, particularly preferably 9% or more, depending on the intended use of the obtained polymer.
It has a purity of 8% or more.

These norbornene-based polymers can be used alone or as a mixture of a plurality of monomers. Preferably, a mixture containing 50% or more of dicyclopentadiene and, in addition, tricyclopentadiene and / or tetracyclopentadiene is used. It is.

Cycloolefins such as cyclobutene, cyclopentene, cyclooctene, cyclooctadiene, cyclododecene, cyclododecatriene, tetrahydroindene and methyltetrahydroindene, which can be ring-opening copolymerized with the norbornene monomer, are They can be mixed and used within a range that does not impair the object of the present invention.

When dicyclopentadiene is used, a part of the dicyclopentadiene is converted into a cyclopentadiene oligomer such as tricyclopentadiene or tetracyclopentadiene by heat treatment in advance, or vinylnorbornene or methylvinylnorbornene as an impurity is used. Can be isomerized to tetrahydroindene or methyltetrahydroindene. The heat treatment is usually performed at 120 to 250 ° C. for about 0.5 to 10 hours.

Further, an antioxidant can be added to the norbornene monomer used in the present invention, if necessary. Note that ordinary commercially available dicyclopentadiene already contains an antioxidant such as 2,6-di-t-butyl-4-methylphenol and 4-t-butylcatechol. In use, the contained antioxidant can be removed or newly added.

The antioxidant to be used is not particularly limited as long as it has an antioxidant ability, and preferred are hindered phenol-based antioxidants, and 2,6-di-
t-butyl-4-methylphenol, 2,6-di-t-
Butyl-4-ethylphenol, stearyl-β-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, tetrakis- [methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 2,2'-methylenebis (4-methyl-6-t-butylphenol),
2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-
Butylphenol), 1,3,5-trimethyl-2,
4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′,
5'-di-t-butyl-4'-hydroxybenzyl)-
S-triazine-2,4,6- (1H, 3H, 5H) trione and the like. The amount of antioxidant added is usually 1
It is 0 to 10,000 ppm.

The term "fluorinated surfactant" means one having a fluorine-containing group and a lipophilic group or / and a hydrophilic group in one molecule. The fluorine-containing group is an oxyethylene group, an oxypropylene group, or a group obtained by substituting a part or all of the hydrogen atoms of an alkyl group with a fluorine atom, preferably having 4 to 4 carbon atoms
20 perfluoroalkyl groups. The lipophilic group indicates an alkyl group, an alkenyl group, an alkynyl group or an aromatic group. An alkyl group has 1 to 20 carbon atoms, an alkenyl group has 2 to 20 carbon atoms, an alkynyl group has 2 to 20 carbon atoms, and an aromatic group has an aryl group such as carbon atoms. There are 6 to 20 aryl groups and the like, and the alkyl group, alkenyl group, alkynyl group or aromatic group may have a substituent. The hydrophilic group refers to an acid such as sulfonic acid, a metal salt of an acid, an alkali metal salt, an amide, and an ester. In addition, polyalkylene oxides having a degree of polymerization of 4 to 50, such as polyethylene oxide and polypropylene oxide, and acrylate oligomers can also be used, and these may be substituted with the lipophilic group and / or the hydrophilic group. This commercial product is Megafac F-12
0, Megafac F-150 (both trade names, manufactured by Dainippon Ink and Chemicals, Inc.) and the like.

Examples of the fluorine-based nonionic surfactant include:
Fluorosurfactants of the type in which part or all of the hydrogen atoms of the oxyethylene group, oxypropylene group, and alkyl group in the surfactant molecule are substituted with fluorine atoms, preferably perfluoroalkyl having 4 to 20 carbon atoms Those obtained by adding a polyalkylene oxide having a polymerization degree of 4 to 50 to a group,
For example, a perfluoroalkyl polyethylene oxide adduct, a perfluoroalkyl polypropylene oxide adduct, preferably an acrylate oligomer (perfluoroalkyl group-containing acrylate oligomer) containing a similar perfluoroalkyl group and a nonionic lipophilic group is used. It is desirable. Here, the nonionic lipophilic group refers to an alkyl group, an alkenyl group, an alkynyl group or an aromatic group. The alkyl group has 1 to 20 carbon atoms.
Examples of the alkyl group and alkenyl group include alkenyl groups having 2 to 20 carbon atoms, alkynyl groups include alkynyl groups having 2 to 20 carbon atoms, and aromatic groups include aryl groups such as aryl groups having 6 to 20 carbon atoms. , The alkyl group,
The alkenyl group, alkynyl group or aromatic group may have a substituent. This commercial product is MegaFac F-
142D, Megafac F-177, Megafac F-
178RM (both trade names manufactured by Dainippon Ink and Chemicals, Inc.) and Florard FC-430 (Sumitomo 3M Limited)
Product name).

The amount of the fluorine-based nonionic surfactant to be added is not particularly limited, but is usually 0.02 to 100 parts by weight of the metathesis polymerizable cycloolefin-based compound.
The amount is 1 to 30 parts by weight, preferably 0.1 to 10 parts by weight, particularly preferably 0.1 to 5.0 parts by weight.

In the present invention, in consideration of the physical properties, appearance and molding workability of the desired cured product, the resin composition may contain a filler, a modifier, a polymerization rate regulator, a foaming agent, Additives selected from foaming agents, coloring agents, stabilizers (ultraviolet absorbers, light stabilizers, antioxidants, antioxidants), adhesion promoters, and flame retardants can be added.

The filler used in the present invention refers to a generally known inorganic / organic filler of a granular material for the purpose of improving mechanical properties such as shrinkage and elasticity of the cured product and the mechanical properties of the cured product. A fiber reinforcement for the purpose of improving properties.

Examples of the powdery filler used in the present invention include crystalline silica, fused silica, synthetic silica, silica sand, calcium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium oxide, clay, expanded graphite, and fluorine. Inorganic fillers such as aluminum fluoride, wood flour, polyester, silicone, polystyrene acrylonitrile-
Organic fillers in the form of beads, such as butadiene-styrene (ABS), may be used. 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. Among them, silica and aluminum hydroxide are preferred from the viewpoint of electrical properties and thermal conductivity. Commercial products include CRT-AA, CRT-
D, RD-8, SO-R series, SO-H series (trade name, manufactured by Tatsumori Corporation), COX-31 (trade name, manufactured by Micro Corporation), C-303H, C-315H, C-3
08 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), SL-700
(Trade name, manufactured by Takehara Chemical Industry Co., Ltd.). The compounding amount of these inorganic fillers is 0 to 95% by weight, preferably 10 to 95% by weight, more preferably 30 to 95% by weight in the resin.
% By weight. If the amount exceeds 95% by weight, the mechanical properties of the cured resin product tend to decrease. More preferably, the content is 30 to 75% by weight. In order to stabilize the electrical characteristics and avoid corrosion of the metal conductor, it is preferable that the purity of the filler is as high as possible. For example, for silica, purity 9
It is preferably at least 9.5%. Further, the average particle size is 0.1.
Those having a thickness of 1 to 100 μm are preferred, and those having a thickness of 1 to 50 μm are particularly preferred. By combining those having different average particle sizes, the fine packing property and the fluidity can be improved. Further, the shape of the inorganic filler is preferably spherical. The amount, purity, particle size, shape, and the like of these fillers can be appropriately determined depending on the purpose.

In the present invention, a fiber reinforcing material can also be used. Examples thereof include inorganic reinforcing materials such as glass fiber, carbon fiber, and metal fiber, and olefin fibers such as aramid fiber, polyester fiber, and polyethylene and polypropylene. Preferably, glass fiber or carbon fiber reinforcement is used. These reinforcing materials may be in any form of long fibers, short fibers and powder. Roving in which the strands are aligned to form a bundle, roving cloth weaving the roving, continuous strand mat in which random coil-shaped long fibers are molded into a mat shape, chopped strands in which long fibers are cut, and gluing of chopped strands with a binder Chopped strand mats, surface mats, twill weave mats or three-dimensional glass mats combining cloth and strands (trade name: Parabeam, manufactured by Chori Co., Ltd.), non-woven fabrics, continuous strands, etc. A preform in which a strand is three-dimensionally formed can be used.

Examples of reinforcing materials other than fibers include milled glass, cut fibers, microfibers, microballoons, glass flakes and the like, and these can be used in combination. The aspect ratio and shape are appropriately selected according to the purpose.

The amount of the reinforcing material to be used is preferably 1 to 500 parts by weight, more preferably 5 to 400 parts by weight, per 100 parts by weight of the metathesis polymerizable cycloolefin compound.
Parts by weight, more preferably 10 to 300 parts by weight.

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), 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 polar groups may be grafted. Further, physical properties can be improved by blending epoxy resin, urethane resin, polyester resin, silicone resin, phenol resin, polyimide resin, polyamide resin, polyamideimide resin and derivatives thereof. 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 are also included.

Examples of the petroleum resin include those produced from a known C5 or C9 fraction purified from an ethylene plant. For example, Quinton (trade name of Zeon Corporation) or Norsolex (Zeon Corporation)
Trade name, thermoplastic polynorbornene resin). These petroleum resins preferably have a number average molecular weight (value converted by a gel permeation chromatography method using a standard polystyrene calibration curve) of 1000 or more, and have a functional group such as a hydroxyl group or an ester group in the resin skeleton. Is more desirable.

The amount of these modifiers depends on the physical properties of the desired cured resin, but is generally in the range of 0.2 to 50 parts by weight per 100 parts by weight of the metathesis polymerizable 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 part 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, as well as 1-hexene, allyl compounds, and compounds represented by the formula (7).
The compound represented by (8) is also included. These can be used in an amount of 0.005 to 20 parts by weight based on 100 parts by weight of the metathesis polymerizable cycloolefin compound. Since this usage amount is for the purpose of controlling the pot life of the resin composition, adjust the mixing amount appropriately, such as reducing the pot quantity when the pot life is short and increasing it when wanting to lengthen it. Can be.

Examples of the antifoaming agent include known antifoaming agents such as silicone-based oil, fluorine-based oil, and polycarboxylic acid-based polymer. Usually, 0.001 to 100 parts by weight of the metathesis-polymerizable cycloolefin-based compound is used. ~ 5
Parts by weight can be added.

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 and N'N-dinitrosopentane. Commonly known chemical foaming agents such as azo compounds such as methylenetetramine and compounds that generate nitrogen gas by decomposition such as nitroso compounds are exemplified.

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, 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. These pigments can be added in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the metathesis polymerizable cycloolefin compound.

As the stabilizer used in the present invention, generally known ultraviolet absorbers, light stabilizers, antioxidants, antioxidants and the like can be mentioned.

Examples of the ultraviolet absorber include salicylic acid ultraviolet absorbers such as phenyl salicylate and para-t-butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2,2'-dihydroxy. Benzophenone-based ultraviolet absorbers such as -4,4'dimethoxybenzophenone, 2- (2'-hydroxy-5'-methylphenyl)
Benzotriazole, 2- (2'-hydroxy-3 ',
5'-di-t-butylphenyl) benzotriazole,
Benzotriazole-based ultraviolet absorbers such as 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2-ethylhexyl-2-cyano-
Examples include cyanoacrylate ultraviolet absorbers such as 3,3'-diphenylacrylate and ethyl-2-cyano-3,3'-diphenylacrylate. These may be used alone or in combination of two or more. The addition amount of these ultraviolet absorbers is appropriately determined depending on the use environment and required characteristics of the cured product, but is usually 0.05 to 20 parts by weight based on 100 parts by weight of the metathesis polymerizable cycloolefin-based compound.

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-2,2,6,6-
Hindered amine light stabilizers such as tetramethylpiperidine polycondensate are exemplified. The light stabilizer can be added in an amount of 0.05 to 20 parts by weight based on 100 parts by weight of the metathesis polymerizable cycloolefin compound.

As antioxidants, parabenzoquinone,
Quinones such as tolquinone and naphthoquinone, hydroquinone, para-t-butylcatechol, 2,5-di-t-
Hydroquinones such as butyl hydroquinone, di-t
Butyl para-cresol hydroquinone monomethyl ether, phenols such as pyrogallol, copper salts such as copper naphthenate and copper octenoate, quaternary ammonium salts such as trimethylbenzylammonium chloride, trimethylbenzylammonium maleate, phenyltrimethylammonium chloride, Oximes such as quinone dioxime and methyl ethyl ketoxime; amine hydrochlorides such as triethylamine hydrochloride and dibutylamine hydrochloride; 3,6,9-trioxaundecyl-1,11
And sulfur-based substances such as -bis (3-dodecylthiopropionate), and oils such as mineral oil, essential oil, and fatty oil. These antioxidants are classified according to conditions such as compatibility with the filler, intended molding workability, and resin storage stability.
Add in varying amounts. The amount added is generally 0.000.00 parts by weight per 100 parts by weight of the metathesis polymerizable cycloolefin compound.
It can be used in the range of 001 to 10 parts by weight.

Examples of the adhesion-imparting agent used in the present invention include generally known silane coupling agents.

The silane coupling agent is usually represented by the formula YSiX (Y is a monovalent group having a functional group and binding to Si, X is a monovalent group having a hydrolyzing property and binding to Si). expressed. Examples of the functional group in Y include vinyl,
There are groups such as amino, epoxy, chloro, mercapto, methacryloxy, cyano, carbamate, pyridine, sulfonyl azide, urea, styryl, chloromethyl, ammonium salts, alcohols and the like. X includes, for example, chloro, methoxy, ethoxy, methoxyethoxy and the like.

As specific examples, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, γ
-(2-aminoethyl) -aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N, N-
Dimethylaminophenyltriethoxysilane, mercaptoethyltriethoxysilane, methacryloxyethyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane hydrochloride, etc. Examples thereof include polymer-type polysiloxane derivative compounds, and these can be used in combination. The silane coupling agent is usually used in an amount of 0.001 to 100 parts by weight of the metathesis polymerizable cycloolefin compound.
-5 parts by weight can be added.

As the flame retardant, hexabromobenzene,
Tetrabromobisphenol A, decabromodiphenyl oxide, tribromophenol, dibromophenyl glycidyl ether, perchloropentacyclodecane,
Halogen compounds such as heptate derivatives are used alone or in combination of two or more. 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. Flame retardants also include auxiliary flame retardants.

Further, examples of the auxiliary flame retardant include antimony trioxide, iron oxide, aluminum hydride and the like. When these are used in combination with the flame retardant, the flame retardant effect is further enhanced. The halogen-based flame retardant can be used usually in an amount of 1 to 50 parts by weight based on 100 parts by weight of the metathesis polymerizable cycloolefin-based compound. The auxiliary flame retardant such as antimony trioxide can be used in the range of 1 to 15 parts by weight based on 100 parts by weight of the metathesis polymerizable cycloolefin compound. Hydrates such as commercially available aluminum hydroxide and magnesium hydroxide can also be used as fillers for flame retardancy as plastic fillers. It is preferable to use these additives in the range of 10 to 300 parts by weight based on 100 parts by weight of the metathesis polymerizable cycloolefin compound.

In addition, commercially available wetting agents and dispersants such as BYK series manufactured by BYK-Chemie can be added to improve the wettability between the filler and the metathesis polymerizable cycloolefin compound. Further, in order to improve molding workability, a release agent such as silicone oil or zinc stearate can be added. A thixotropic agent can also be added. Thixotropic agents are generally known. For example, silica fume (Nippon Aerosil Co., Ltd.)
Product name: # 200, R972, RX200, etc.),
Bentonite and the like. Further, a silica balloon (Baomasil manufactured by DuPont) can also be used. Further, for example, Dispalon manufactured by Kusumoto Kasei Co., Ltd. or an organic thixotropic agent provided by BYK can be used. The addition amount is preferably 0.01 to 20 parts by weight based on 100 parts by weight of the metathesis polymerizable cycloolefin compound. If the amount is less than 0.01 part by weight, the effect as a thixotropic agent tends to be insufficient, and if it exceeds 20 parts by weight, the fluidity tends to decrease.

Further, an organic peroxide can be added. Examples of the organic peroxide include cumene hydroperoxide, tert-butylperoxy 2-ethylhexanate, methyl ethyl ketone peroxide, benzoyl peroxide, acetylacetone peroxide, bis-4-tert-butylcyclohexanedicarbonate, and 2,5- Known compounds such as dimethyl-2,5-bis (tert-butylperoxy) -3-hexyne may be mentioned, and two or more of these may be used in combination. The amount of addition is usually 100 metathesis polymerizable cycloolefin compound.
It is preferably 0.1 to 10 parts by weight based on parts by weight.

[0065] The resin composition of the present invention does not contain a solvent.
The solvent is a generally known non-reactive diluting solvent such as benzene, toluene, xylene, ethyl acetate, and methyl ethyl ketone. However, among the above additives, the solvents contained in the commercial products are neglected. But,
Even in this case, it is preferable that the solvent is less than 2% by weight in the metathesis polymerizable cycloolefin compound in order to prevent swelling during curing.

In order to adjust the viscosity of the metathesis polymerizable resin composition and the mechanical and electrical properties of the cured product, a low-viscosity reactive dilution such as an acrylic monomer, a methacrylic monomer, a vinyl monomer or diallyl phthalate is usually used. Agents may be used, and these may be used alone or in combination of two or more.

The polymerization can be usually carried out by adding a catalyst to the metathesis-polymerizable cycloolefin compound and dissolving it, followed by heating. The temperature at which the catalyst is added to and dissolved in the resin solution is usually 0 to 80C, preferably room temperature to 50C. The heating operation for obtaining the polymer can be performed in two stages even with one-stage heating.
Step heating may be used. 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, preferably Is 10 to 100 ° C. and 2
The temperature at the stage is usually 20 to 200 ° C., preferably 3 to 200 ° C.
0-180 ° C. Further, the polymerization time can be appropriately determined depending on the amount of the catalyst and the polymerization temperature, but is usually from 1 minute to 1 minute.
50 hours.

Examples of the method for forming the electric / electronic component of the present invention include injection molding at atmospheric pressure, vacuum injection molding, pressure injection molding, impregnation molding, RTM molding, dipping, hand lay-up and spraying. Examples include a lamination molding method such as up, a press molding method, a filament winding method, a centrifugal molding method, a vacuum or pressure back method, a continuous molding method, a pultrusion molding method, an injection molding method, and a transfer molding method. When the metathesis polymerization catalysts represented by the general formulas (1) to (3) of the present invention are used, it is not necessary to form an inert atmosphere in molding them.

As the electric / electronic parts of the present invention, for example, as a communication part, a quartz or plastic optical fiber light guide unit (optical integrated circuit device), a photoelectric conversion device,
Electronic and electrical components for communication including antennas and integrated circuits, R
IC tags (ID tags, R tags) used as automatic recognition components such as F (Radio Frequency) modules, contact or non-contact IC cards, tags, and marks
F tag). In addition, ignition coils, flyback transformers, high-voltage transformers for lighting discharge lamps, rotating machines or rotating electrical machines, generators, electric motors, electric coil parts such as electromagnetic clutches, insulating bushings, pressure / rotation / flow rate / solar radiation・ Sensors for sensing temperature, distance, acceleration, angular velocity, magnetism, etc .; electronic components consisting of circuit boards made of resin and ceramic, such as igniters and ECUs, and semiconductor element-related components; Examples include circuit devices, semiconductor modules, transistors, capacitors, and circuit boards. Further, a light-emitting display device, a liquid crystal display device, or the like may be used depending on a processing method. In addition, a sliding resistor treated with a composite with graphite and a variable resistor using the same are also included. Further, there may be mentioned an electromagnetic valve for controlling a gas or liquid fluid, a fuel cell binder and partition cells, a magnet switch, an electrical connector, a battery component such as a relay, a secondary battery, a fuel cell, a solar cell, and the like. These components can be used for any purpose such as industrial, consumer, vehicular, and military use.

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

[0071]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means “parts by weight” unless otherwise specified.

<Resin liquid 1> Dicyclopentadiene (produced by Maruzen Petrochemical, purity 99%, DCPD) 74 parts by weight of cyclooctadiene (produced by Degussa-Hüls, purity 99%) per 25 parts by weight of an antioxidant A resin liquid 1 was prepared by adding 1 part by weight of 2,6-di-tert-butyl-4-methylphenol and 0.05 part by weight of a polymerization rate regulator triphenylphosphine (reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.). did.

<Preparation of Cured Product> The resin temperature was adjusted to 25 ° C., a metathesis polymerization catalyst shown in the following (9) was added, and the mixture was stirred for 5 minutes to completely dissolve the catalyst. Thereafter, a predetermined surfactant was added, and the mixture was further stirred for 5 minutes using a stirrer. Each resin liquid was coated on a metal Petri dish (φ60 × 13
mmt) and 1 hour at 25 ° C, followed by 100 ° C
For 2 hours. The test surfactants and formulations are shown in Tables 1 and 2.

[0074]

Embedded image <Test items><Curingdegree> Vacuum Riko TG-DTA (thermal balance analyzer T
GD-7000) at RT to 400 ° C at 10 ° C /
The temperature was raised in min, the loss on heating at 250 ° C. was measured, and the degree of cure of the test sample was calculated by the following formula.

Curing degree% = weight of test piece at 250 ° C. (g)
/ RT Weight of Test Specimen (g) <Hardness> After a test sample is heated and degraded at 130 ° C. in an air atmosphere for a predetermined time, a spring type hardness tester HD-101N manufactured by Ueshima Seisakusho (Type A) is used. The hardness was measured in accordance with JIS K6253 using a spring-type hardness tester GS-701N (Type E) manufactured by Teclock Corporation. <Discoloration Depth> After a test sample was heated and degraded at 130 ° C. for a predetermined time in an air atmosphere, it was cut, and the length in the depth direction of a discoloration area due to oxidation was measured.

Table 2 shows the results of the examples and the comparative examples.
The resin composition of the present invention can provide a material having excellent heat resistance as compared with a conventional composition.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

According to the electric / electronic component of the present invention, a long-life, high-durability electric / electronic device corresponding to high density and high integration can be widely provided.

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Claims (5)

[Claims] 1. Metathesis polymerization catalyst (A), one or two
A metathesis polymerizable resin composition comprising at least one kind of metathesis polymerizable cycloolefin compound (B) and a fluorine surfactant (C). 2. The metathesis polymerizable resin composition according to claim 1, wherein the fluorinated surfactant (C) is a fluorinated nonionic surfactant. 3. The metathesis polymerizable resin composition according to claim 1, comprising 1 to 500 parts by weight of a filler based on 100 parts by weight of the metathesis polymerizable cycloolefin compound (B). 4. The composition further comprises at least one selected from the group consisting of a modifier, a polymerization rate regulator, a foaming agent, an antifoaming agent, a colorant, a stabilizer, an adhesiveness-imparting agent and a flame retardant.
The metathesis polymerizable resin composition according to claim 1, 2 or 3. 5. An electric / electronic part using the metathesis polymerizable resin composition according to claim 1.