WO1999058592A1

WO1999058592A1 - Resin composition and process for producing cured article using the same

Info

Publication number: WO1999058592A1
Application number: PCT/JP1999/002520
Authority: WO
Inventors: Tomoaki Aoki; Toyoji Ohshima; Shunichi Numata; Toru Kikuchi; Hiromasa Kawai; Masami Yusa; Hitoshi Yamazaki; Robert Shu Chen Chu; Kazuyuki Tanaka; Yoshiki Inoue
Original assignee: Hitachi Chemical Company, Ltd.
Priority date: 1998-05-14
Filing date: 1999-05-14
Publication date: 1999-11-18
Also published as: KR20010052342A; TWI237646B; AU3730899A; KR100372985B1

Abstract

A resin composition comprising (a) a cycloolefin compound capable of undergoing metathesis polymerization, (b) a metathesis polymerization catalyst represented by formula (A), and (c) a filler, reinforcement, or additive; and a process for producing a cured article which comprises curing the composition. In formula (A), M represents ruthenium or osmium; X?1 and X2¿ each independently represents an anionic ligand; L?1 and L2¿ each independently represents a neutral electron-donating group; R?1 and R2¿ each represents an organic group; and R3 represents hydrogen, aryl, or alkyl.

Description

TECHNICAL FIELD The present invention relates to a resin composition for metathesis polymerization and a method for producing a cured product using the same. These resin compositions or cured products are useful as insulating materials for electronics and electricity, molding materials for household equipment such as septic tanks and bathtubs, and industrial materials such as corrugated sheets and pipes.

BACKGROUND ART It is known that ring-opening polymerization of cycloolefins is carried out by a metathesis polymerization catalyst system. For example, J. Am. Chem. Soc, 1960, Vol. 82, p. 2337 describes that ring-opening polymerization of norbornene is carried out by a metathesis catalyst system, and Angew. Cem. Int. Edn., 1964, Vol. 3, p. 723 shows that cyclopentene is a metathesis catalyst system.

Ring opening polymerization by [MoCl ₅ / Al (C ₂ H ₅ ) ₃ ] is described.

A method for producing a polymer by ring-opening polymerization of cycloolefins is also known. For example, Japanese Unexamined Patent Application Publication Nos. Sho 50-130900 and Sho 52-330000 disclose a metathesis catalyst system comprising a halide such as tungsten or molybdenum and an organoaluminum compound. A method for producing a ring-opening polymer using the method is disclosed. On the other hand, a method is also known in which a norbornene-type cycloolefin such as tricyclopentene is bulk-polymerized to obtain a crosslinked polymer molded product. For example, JP-A-58-127728 and JP-A-58-12913 disclose a catalyst component of a female catalyst system and a mixture with a D CPD. There is disclosed a method for producing a crosslinked polymer molded product by a reaction injection molding (RIM) method from a solution A and a solution B comprising a mixture of an activator of a female catalyst system and D CPD.

JP-A-59-51911 discloses a catalyst component selected from organic ammonium salts of tungsten and molybdenum and a catalyst component selected from alkoxyalkyl aluminum halides and aryloxy aluminum halides. A method for producing a crosslinked polymer molded article by reaction injection molding of norbornene-type cycloolefin using a metathesis catalyst system combined with an activator is disclosed.

Further, Japanese Patent Application Laid-Open No. 3-250409 discloses a catalyst component selected from tandastene hexachloride and tungsten oxytetrachloride and an activation selected from getyl aluminum chloride and ethyl ethyl dichloride. A method for producing a dicyclopentene polymer crosslinked by a reaction injection molding method using a mesythesis catalyst system combined with an agent is disclosed.

In the metathesis catalyst system described above, it has been found that the catalyst component is activated by an activator and causes ring-opening polymerization of norbornene-type cycloolefins. In the case of performing the above reaction injection molding, the solution A and the solution B are collision-mixed, and the mixed solution is immediately poured into a mold in a liquid state, and is subjected to ring-opening polymerization in a lump. Also, this It is known that the cured product thus obtained has excellent mechanical properties, electrical properties, water resistance and the like.

However, the organoaluminum compound used as the activator has high reactivity, and immediately reacts with water or oxygen in the presence of water and oxygen to lose the catalyst activating effect.

Therefore, when performing reaction injection molding, the molding materials (solution A and solution B) should be stored in a container filled with an inert gas or divided to minimize the intrusion of water and oxygen in the atmosphere. It was necessary to perform bulk polymerization in a space formed with the mold closed. For this reason, the molding material could not be introduced into the mold while being in contact with the atmosphere, and it was difficult to produce a molded product by a general-purpose compression molding method.

DISCLOSURE OF THE INVENTION An object of the present invention is to solve the above problems and provide a resin composition suitable for obtaining various molded products from a cycloolefin-based compound in an ordinary working environment.

The present inventors have studied a resin composition in which a polymerizable cycloolefin compound is polymerized and molded using a polymerizable polymerization catalyst. As a result, when a specific polymerized polymerization catalyst is used, the resin composition is used in a normal working environment. Under such circumstances, they have found that a molded article having excellent properties such as water resistance, tough mechanical properties, and electrical properties can be obtained, and thus completed the present invention. That is, the present invention

(a) a metathesis polymerizable cycloolefin compound, (b) a polymerization catalyst represented by the following formula (A):

, 3

M = CR ^J

(A)

X ¹ L ^J c = c

H

(M represents ruthenium or osmium,

X ¹ and X ² each independently represent an anionic ligand,

L ¹ and L ² each independently represent a neutral electron donating group,

R ¹ and R ² are each independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group, and a carbon atom having 1 to 18 carbon atoms. Poxylate group, alkoxy group having 1 to 18 carbon atoms, alkenyloxy group having 2 to 18 carbon atoms, alkynyloxy group having 2 to 18 carbon atoms, aryloxy group, alkoxycarboxy having 2 to 18 carbon atoms A hydrogen 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 a carbon number. And represents an alkyl group of 1 to 18. And (c) a resin composition comprising at least one third component selected from fillers, reinforcing materials and additives.

The resin composition contains component (b) in an amount of 0.001 to 20 parts by weight per 100 parts by weight of component (a), and contains component (c) as component (a) and component (b). And preferably 0.001 to 97% by weight based on the total amount of component (c).

Further, the present invention provides a method for producing a cured product, characterized by heating and curing the above resin composition. BEST MODE FOR CARRYING OUT THE INVENTION The metathesis polymerizable cycloolefin compound in the component (a) used in the present invention may be any polymerizable cycloolefin useful in a methesis polymerization. Among them, norbornene-based compounds such as substituted or unsubstituted norbornene, dicyclopentane, and dihydrocyclopentane are preferably used.

Examples of the norbornene-based compound include bicyclic norbornenes such as norpolene, methylnorbornene, dimethylnorbornene, ethylnorbornene, ethylidenenorbornene, butylnorbornene, etc., dicyclopentagen (dimer of cyclopentadiene), Tricyclic norbornene, tetracyclododecene, methyltetracyclododecene, dimethylcyclotetradodecene, etc., tetracyclic norbornene, tricyclopentade, etc. Norbornene with five or more rings, such as the trimer of Lopene-Yugen, and the tetramer of Tetrasic-Loveen (a tetramer of Cyclopene-Yugen). Further, a compound having two or more norbornene groups, for example, norpolnadiene, tetracyclododecagen, symmetric tricyclopentane, or the like can also be used as the polyfunctional crosslinking agent.

Of these, dicyclopropene, methyltetracyclododecene, and ethylenidolnorne are available for their availability and economy. , Tricyclopentadiene and tetracyclopentadiene are preferred, and dicyclopentadiene is particularly preferred.

These norbornene-based compounds can be used alone or as a mixture of a plurality of compounds. However, preferably, the dicyclopentene of 50% by weight or more and the tricyclopentene and / or terephthalene are used. It is a mixture containing tracyclopentene. In addition, cyclobutene (cyclopentene), cyclobutene, cyclopentene, cyclooctadene, cyclododecene, tetradroindene, methyltetrahydrindene, etc. which can be ring-opening copolymerized with the above norpolene compounds. These cycloolefins can be mixed and used as long as the object of the present invention is not impaired. The usual commercially available dicyclopentenes include impurities such as vinyl norbornene, tetrahydrodenden, methylvinylnorbornene, methyl tetrahydrodenden, methyldicyclobenzene, dimethyldicyclopentagen, and tricyclopentane. Pentagen of various purity is commercially available. As the dicyclopentene used in the present invention, one having a purity of at least 80% by weight, preferably at least 90% by weight is used, although it varies depending on the intended use of the obtained polymer.

Prior to using the Jiksik pen pen, a part of the jisk pen will be heat-treated in advance so that a part of the jig pen can be used. It can be a sesame or an isomer of vinyl norbornene / methylvinyl norbornene, which is an impurity, to tetrahydroidone / methyltetrahydroidene. Heat treatment Is usually 120 to 250 hours, which is about 0.5 to 10 hours. Further, an antioxidant of 1.5 to 10% by weight can be added to prevent polymerization during the heat treatment.

Further, an antioxidant can be added in advance to the norbornene-based compound used in the present invention, if necessary. In addition, ordinary commercially available di-six-opening pen phenols already contain antioxidants such as 2,6-di (t-butyl) -4-methylphenol and 4- (t-butyl) catechol. . In use, the contained antioxidant can be removed or added newly.

The metathesis-polymerizable cycloolefin compound is a polymer obtained by partially polymerizing the metathesis-polymerizable cycloolefin compound.

(This also includes what is called semi-cured or B-stage.) Metathesis polymerizable cycloolefin compound and formula

If the metathesis polymerization catalyst of (A) is mixed, a polymer is formed with time, although the degree varies, and the component (a) in the composition after mixing contains the metathesis polymerizable cycloolefin compound and the polymer. It becomes a mixture. Here, the production rate of the polymer can be appropriately adjusted by changing the conditions (amount, type, temperature, time, etc. of the metathesis polymerization catalyst).

The component (b) used in the present invention is a metathesis polymerization catalyst represented by the formula (A) as described above. Unlike conventional two-component metathesis catalysts that combine a catalyst component and an activator, this catalyst is a cycloolefin-based catalyst that does not easily lose its catalytic activity due to oxygen or moisture in the air. It is a catalyst that can be used for ring-opening polymerization of a compound by a methesis reaction.

In addition, the anionic ligand in X ¹ and X ² in the formula (A) is A group that has a negative charge when coordinated to the central metal is removed. Such groups include, for example, hydrogen, Bruno, _{_{_{androgenic, CF 3 C0 2, CH 3}}} C0 2, C FH 2 C0 2, (CH 3) 3 CO, (CF 3) 2 (CH 3) CO, ( CF ₃ ) (CH ₃ ) ₂ CO. Alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, phenyl group, phenoxy group, tosyl group, mesyl group, trifluoromethanesulfonate group, etc. Particularly preferred are both halogen (particularly, chlorine).

L ¹ and L ² each independently represent a neutral electron donating group. Neutral charged groups are those that have a neutral charge when decoordinated to a central metal. Examples of such a group include, for example, PR ⁴ R ⁵ R ⁶ (where R ⁴ is a secondary alkyl group or a cycloalkyl group, R ⁵ and R ⁶ are each independently an aryl group, a carbon number of 1 to A primary alkyl group, a secondary alkyl group, or a cycloalkyl group of 10), a phosphine-based electron donating group represented by the formula: pyridine, p-fluoropyridine, an imidazolylidene compound, or the like. is there. Preferred L ¹ and L ² are both p- (cyclohexyl) ₃ , —p— (cyclopentyl) ₃ , or —p— (isopropyl) ₃ , but L ¹ and L ² are different from each other. It may be a substituent. Q ¹ and Q ² each independently represent hydrogen, an alkyl group, an alkenyl group, or an aromatic group. Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, examples of the alkenyl group include alkenyl groups having 2 to 20 carbon atoms, and examples of the aromatic group include an aryl group. The group may have a substituent.

Methods for synthesizing the above compounds (catalysts) are already known. For example, as shown in Organometallics, Vol. 16, No. 18, p. 3867 (1997), the method using propargyl chloride See scheme

Ru (H) (H ₂ ) C 1 (P cy ₃ ) ₂ cy

R ₇ and

A specific example of such a compound (catalyst) is a Ru-forced pen catalyst as shown in the following formula.

(1) (2)

(3) An example of catalyst synthesis is shown below. Synthesis example (see the above scheme, R ⁷ and R ⁸ : methyl group)

In a 500ml Fisher-Porter bottle, cyclohexene benzene dichloride (21mmol), tricyclohexylphosphine

(42 mmol), sodium hydroxide (7.2 g) and 250 ml of sec-butanol removed from oxygen were added, and the mixture was heated at 90 under 2 atm of hydrogen. Pressurization is repeated several times until hydrogen absorption is completed, and stirring is continued for a while. Cool to room temperature while applying hydrogen pressure to obtain a pale yellow precipitate. 30 ml of water was added, and the precipitate was filtered and dried in a stream of hydrogen to obtain Ru (H) ₂ (H ₂ ) 2 (Pcy ₃ ) ₂ (yield about 80%).

Next, this Ru (H) ₂ (H ₂ ) ₂ (Pcy ₃ ) ₂ (1.5 mmol) is dissolved in 30 ml of a dichlorobenzene solution and cooled to −30. Add 3-chloro-3-methyl-1-butyne (1.5 mmol). The solution immediately turns reddish purple and is allowed to react for 15 minutes. Remove the cooling bath and add degassed methanol (20 ml) to precipitate purple crystals. This is washed with methanol and dried to obtain a Ru carbene catalyst (Cl) ₂ (Pcy ₃ ) ₂ Ru = CH-CH = C (CH ₃ ) ₂ of the above formula (1) (yield 95%) „(Reference: Organometallics Vol. 16, No. 18, p. 3867 (1997))

The amount of the above-mentioned polymerization catalyst, ie, the amount of the component (b) to be used is 0.000 to 100 parts by weight of the metathesis-polymerizable cycloolefin compound of the component (a) and / or 100 parts by weight of the polymer thereof (reference). It is 1 to 20 parts by weight, preferably 0.01 to 5 parts by weight. If the amount is less than 0.001 part by weight, the curing will be poor, and if it exceeds 20 parts by weight, the case will be economical.

The resin composition according to the present invention comprises, in addition to the component (a) and the component (b), a filler, a reinforcing material, and an additive (a filler and a reinforcing material). At least one third component (component C) selected from other materials.

As used herein, the term “filler” refers to a filler contained for the purpose of improving mechanical properties such as shrinkage ratio and elastic modulus of the obtained cured product, and includes powdery or granular inorganic filler and organic filler. There is.

Examples of the inorganic filler include silica, silica sand, calcium carbonate, aluminum hydroxide, magnesium hydroxide, and clay, and examples of the organic filler include wood powder, polyester, and polystyrene beads. . The grain size, shape, grade, etc., of the cured product can be appropriately determined depending on the use, physical properties, etc. of the cured product. The amount (content) of the filler may be appropriately determined depending on the use, physical properties, etc. of the cured product. However, the metathesis polymerizable material of the component (a), the lip-based refin-based compound and / or its polymer 10 1 to 2000 parts by weight based on 0 parts by weight is preferred.

The reinforcing material is included for the purpose of improving the mechanical properties of the cured product, and a typical one is a fiber reinforcing material. Examples of the fiber reinforcing material include inorganic reinforcing material such as glass fiber, carbon fiber, and metal fiber, fiber reinforced fiber, polyester fiber, and olefin-based fiber such as polyethylene and polypropylene, and preferably glass. Fiber, aramide fiber or carbon fiber. These reinforcements may be long fibers or short fibers. Rovings in which strands are aligned to form a bundle, roving cloth weaving rovings, continuous stainless steel mats in which random coil-shaped long fibers are molded into a mat shape, chopped doss in which long fibers are cut Tipped and chopped strands are glued with a binder and molded into a mat shape. Three-dimensional glass mats (commercially available from Chori Co., Ltd., trade name: Parabim), which are a combination of single mats, twilled mats or crosses, and strands, non-woven fabrics, continuity strands and fabrics A preform in which a land is three-dimensionally formed can be used.

As a reinforcing material in a form other than the fiber, a milled glass, a cut fiber, a micro fiber, a micro balloon, a scaly glass powder, and the like can be used, and a fiber reinforcing material and a combination thereof can be used. Select the aspect ratio and shape as appropriate for the purpose.

The use amount (content) of these reinforcing materials is preferably 5 to 200 parts by weight based on 100 parts by weight of the metathesis polymerizable cycloolefin compound and the polymer thereof of the component (a). .

As the component (c), in addition to the filler and the reinforcing material, various additives can be contained for the purpose of improving the physical properties, appearance, molding workability, and the like of the cured product. Such additives include modifiers, polymerization rate regulators, defoamers, foaming agents, release agents, colorants, and stabilizers (UV absorbers, light stabilizers, antioxidants) , Adhesives, flame retardants, wetting agents, dispersants and organic peroxides.

Examples of the modifying agent include elastomers, natural rubbers, butene-based rubbers, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene, and the like. —Copolymers such as maleic acid copolymers and ethylene-vinyl acetate copolymers, and thermoplastic resins such as polymethyl methacrylate, polyvinyl acetate and polystyrene. Further, these copolymers and thermoplastic resins may be esterified, or polar groups may be graphed. Also, higher fatty acids such as oleic acid and linoleic acid, higher alcohols having 5 or more carbon atoms, Grade diols and the like can also be mentioned. In addition, epoxy resin, urethane resin, polyester resin, silicone resin, phenol resin, polyimide resin, polyamide resin, polyamide imide resin, and cyclic olefin polymer And their derivatives can be blended to improve physical properties. Further, for example, a compound obtained by reacting an epoxy compound with norbornene monocarboxy liquid, a compound obtained by reacting an isocene compound with norbornene-ol, a high-mix acid-modified polyester, There are also petroleum resins.

Petroleum resins include those manufactured from a known C5 or C9 fraction purified from ethylene plant, such as Quinton (trade name, manufactured by Zeon Corporation) Plastic polynorbornene resin Nisorex (trade name, manufactured by Nippon Zeon) and the like. These petroleum resins preferably have a number average molecular weight of 100 or more, and more preferably have a functional group such as a hydroxyl group or an ester group in the resin skeleton.

The amount used (content) depends on the physical properties of the desired cured resin, but is preferably 0.5 to 500 parts by weight per 100 parts by weight of the component (a).

Examples of the polymerization rate regulator include phosphoric acid salts such as triisopropyl phosphine, triphenyl phosphine, tricyclohexyl phosphine, and dicyclohexyl phenyl phosphine. This amount (content) is usually 0.005 to 20 parts by weight based on 100 parts by weight of the component (a). Since the polymerization rate regulator controls the usable time (pot life) of the resin composition, if the time is short, the amount is small and long. Use a lot when you want.

Examples of the defoaming agent include defoaming agents such as silicone oil, fluorine oil, and polycarboxylic acid polymer. The amount (content) of the defoaming agent is 100 parts by weight of the component (a). It is usually 0.001 to 5 parts by weight.

Examples of the foaming agent include low-boiling hydrocarbon compounds such as pentane, propane, and hexane; known physical foaming agents such as carbon dioxide and water vapor; and azobisisobutyronitrile ゃ, Ν'-dini torso pentamethylene tetramine. Known chemical foaming agents such as compounds that generate nitrogen gas by the decomposition of azo compounds and nitroso compounds of the above.

Coloring agents include inorganic pigments such as titanium dioxide, titanium black, cobalt blue, and cadmium yellow, carbon black, and aniline black.) 3-Naphthol, phthalocyanine, quinacridone, azo, quinophthalone, Organic pigments such as indanthrene blue can be mentioned, and each is blended according to a desired color tone. These may be used in combination of two or more. Usually, the amount (content) of these pigments is 0.1 to 50 parts by weight based on 100 parts by weight of the component (a).

Examples of the stabilizer include an ultraviolet absorber, a light stabilizer, an antioxidant, and a processing stabilizer.

Here, examples of the ultraviolet absorber include salicylic acid-based ultraviolet absorbers such as phenylzarylate, p- (t-butyl) phenylsalicylate, 2,4-dihydroxybenzophenone, and 2,4-dihydroxybenzophenone. Benzophenone-based ultraviolet absorbers such as —hydroxy—4-methoxybenzophenone and 2,2′-dihydroxy-4,4′-dimethoxybenzophenone; 2- (2'-hydroxy 5'-methylphenyl) benzotriazole, 2- (2'-hydroxy 3 ', 5'-di (t-butyl) phenyl) benzotriazole, 2- ( 2'-Hydroxy-1 3 ', 5'-di (t-amyl) phenyl) benzotriazole UV absorber such as benzotriazole, 2-ethylhexyl-2-cyano-3,3'-diphenyl And cyanoacrylate-based UV absorbers such as rucrerate and ethyl 2-cyano-3,3'-diphenylacrylate. These may be used alone or in combination of two or more. The amount (content) of these UV absorbers may be appropriately determined according to the usage 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 component (a). Department.

Examples of light stabilizers include bis (2,2,6,6-tetramethyl-4-pyridyl) sebacate and bis (1,2,2,6,6-pentylmethyl-4-piperidyl). Di-nil) sebacate, dimethyl succinate · 11- (2-hydroxylethyl) 1-4-hydroxy 2,2,6,6-tetramethylbiperidine No. The amount (content) of this light stabilizer is usually 0.05 to 20 parts by weight based on 100 parts by weight of the component (a).

Examples of antioxidants include quinones such as parabenzoquinone, tolquinone, and naphthoquinone, hydroquinone, p- (t-butyl) catechol, and 2,5-di-t-butylhydroquinone. Hydroquinones, di-tert-butyl parahydroxyl hydroquinone monomethyl ether, phenols such as pyrogallol, copper salts such as copper naphthenate copper octoate, trimethylbenzylammonium chloride Quaternary ammonium salts such as trimethylbenzyl ammonium maleate and phenyl trimethyl ammonium chloride And oximes such as quinondioxime-methylethylketoxime; amide hydrochlorides such as triethylamine hydrochloride and dibutylamine hydrochloride; and oils such as mineral oil, essential oil and fatty oil. The type and amount of these antioxidants are appropriately selected depending on conditions such as compatibility with the filler, intended molding workability, and resin storage stability. The amount of use (content) is usually 100 to 100 ppm (0 to 001 to 1 part by weight) based on 100 parts by weight of the component (a).

Examples of the processing stabilizer include phosphorus-based processing stabilizers such as tris (2,4-di (t-butyl) phenyl) phosphite, and 5,7-di (t-butyl) -3— (3,4- Lactone-based processing stabilizers such as dimethylphenyl) -3H-benzofuran-1-one, 2,5,7,8-tetrametheryl-2 (4 ', 8', 12'-trimethyltridecyl ) Chroman-6-ol and other bismuth E-based processing stabilizers.

Examples of the adhesion-imparting agent include a silane-based coupling agent. As the silane coupling agent, the formula YSiX ³ (Y is a monovalent group having a functional group and binding to Si, and X ³ is a monovalent group having a hydrolyzing property and binding to Si) is used as the silane coupling agent. It is represented by Examples of the functional group in Y include vinyl, amino, epoxy, black, mercapto, methacryloxy, cyano, olebamate, pyridine, sulfonyl azide, urea, styryl, chloromethyl, and ammonium. There are groups such as salt and alcohol. It is a X ^3, for example black hole, main butoxy, E butoxy, there are main Tokishe butoxy and the like. Specific examples include vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, Ύ- (2-aminoaminoethyl) -aminoprobi-trimethoxysilane, and alpha-trimethoxysilane. Mercaptopropyl trimethoxysilane, agglutoxypropyl trimethyoxysilane, acrylonitrile Cyprovir trimethoxysilane, N, N-dimethylaminophenol triethoxysilane, mercaptoethyl triethoxysilane, methacryloxyshethyl dimethyl (3-trimethoxysilyl lip pill) ammonium chloride , 3-(N-styrylmethyl-2-aminoaminoethyl) propyl trimethoxysilane hydrochloride and the like, and these can be used as a mixture. Examples of polymer-type alkoxy-modified silane coupling agents include MAC-2101 and FZ-3778 (trade name, manufactured by Nippon Tunica). These may be used alone or in combination with the silane coupling agent. It can also be used. The amount (content) of the silane-based coupling agent is usually 0.001 to 5 parts by weight based on 100 parts by weight of the component (a).

Hexabromobenzene, tetrabromobisphenol A, decabromodiphenyl oxide, tribromophenol, dibromophenyl glycidyl ether, cyclopentene cyclohexane, and hexanoic acid are flame retardants. Halogen compounds such as derivatives are used alone or in combination of two or more. In addition, phosphoric acid compounds such as triphosphate (dichloropropyl), triphosphate (dibromopropyl), and boric acid compounds can also be used. Further, examples of the auxiliary flame retardant include antimony trioxide, iron oxide, aluminum hydride, and the like. When these are used in combination with the flame retardant, the flame retardant effect is further enhanced. The amount (content) of the halogen-based flame retardant is usually 1 to 50 parts by weight based on 100 parts by weight of the component (a), and the auxiliary flame retardant such as antimony trioxide is usually 1 to 50 parts by weight. It is 15 parts by weight. Hydrates such as aluminum hydroxide and magnesium hydroxide can also be used for flame retardancy. The amount (content) of these components is 100 parts by weight of the component (a). On the other hand, it is usually 10 to 300 parts by weight.

Further, an organic peroxide can be added. Organic peroxides include, for example, cumene hydroperoxide, t-butylperoxy-12-ethylhexanate, methylethylketone peroxyside, benzoyl peroxide, acetylacetonperoxide, bis-14- (t-butyl) cyclo, and the like. Known ones such as hexanedicarbonate and 2,5-dimethyl-2,5-bis (t-butylvinyloxy) hexine-13 may be mentioned, and two or more of these may be used in combination. The addition amount is usually 0.1 to 10 parts by weight based on 100 parts by weight of the component (a).

In addition, in order to improve the wettability between the metathesis-polymerizable cycloolefin compound and / or its polymer (component a) and the filler, a wetting agent or a dispersant (for example, BYK series manufactured by BYK Etc.) can be contained. Further, in order to improve molding workability, a release agent such as a silicon-based oil / zinc stearate can be contained.

The resin composition of the present invention comprises a metathesis-polymerizable cycloolefin-based compound, which is dissolved by adding a methyl-thesis polymerization catalyst of the formula (A) to at least one selected from a filler, a reinforcing material, and an additive. Is obtained by adding the third component (component c). At this time, the temperature at which the catalyst is added to and dissolved in the cycloolefin-based compound and the temperature at which the third component is added are generally 0 to 70, preferably room temperature to 50.

The resin composition of the present invention is cured by heating to obtain a molded product. The heat curing operation may be one-stage heating, two-stage heating, or multi-stage heating. When using one-step heating, the temperature is usually 0 to 250, preferably 20 to 200. In the case of two-stage heating, the temperature of the first stage is usually 0 to 150, preferably 10 to: L 0, and the temperature of the second stage is usually 20 to 200, preferably 30 to: L80 :. 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 50 hours.

In order to obtain a molded product, for example, a laminate molding method such as a hand lay-up spray-up, a press molding method, a filament winding method, an injection molding method, a centrifugal molding method, a vacuum or pressure bag method, and a continuous molding method. Known methods such as a pultrusion molding method, an injection molding method, an RTM (resin transfer molding) molding method, a dive, an impregnation molding method, and a transfer molding method can be used.

In addition, the resulting molded product (cured product) has excellent mechanical properties, electrical properties, and boiling resistance.

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

(Preparation of DCPD resin solution)

10 parts by weight of tricyclopentene (to be referred to as TCPD) was added to 90 parts by weight of dicyclopentene (to be referred to as DCPD) having a purity of about 98% by weight to prepare a DCPD resin solution.

(Preparation of test piece)

The Ru carbene catalyst represented by the formula (1) was added to the DCPD resin solution in the room 5 and stirred for 5 minutes to completely dissolve the catalyst. In the case of a formulation that adds a filler, the resin solution containing this catalyst is added. Then, a filler was added, and the mixture was stirred for 5 minutes using a stirrer. This resin solution (that is, the resin composition with the composition shown in Table 3) was cast using two iron plates (300 mm X 300 mm X 6 mm) with a release agent and a 5 mm spacer. Injected into mold. Table 1 shows the fillers and reinforcing materials used. In addition, the fiber reinforced test specimen was hand-lay-up molded on a glass plate. Each was left at room temperature for 1 hour and then heated according to the prescribed curing conditions shown in Table 2 to obtain a cured product. table 1

Symbol Filler Reinforcement

A Aluminum hydroxide

(Sumitomo Chemical C-308)

-Saying, 'Rika

B (Tokai Mineral SS-100) Glass mat

C (MC-450N manufactured by Nitto Boseki)

Table 2

Symbol Initial cure Post cure

I 35 ° (:, 3 hours 125 ° (:, 3 hours

II 30 ° C, 3 hours 100 ° C, 3 hours III 35 ° C, 3 hours 80 ° C, 3 hours

Comparative Example 1>

In a 2-liter, four-necked flask equipped with a stirrer, condenser, nitrogen gas inlet tube and thermometer, 380 parts of propylene glycol, 624 parts of neopentyl glycol, 744 parts of isofluoric acid Then, the temperature was increased to 150 in 1 hour using a mantle heater while slowly flowing nitrogen gas, and further increased to 220 in 6 hours. The mixture was kept at that temperature for 5 hours to obtain an intermediate having an acid value of 8. After cooling, 539 parts of maleic anhydride was added thereto, and the temperature was raised to 150 over 1 hour, and further raised to 210 over 4 hours. The reaction proceeded while keeping the temperature at that temperature, and an unsaturated polyester having an acid value of 25 was obtained. A styrene monomer in which 0.01% by weight of hydroquinone was dissolved was dissolved so as to have an unsaturated polyester content of 60% by weight, and a 6% by weight solution of cobalt naphthenate was used as an accelerator. 0.5 parts by weight added, the viscosity at 25 promotes 0.4 Pa's An unsaturated polyester resin solution containing the agent was used.

In the same D CPD resin solution as in the example, getyl aluminum chloride was adjusted to 40 mmol / L, n-propyl alcohol was adjusted to 52 mmol / L, and silicon tetrachloride was adjusted to 20 mmol / L. Each solution was added in a dry box purged with nitrogen as described above. Similarly to the solution A, a solution B was prepared by adding tridecylammonium molybdate to the D CPD resin solution at a concentration of 10 mmol / L. The solution A and the solution B were mixed in an equal amount in a nitrogen-purged dry box, and poured into a mold at 20 ° C for 20 minutes to prepare a casting.

In the same manner as in Comparative Examples 2 and 3, D CPD-A solution and B solution were prepared, and mixed and cast into a mold in a room (in the air) to form a cured product. Evaluation of cured products>

The evaluation method of the obtained cured product is as follows. a. Mechanical properties

It was measured by a bending test (based on JIS-K-7203).

Test piece shape: 120mm X 12mm X 5mm

Test speed: δπιπιΖmin

Test span: 80mm

Number of tests: n = 5 b. Degree of cure

Using TG-DTA (thermal balance analyzer) manufactured by Vacuum Riko, the temperature was raised from room temperature to 600 at 10 minutes in Z, and the heating loss of 400 was measured. The degree of cure of the sample was calculated.

Degree of cure (%) =

Specimen weight at 400 ( _g ) / specimen weight at room temperature (g) c. Glass transition temperature

The glass transition temperature was measured using a DSC-7 model manufactured by PerkinElmer. d. Boiling resistance

The cured product of the above shape was immersed in hot water at about 95 for 300 hours, and the bending strength of the test piece after the boiling test was measured in the same manner as in the above bending test, and the bending strength was maintained. The rate was calculated by the following formula.

Flexural strength retention (%) =

(Bending strength before boiling test No. Bending strength before boiling test) X 100 e. Electrical characteristics

The electrical characteristics of the castings were measured for dielectric loss tangent (tan 5) using an LCR meter HP4275A manufactured by Hewlett-Packard Japan. The test was performed at a temperature of 25, a humidity of 60%, and a frequency of 10 kHz. Table 3 shows the results of Examples and Comparative Examples. The resin composition of the present invention using a specific polymerization catalyst contains a filler, and even when a cured product is prepared in the air, the degree of curing of the obtained cured product is high, and various characteristics are also obtained by conventional metathesis polymerization. It was better than cured products or unsaturated polyester resin cured products. In Table 3, MEKPO represents methylethylketone peroxyside. Table 3 t

*: Made by Wako Pure Chemical Industries, special reagent

INDUSTRIAL APPLICABILITY As described above, the use of the resin composition of the present invention enables general-purpose molding of cycloolefin-based compounds in a normal working environment without eliminating contamination of atmospheric water or oxygen. A molded product can be manufactured by applying a method (not only a closed mold molding method but also various open-mold molding methods).

Further, the cured product produced by the production method of the present invention is used in applications requiring water resistance, tough mechanical properties, excellent electrical properties, etc., for example, for electronic and electrical applications such as coils, wiring boards, and semiconductors. It can be used as an insulation material, a purification material, a bathtub, a wall panel, a molding material for housing equipment such as a pleasure port, and an industrial material such as a corrugated sheet and a pipe.

Claims

The scope of the claims

1. (a) a methesis-polymerizable cycloolefin compound; (b) a metathesis polymerization catalyst represented by the following formula (A):

R

/

M = C R "

(A)

X L C = C

H R

(M represents ruthenium or osmium,

X ¹ and X ² each independently represent an anionic ligand,

L ¹ and L ² each independently represent a neutral electron donating group,

R ¹ and R ² are each independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group, a carboxy group having 1 to 18 carbon atoms. Rate group, alkoxy group having 1 to 18 carbon atoms, alkenyloxy group having 2 to 18 carbon atoms, alkynyloxy group, aryloxy group having 2 to 18 carbon atoms, alkoxycarbonyl having 2 to 18 carbon atoms Group, an alkylthio group having 1 to 18 carbon atoms, an alkylsulfonyl group having 1 to 18 carbon atoms or an alkylsulfinyl group having 1 to 18 carbon atoms, and R ³ is hydrogen, aryl group or 1 to 18 carbon atoms. It represents 18 alkyl groups. ), And (c) at least one third component selected from fillers, reinforcements and additives;

A resin composition comprising:

2. Component (b) is contained in an amount of 0.001 to 20 parts by weight based on 100 parts by weight of the component (a),

2. The resin composition according to claim 1, wherein the resin composition contains 0.001 to 97% by weight of the component (c) based on the total amount of the component (a), the component (b), and the component (c). .

3. A method for producing a cured product, wherein the resin composition according to claim 1 or 2 is cured by heating.