WO2000050513A1 - Cycloolefin composition, process for producing the same, molding material, and molded object - Google Patents

Abstract

A cycloolefin composition which comprises a cycloolefin monomer capable of undergoing metathesis polymerization, a coupling agent which is a metallic coupling agent or a reactive polysiloxane, and a metathesis polymerization catalyst; a process for producing the composition; a molding material comprising the composition; and a molded object which is a cured article obtained from the molding material.

Description

 Description Cyclorefin composition and method for producing the same

 Molding material and molded body

TECHNICAL FIELD The present invention relates to a cycloolefin composition containing cycloolefins, a method for producing the same, a molding material using the composition, and a molded article obtained by curing the molding material.

BACKGROUND ART It has long been known that cycloolefins undergo ring-opening polymerization in a metathesis polymerization catalyst system. For example, in J. Am. Chem. Soc, 1960, Vol. 82, p. 2337, it is described that norbornene is subjected to ring-opening polymerization by a polymerization catalyst system, and Angew. Chem. Int. Edn., 1964, Vol. 3, p. 723 shows that cyclopentene is a

It is described that ring-opening polymerization is carried out by [MoCl ₅ / Al (C ₂ H ₅ ) ₃ ].

In addition, a method for producing a polymer by ring-opening polymerization polymerization of cycloolefins is also known. For example, Japanese Unexamined Patent Publication No. 50-130900 and Japanese Patent Publication No. A method for producing a ring-opening polymerized polymer by using a metathesis catalyst system comprising a halide such as stainless steel or molybdenum and an organic aluminum compound is disclosed.

 On the other hand, a method is also known in which a norbornene-type monomer such as dicyclopentenetricyclopentene is bulk-polymerized by reaction injection molding (RIM) to obtain a crosslinked polymer molded product. This reaction injection molding is a molding method in which two types of solutions that react with each other are impinged and mixed, and the mixed solution is immediately poured into a mold in a liquid state, and the mixture is subjected to open-cell-based sis polymerization.

 For example, JP-A-58-127728 and JP-A-58-12913 disclose a solution comprising a mixture of a catalyst component and a monomer of a mesothesis catalyst system. There is disclosed a method of obtaining a crosslinked polymer molded product by reaction injection molding of A with a solution B comprising a mixture of an activator of a monomeric catalyst system and a monomer.

 Japanese Patent Application Laid-Open No. 59-51911 discloses a catalyst component selected from an organic ammonium salt of tungsten and molybdenum, and a catalyst component selected from an alkoxyalkylaluminum halide and an aryloxyaluminum halide. A method for producing a crosslinked polymer molded product by reaction injection molding of a norbornene-type monomer using a catalyst catalyst system combined with a selected activator is disclosed.

Also, Japanese Patent Application Laid-Open No. Hei 3-250949 discloses that a catalyst component selected from tungsten hexachloride and tungsten tetrachloride, and an activity selected from getylaluminum chloride and ethylethyl dichloride. A method for producing a dicyclopentene polymer crosslinked by a reaction injection molding method using a reaction catalyst in combination with an agent is disclosed. It has been found that in these metathesis catalyst systems, the catalyst component is activated by an activator and causes the norbornene-type monomer to undergo polymerization by polymerization. In addition, it has been found that in the catalyst system for catalyst synthesis, the catalyst component is activated by a cocatalyst (activator) component to cause ring-opening polymerisation of norbornene-type cycloolefins.

 It is known that the cured product (that is, a polymer of cycloolefin) thus obtained is generally excellent in mechanical properties, electrical properties, water resistance and the like. For example, a bending test shows a yield phenomenon, has a very large deflection rate, and is tougher than other thermosetting resins such as epoxy resins and unsaturated polyester resins.

 However, in the cycloolefin composition, when a filler is added, the viscosity of the compound increases significantly, and the workability deteriorates. For this reason, it has conventionally been considered desirable to add a force-reducing agent in order to lower the viscosity when using a filler <see, for example, Japanese Patent Application Laid-Open No. H08-185855). No. 8 discloses a norbornene-based silane coupling agent, and Japanese Patent Application Laid-Open No. H02-2767682 discloses an aryl-based silane coupling agent and a vinyl-based silane coupling agent. In Japanese Patent Application Laid-Open No. 9-183833, a general silane coupling agent is disclosed.

However, when a silane coupling agent is used, the elasticity of the polymer increases due to the adhesion between the resin and the filler, and the deflection during the bending test also decreases. However, there is a problem that the toughness, which is one of the features of the cycloolefin composition, is lost. DISCLOSURE OF THE INVENTION The present invention provides a cycloolefin composition excellent in workability and mechanical properties even when a filler is used, a method for producing the composition, a molding material, and a molded article. Aim.

 In order to achieve this object, the present inventors have studied various types of coupling agents, and as a result, by using a specific coupling agent, the toughness of the cycloolefins and the composition have been improved. The present inventors have found that a large amount of filler can be added while maintaining workability, and the present invention has been accomplished. That is, in the present invention, a cycloolefin composition containing a cycloolefin monomer capable of polymerizing a polymer, a coupling agent, and a polymerizing polymerization catalyst is used as the coupling agent. And a metal-containing coupling agent or a reactive polysiloxane. The cycloolefin composition of the present invention can include a filler.

 Further, the present invention provides a method for producing the composition of the present invention, a molding material containing the composition, and a molded product that is a cured product thereof.

The metal-containing coupling agent quickly reacts with cycloolefins and the filler, and can improve workability while maintaining mechanical properties. The metal-containing coupling agent used in the present invention is different from conventional silane coupling agents, and is also effective for fillers having no hydroxyl group such as calcium carbonate. In addition, if the heat treatment time for reacting the coupling agent with the filler is short, it is necessary. There is also an advantage.

 In addition, since reactive polysiloxane can absorb the distortion of both phases of the resin and the filler, it is necessary to maintain the toughness of the polymer and maintain other properties equal to or higher than those of the conventional technology. It can be. Since the reactive polysiloxane used in the present invention is excellent in adhesiveness, it is possible to avoid a decrease in water resistance and electrical insulation due to an interfacial peeling phenomenon between the filler and the resin, which is desirable.

BEST MODE FOR CARRYING OUT THE INVENTION

A. Cyclorefin monomers

 The cycloolefin monomer used in the present invention may be any monomer as long as it is useful in metathesis polymerization. Of these, substituted or unsubstituted norbornene-type cycloolefins such as norbornene, dicyclopentene, and dihydroxycyclopentene are preferably used.

 Norbornene-type cycloolefins include:

 Bicyclic norbornenes such as norbornene, methylnorbornene, dimethylnorbornene, ethyl norbornene, ethylidenyl norbornene, and butyl norbornene;

Tricyclic norbornenes such as dicyclopentene digen (a dimer of cyclopentene digen), dihydroxycyclopentene, methyldicyclopentene, and dimethyldicyclopentene, tetracyclododecene, methyltetracyclododecene, dimethylcyclotetrade Tetracyclic norbornenes such as radodecene; and Norbornene with five or more rings, such as tricyclopentene (trimer of cyclopentene) and tetracyclene (trimer of cyclopentane). In addition, cyclobutene, cyclopentene, cyclooctene, cyclooctene, cyclotriene, cyclododecatrien, and the like can also be used. Further, a dicyclopentene-based petroleum resin obtained by thermal polymerization and cationic polymerization of dicyclopentene can also be used. These cycloolefins can be used alone or in combination of two or more.

 In addition, a compound having two or more norbornene groups, for example, norbornadiene, tetracyclododecadiene, a symmetric tricyclopentadiene or the like can also be used as a polyfunctional crosslinking agent. Of the above cycloolefins, dicyclopentene, methyltetracyclododecene, ethylidenyl norbornene, tricyclopentene, and tetracyclopentene are preferred because of their availability, economy, etc. Therefore, dicyclopentene is particularly preferred.

The usual commercially available dicyclopentenes are vinyl norbornene, tetrahydroidene, methylvinylnorpolene, methyltetrahydroidene, methyldicyclopentane, dimethyldicyclopentane, and methyldicyclopentane. It may contain as an impurity impurities such as cyclopentene, and dicyclopentene of various purity is commercially available. The dicyclopentene used in the present invention varies depending on the intended use of the obtained polymer, but usually has a purity of at least 80%, preferably has a purity of at least 90%. Is used. By using heat beforehand, a part of dicyclopentene can be converted to cyclopentene oligomer, such as tricyclopentene and tetracyclopentene, by using heat treatment before using it. In addition, it is possible to isomerize vinyl norbornene / methylvinylnorbornene, which is an impurity, to tetrahydroidone / methyltetrahydroidene. Such preliminary heat treatment is usually performed at 120 to 250 for about 0.5 to 10 hours.

 An antioxidant can be added to the cycloolefins used in the present invention as needed. Note that ordinary commercially available dicyclopentene already contains antioxidants such as 2,6-di (t-butyl) -14-methylphenol and 41-t-butyl catechol. In use, the contained antioxidant may be removed or newly added.

The antioxidant to be used is not particularly limited as long as it has an antioxidant ability, but a preferable example is a hindered phenol-based antioxidant. For example, 2,6-di (t-butyl) -14-methylphenol, 2,6-di (t-butyl) -14-ethylphenol, stearyl-5- {3,5-di (t-butyl) ) 14-Hydroxyphenyl} propionate, Tetrakis- [methylene-13- {3 ', 5,1-di (t-butyl) -14,1-hydroxyphenyl} propionate] 2,2'-Methylenebis (4-ethyl-6-t-butylphenol), 4,4,1-methylenebis {2,6-di (t-butyl) phenol] 1,3,5-trimethyl 1,2,4,6-tris {3,5-di (t-butyl) -14-hydroxybenzyl} benzene, 1,3 5 — Tris {3,, 5, di- (t-butyl) -14,1-hydroxybenzyl} — S—triazine-2,4,6- (1H, 3H, 5H) trion Is mentioned. In addition, an amine-based, zeolite-based, and phosphorus-based antioxidant and a thermal degradation inhibitor can also be used. These may be used alone or in combination of two or more. The amount of the antioxidant to be added is usually 10 to 10 and OOO ppm relative to cycloolefins. In addition, an ultraviolet absorber, a light stabilizer and the like may be used in combination.

 In order to adjust the polymerization reaction, triphenylphosphine, tricyclohexylphosphine, tricyclopentylphosphine, tributylphosphine, tributylphosphine and tributylphosphine are used. A reaction modifier such as isopropyl phosphine may be added. The appropriate amount of the reaction modifier is usually from 0.001 to 10 parts by weight based on 100 parts by weight of the raw material monomer.

 B. Filler

 The compositions and molding materials of the present invention can include fillers. Examples of the filler suitable for the present invention include oxide-based, hydroxide-based, carbonate-based, sulfate-based, and silicate-based fillers. As the filler, one type may be used alone, or two or more types may be used in combination. The shape can be powdery, fibrous, plate-like or the like, and is not particularly limited.

 Examples of the oxide-based filler include silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, and the like. .

Hydroxide-based fillers include calcium hydroxide and magnesium hydroxide. Gnesium, aluminum hydroxide, basic magnesium carbonate, and the like.

 Examples of the carbonate-based filler include calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, and nodal mouth talcite.

 Examples of the sulfate-based filler include calcium sulfate, barium sulfate, and gypsum fiber.

 Examples of the silicate-based filler include calcium silicate (wollastonite, zonolite), talc, creed, kaolin, my strength, montmorillonite, bentonite, activated clay, Sepiolite, imogolite, cericite, glass powder, glass fiber, glass beads, glass balloon, shirasu balloon, etc. are used. As the nitride-based filler, aluminum nitride, boron nitride. Element.

 Examples of the carbon-based filler include carbon black, graphite, carbon fiber, carbon balloon, charcoal powder, and expanded graphite.

 Other fillers include various metal powders, metal fibers, viscous materials such as potassium titanate, powders of thermoplastic resins and thermosetting resins, silica sand, crushed stone, and gravel. Natural products.

Of these fillers, glass, silica, alumina, magnesium hydroxide, aluminum hydroxide and silica sand are particularly preferred. The filler is added in an amount of 1 to 99% by weight, preferably 5 to 95% by weight, more preferably 30 to 90% by weight based on the total weight of the composition. I do. c. Coupling agent

 The composition and the molding material of the present invention contain, as a coupling agent, at least one of a metal-containing coupling agent and a reactive polysiloxane. One of these may be used alone, or both may be used in combination.

 The amount of the coupling agent used in the present invention is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the filler. New The reason is that if the amount used is smaller than this ratio, the wettability between the filler and the resin becomes insufficient, and the effect of improving the mechanical properties etc. of the composite material may not be sufficiently obtained. It is. Further, even if the amount used is larger than this ratio, the mechanical properties and water resistance are not further improved, which is not preferable from the viewpoint of economy.

 The sealing agent may be used for pre-treating the filler, or may be added when the resin material and the filler are mixed. When the filler is to be treated in advance, it can be carried out in the same manner as the conventional treatment method using a silane capping agent. For example, in the case of a powdered inorganic filler, a coupling agent is added directly or after diluting with a solvent, mixed with a stirrer such as a Henschel mixer or a super mixer, and then subjected to a heat treatment to cut the mixture. Sizing agent and inorganic filler may be reacted. The heat treatment is preferably performed at room temperature to 140 for 0.5 to 6 hours. In the case of a fibrous filler, the fibers may be immersed in a solution obtained by diluting a coupling agent and then treated under the same heating conditions.

In addition, when a capping agent is added at the time of mixing the resin material and the filler, for example, the capping agent may be added to the resin material or the filler. After the addition and dispersion in the resin, the resin material and the filler are mixed, and then, if necessary, the same heat treatment as in the case where the above-described filler is pretreated may be performed.

 (a) Metal-containing pressing agent

 The metal-containing coupling agent used in the present invention is a compound containing a metal atom in a molecule, and is used in a composite system of an inorganic material and an organic material or a composite system of different organic materials. A material that binds both to or improves affinity with chemical reactivity

As such a metal-containing coupling agent, generally, a metal having a hydrolyzable group bonded to a metal is used. Examples of the metal contained in the metal-containing coupling agent include titanium, aluminum, zirconium, iron, calcium, magnesium, and zinc, and titanium, aluminum, and zirconium are particularly preferred. The hydrolyzable group is not particularly limited, but is preferably an alkoxyl group. Examples of the titanic coupling agent suitable for the present invention include isoprovir triisostearoyl cyanate, Isoprovir tri-n-dodecylbenzenesulfonyl nitrate, isoprovir tris (dioctylpyrophosphate) titanate, tetrasilop-mouth pyrvis (dioctylphosphite) titanate, Tetraoctylbis (ditridecyl phosphite) titanate, tetra (2,2-diaryloxymethyl-1 1-butyl) bis (ditridecyl phosphite) titanate, bis (dithiol) Octylpyrophosphate) oxyacetate titanate, bis (dioctylbi-phosphate) ethylene titanate, isopropy Door Rioku Tano Iruchi evening Natick door, Lee Sopuro Pirujimetaku Li Roirui triisostearate Caroline, Isopropyrui Sostearoyl carbohydrate, Isoprovir tritium (dioctyl phosphate) titanate, Isopropyl triglyceride, Carbohydrate, Isopropyl Tri- (N-aminoethyl-amino-ethyl) titanate, Tetraisopropyl propyl titanate, Tetra normal butyl titanate, Butyl titanate dimer, Tetrakis (2-ethylhexyl) titanate, Tetrastearyl titanate, tetramethyl titanate, diethoxybis (acetyl acetate) titanium, diisopropylbis (acetyl acetate) titanium, diisopropoxybis (ethyl acetate acetate) titanium, isopropoxy (2 — Ethel I 1, 3 — Hexandiolat Titanium, di (2-ethylhexoxy) bis (2-ethyl-1,3, -hexanediolate) titanium, di (n-butoxy) bis (tritanoylamine) titanium, tetracetylacetone Examples include titanium and hydroxybis (lactato) titan.

 Examples of the aluminum-based metal-containing coupling agent suitable for the present invention include acetoalkoxyaluminum diisopropylate and the like, and examples of the zirconium-based include zirconium acetylacetone and bisethylacetonate. Can be

 One of these may be used alone, or two or more thereof may be used in combination.

Of these metal-containing coupling agents, tetra (2,2-diaryloxymethyl-1-butyl) bis {di (tridecyl)} phosphite, bis (dioctylpyrrolate) Phosphate) Oxyacetate titanate, Isoprovirt® Lister mouth filter, and acetate alkoxy aluminum diisolate Profiles are particularly preferred. These are because they do not have an amino group or the like that inhibits the curing of the polymerization by polymerization, and have a high coupling effect.

 Further, in addition to the above-mentioned metal-containing coupling agent, another coupling agent such as a silane coupling agent may be used in combination. In particular, when a titanium compound is used as the metal-containing coupling agent, the titanium compound also acts as a catalyst for the silanol condensation reaction of the silane coupling agent. Are preferably used in the present invention.

 Examples of silane coupling agents that can be used in combination include, for example, vinylsilane compounds (vinyltrimethoxysilane, vinyltriethoxysilane, etc.), epoxysilane compounds (5- (3,4-epoxycyclohexyl) ethyl) Limethoxysilane, α-glycidoxypropyl trimethoxysilane, etc.), aminosilane compounds (α-aminopropyl triethoxysilane, N- (aminoethyl) -aminopropylmethyldimethylmethoxysilane, etc.), Known silane coupling agents such as acryloylsilane compounds (such as acryloxyprovir trimethoxysilane) or alkylsilane compounds (such as methyltrimethoxysilane and methyltriethoxysilane); , Dimethoxydimethylsilane, Alkoxysilanes such as ethoxy dimethyl silane, tetramethoxy silane, and tetra ethoxy silane can be used.

(b) Reactive polysiloxane

The reactive polysiloxane used in the present invention is not particularly limited as long as it has a hydrolyzable group bonded to a silicon atom. Examples of the hydrolyzable group include a hydrogen atom and an alkoxy group. Groups, an amino group, an amino group, an aminooxy group, a mercapto group, an alkenyloxy group, etc., and an alkoxyl group is preferable.

 The reactive polysaccharides suitable for the present invention are represented by the following general formula

Compounds represented by any of (1) to (3) are mentioned.

R R R R R

M ^1- (SiO) _a — (SiO) _b — (SiO) _d — (SiO) _e — Si— M ¹ ··· (1)

I I I I I

R Y Z Q R

R R R R

_{^{M 2 - (SiO) f -}} (SiO) g - (SiO) h - Si - M; (2) RYZR

R R R R

M ³ — Si— 0— (SiO) j— (SiO) _k — Si— M (3) RRZR where each R is independently selected from a hydrogen atom, a monovalent hydrocarbon group or an alkyl halide. Represents a group. R in one molecule may be the same, or may be partially or entirely different from each other. Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a dodecyl group, a phenyl group and a phenethyl group. In addition, examples of the halogenated alkyl group include a trifluoropropyl group and a chloropropyl group. R is a monovalent hydrocarbon group or a halogenated alkyl group. A kill group is preferred, especially a methyl group and a fluoroalkyl group.

 Y represents an organic reactive functional group represented by the following general formula (4).

-R ¹ -X… (4)

Here, R ¹ represents a direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and X represents a functional group having organic reactivity. In addition, as the R ^1, for example, _{- CH 2 -, -CH 2 CH} 2 -, -CH 2 CH 2 CH 2 -,

_{-CH (CH 3) CH 2 -} , - (CH 2) 4 -, - (CH 2) 6 -, - (CH 2) 8 -,

_{-CH 2 CH 2 C 6 H 4} -, - (CH 2) 12 -ヽ- (CH _{2) 16} -, and the like, are rather to preferred are pro-pin les down groups. X is, for example, an epoxy group, an amino group, a hydroxyl group, a carboxyl group, an acyl group, a mercapto group, a methyl chloride group, an isocyanate group, a ureido group, a vinyl group, or an amide. Group, imido group, imino group, aldehyde group, nitro group, nitrile group, oxime group, azo group and hydrazone group. Specific examples of the Y group include-(CH ₂ ) ₃ OH,-(CH ₂ ) ₃ SH,

-(CH ₂ ) ₃ NH ₂ ,-(CH ₂ ) ₇ COOH, and the like, but are not limited thereto.

 Z represents a hydrolyzable group or a condensable silylalkyl group represented by the following general formula (5).

-R ² -S i-(OR ⁴ ) _r

 I… (5)

(R ³ ) 3-r

Here, R ² represents an alkylene group having 2 to 5 carbon atoms, R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms independently selected from each other, and r represents 2 Or 3, but 2 is preferred in terms of reactivity. R ² is alkylene down group having a carbon number of 2-5, for example, _{- CH 2 CH 2 -, -CH} 2 CH 2 CH 2 -, -CH (CH 3) CH 2 -, - (CH 2) 4 -, -(CH ₂ ) _{5-and the} like, and preferably an ethylene group. R ³ and R ⁴ are independently selected from a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and include, for example, a methyl group, an ethyl group, a propyl group and a butyl group. R ³ is preferably a methyl group, and R ⁴ is preferably a methyl group or an ethyl group.

Specific examples of the Z group include -CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,

_{-CH 2 CH 2 Si (OC 2} H 5) 3, -CH 2 CH 2 Si (CH 3) (OCH 3) 2,

-CH ₂ CH ₂ Si [OCH (CH ₃ ) ₂ ] I-(CH ₂ ) ₃ Si (CH ₃ ) (OC ₂ H ₅ ) I-(CH ₂ ) ₅ Si (C ₂ H ₅ ) (OC ₂ H ₅ ) ₂ etc. can be mentioned, but it is not limited to these.

 Q represents a polyoxyalkylene group represented by the following general formula (6).

-(CH ₂ ) _p -0- (C ₂ H ₄₀ ) _m- (C ₃ H ₆₀ ) _n -R ⁵ (6) where, R ⁵ is a hydrogen atom, an acyl group or a monovalent carbon Represents a hydrogen group, P is 0 or a positive integer, m and n are 0 or a positive integer of 150 or less, but 2 is preferred. Here, m + n is an integer from 1 to 150. Examples of the acyl group applicable as R ⁵ include, for example, an acetyl group and a propionyl group. Further, examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group and a vinyl group.

M ¹ independently represents a group selected from R, Y, 、 and Q described above. M ² represents a group selected from the R, Y and Z independently of one another. M ³ represents a group selected from R and Y independently of each other. The two M ¹ ! ^! ^{3 in} one molecule may be the same or different from each other. a is an integer from 0 to 500, b is an integer from 0 to 200, d is an integer from 0 to 200, and e is an integer from 0 to 200. . However, when b is 0, M ¹ is Y, and both d and e are integers of 1 or more. When d is 0, M ¹ is Z, and b and e are both integers of 1 or more. When e is 0, M ¹ is Q, and b and d are each an integer of 1 or more.

f is an integer from 0 to 500, g is an integer from 0 to 200, and h is an integer from 0 to 200. However, when g is 0, M ² is Y, and h is an integer of 1 or more. When h is 0, M ² is Z and f is an integer of 1 or more.

j is an integer of 0 to 500, and k is an integer of 0 to 500. However, when k is 0, M ³ is Z.

 In addition, as the compound of the general formula (1), for example, Y is an epoxy group, Z is a condensable silylalkyl group having an alkoxyl group bonded to silicon, and Q is a polyether group. The base compound is sold by Nippon Tunicer Co., Ltd. as MA C—201.

 D. Methesis polymerization catalyst

 The polymerization catalyst used in the present invention can be applied as long as it is a known catalyst system for polymerization polymerization of cycloolefin-based compounds, for example, a two-component catalyst or a two-component catalyst. One-component catalysts are mentioned, but there is no particular limitation. However, a one-component metal carbene catalyst is preferred because of its good stability in air.

Usually, the amount of the catalyst added is 0.001 to 5 parts by weight with respect to 100 parts by weight of the total of cycloolefin monomers. From the economic point of view, it is preferable to use 0.01 to 1 part by weight.

A two-component metathesis polymerization catalyst is a catalyst system that combines a catalyst component and an activator. Examples of the two-component metathesis polymerization catalyst used in the present invention include transition metals such as titanium, vanadium, molybdenum, tungsten, rhenium, iridium, ruthenium, and osmium. Complex metal halides, metallocene or zigzag coordination catalysts, and the like.

Specifically, tungsten compounds, such as tungsten hexachloride, tungsten tetrachloride, tungsten oxide, tungsten oxide, and tridecyl ammonium hydroxide, molybdenum pentachloride, molybdenum oxytrichloride, Molybdenum compounds such as molybdenum oxide and tridecyl ammonium molybdate, tantalum compounds such as tantalum pentachloride, and [(cyclohexyl) ₃ P] ₂ RuCl ₂ , [(Fe Ruthenium compounds such as ( ₂ ) ₃ P] ₃ RuCl ₂ , (cyclohexyl) ₃ P (p-simene) RuCl ₂ , and [(phenyl) ₃ P] ₃ (CO) RuH ₂ A known co-catalyst (activator) is used in combination with the two-component polymerization catalyst system, if necessary. Specific examples thereof include alkylaluminum halides, alkoxyalkylaluminum dimethylhalides, aryloxyalkylaluminum halides and organic tin compounds.

The one-component type metathesis polymerization catalyst is different from the two-component type catalyst system in that the cycloolefin compound is easily reacted with water in the air or water absorbed on the solid surface without losing its catalytic activity. The ring-opening polymerization can be carried out with Specifically, such a one-component polymerization catalyst has a large steric hindrance by using a metal carbene structure of ruthenium or osmium as a central skeleton. A metal carbene-type coordination catalyst stabilized with respect to moisture by taking a structure in which a ligand is coordinated to a central metal is cited.

 Preferred examples of the ruthenium or osmium metal carbene-type coordination catalyst include compounds represented by any of the following general formulas (7) to (9). Among them, the compound represented by the general formula (9) is particularly preferable in terms of high catalytic activity, high synthesis yield, and economic efficiency.

X ¹ LQ

M = C (7)

X 'L Q

X ¹ LQ

M = C = C (8)

X L Q

X ¹ LR

M = C R

 (9)

 X L C = C

H R Here, M represents ruthenium or osmium.

X ¹ and X ^{2 each} independently represent an anionic ligand. An anionic ligand is an atom or group of atoms that has a negative charge when decoordinated to the central metal. This anio P

Hydrogen, halogen, CF ₃ C 0 ₂ , CH ₃ C 0 ₂ , CFH ₂ C 0 ₂ , (CH ₃ ) ₃ CO, (CF ₃ ) ₂ (CH ₃ ) CO,

_{(CF 3) (CH 3)} 2 CO, alkyl group of 1 to five carbon atoms, an alkoxyl group having 1 to five carbon atoms, phenylalanine group, full enol hexyl group, tosyl group, main sill group, Application Benefits Furuorometa Nsuruhone DOO Group. It is particularly preferred that both X ¹ and X ² are both halogen (particularly chlorine). '

L ¹ and L ^{2 each} represent a neutral ligand independently selected.A neutral ligand is an atom or atom having a neutral charge when decoordinated to the central metal. It is an atomic group. Examples of such a group include PR ⁸ R ⁹ R ¹⁰ (where R ⁸ is a secondary alkyl group or a cycloalkyl group, and R ⁹ and R ^{1 Q} are an aryl group, a carbon number. A phosphine-based electron donor represented by the following formulas: 1 to 10 primary alkyl groups and secondary alkyl groups, and cycloalkyl groups. L ¹ and L ^2, both both P (cyclohexyl consequent b) _3, P (consequent Ropenchiru) _3, or P (i Sopuro pill) ₃ Dearuko and particularly preferred arbitrariness.

 Examples of the ligand include pyridine, p-fluoropyridine, imidazolylidene, and the like. As the imidazolylidene compound, a heterocyclic compound represented by the following general formula (10) or (11) is preferable. Among these, it is particularly preferable to use the compound represented by the formula (11) as the ligand.

R "One N f = \ N— R 12

(1 0) ヽ P TJP00 / 01113

twenty one

(1 1)

Here, R ¹¹ and R ¹² are independently selected from an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and a C 2 to 20 carbon atom. Alkynyl group, cycloalkyl group and aryl group. R ¹¹ and R ¹² may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, or an aryl group. May be substituted with a halogen, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, or a phenyl group. From the viewpoint of thermal stability, it is preferable that at ^{least one of} R ¹¹ and: R ¹² is a group represented by the following general formula (12).

In this formula (12), R ¹³ and R ¹⁴ are each hydrogen, an alkyl group having 1 to 3 carbon atoms or an alkoxyl group having 1 to 3 carbon atoms, and R ¹⁵ is hydrogen. , Alkyl, aryl, hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, a Min groups, amide groups, nitro groups, carboxylic acid groups, disulfide groups, carbonate groups, isocyanate groups, carboimido groups, carboalkoxy groups, hydroxyl groups, halogens, etc. is there.

Specific imidazolylidene that can be used as a ligand Examples of the compound include a carbene represented by the following structural formula (13) or (14). Of these, the imidazolylidene compound of the structural formula (13) is particularly preferred from the viewpoint of polymerization activity.

… ( 13 )

 Specific examples of the catalyst suitable for the present invention include the following structural formulas (15) to (17).

(16)

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

R ⁵ and R ⁶ are each independently selected from an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group, and a carbon atom having 1 carbon atom. ~ 18 carboxylate group, 1 ~ 18 carbon atom alkoxyl group, 2 ~ 18 carbon atom alkenyloxy group, 2 ~ 18 carbon atom alkynyloxy group, 2 ~ 18 carbon atom aryloxy group Group, an alkoxy group having 2 to 18 carbon atoms, an alkoxyl 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. R ⁷ represents hydrogen, an aryl group or an alkyl group having 1 to 18 carbon atoms.

Such a metal carbene compound can be obtained by a known synthesis method. For example, a method using propargyl chloride shown in Organometallics Vol. 16, No. 18, p. 3687 (1991) can be mentioned. An example of catalyst synthesis is shown below (see Literature: Organometallics Vol. 16 No. 18 No. 3867 (p. 1997)). Here, cy represents a cyclohexyl group.

 Synthesis example

In a 500 ml Fisher-Porter bottle, add cyclohexyl benzene dichloride (21 mmol), tricyclohexyl phosphine (42 mmol), and sodium hydroxide (7 mmol). 2 g) and 250 ml of sec-butanol, from which oxygen was removed, were heated at 90 ° C. under a hydrogen atmosphere of 20 OkPa. Pressurize several times until hydrogen absorption is completed, and continue stirring overnight. Cool to room temperature while applying hydrogen pressure to obtain a pale yellow precipitate. 30 ml of water was added, and the precipitate was filtered and dried in a stream of hydrogen to obtain Ru (H) ₂ (H ₂ ) ₂ (P (cy) ₃ ) ₂ (yield about 80%). Next, this Ru (H) ₂ (H ₂ ) 2 (P (cy) ₃ ) ₂ (1.5 mmol) is dissolved in 30 ml of dichloride and cooled to 130 ° C. . 3 — Chlorine 3 — Methyl 1 — Butyne (1.5 mmo 1) is added. The solution immediately turns reddish purple, and after reacting for 15 minutes, the cooling bath is removed, and degassed methanol (20 ml) is added, and purple crystals precipitate. After washing with methanol and drying, Ru carbene catalyst (Cl) ₂ (P (cy) ₃ ) ₂ Ru = CH—CH = C (CH ₃ ) ₂ is obtained (yield: 95%). E. Thermoplastic resin

 A thermoplastic resin can be added to the cycloolefin composition and the molding material of the present invention as needed, for example, for improving adhesiveness and reducing shrinkage.

The applicable thermoplastic resin is not particularly limited, and examples thereof include an olefin resin and a modified product thereof (modified olefin resin), a styrene resin and a modified product thereof (modified styrene resin), Aio Nomer resin, polymethyl methyl acrylate, polybutadiene, polyisoprene, polyurethane, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, fluororesin, polyamide, saturated polyester, Petroleum resin and the like.

F. Additive

 The cycloolefin composition and the molding material of the present invention include various substances such as thixotropic agents, coloring agents, defoaming agents, dispersing agents, antioxidants, and plasticizers for the purpose of improving physical properties, appearance, and molding workability. Additives can be contained.

 Examples of the thixotropic agent include inorganic modifying agents such as silica, asbestos powder, and fatty acid-treated carbonated calcium carbonate, organic bentonites, modified polyesterpolyol-type organic modifying agents, and colloid darcili. Mosquito, fatty acid amide wax, stearate amide and the like.

 Coloring agents include inorganic pigments such as titanium oxide, cobalt blue, cadmium oxide, molybdenum red, chromium oxide, and alumina white, black pigment, and aniline black. And organic pigments such as phthalocyanine, quinacridone and the like.

 As the defoaming agent, other commercially available products such as silicone oils and surfactants (for example, commercially available from Byk Chemie and Kusumoto Kasei) can be used.

G. Manufacturing method and molding method

The cycloolefin composition and the molding material of the present invention can be obtained by uniformly mixing the above-mentioned components at room temperature or under heating. If necessary, defoaming may be performed under reduced pressure. The cycloolefin composition or molding material of the present invention, casting, injection A known molding method such as molding, hollow molding, extrusion molding, compression molding, and rotational molding can be applied to form an arbitrary shape. During molding, heating may be performed as necessary.

 The molded article of the present invention can be used not only for electric and electronic components such as wiring boards and insulating materials, but also for building materials such as septic tanks, bathtubs, kitchen top plates, water storage tanks, wall panels, sewage tanks, water pipes, corrugated sheets, It can be applied to various plastic products such as toys, recreational goods such as plunger boats, and daily necessities such as bathroom supplies and kitchen supplies. Examples Hereinafter, the present invention will be described with reference to Examples. In the following Examples and Comparative Examples, “parts” means parts by weight unless otherwise specified. Dicyclopentene is abbreviated as DCPD. In each of the following examples and comparative examples, a female polymerization catalyst represented by the following chemical formula (15) was used.

(15)

A. Examples 1-3, Comparative Examples 1-6

In each of these examples, a DCPD resin solution as a cycloolefin composition was prepared using reactive polysiloxane as a coupling agent, a filler was added thereto, and a propeller blade was used. Then 4 The mixture was stirred at 00 rpm for 5 minutes to prepare a compound (ie, a composite material).

 The obtained compound was heated at 60 ° C for 4 hours, and then cooled to about 35 ° C for use. First, 0.10 parts of a methase polymerization catalyst was added to the compound and mixed, and then the compound was depressurized and defoamed to obtain a molding material as a cycloolefin composition. A test piece was molded using this molding material, and various characteristics were evaluated by the following methods.

 I. Bending characteristics

 (a) Test specimen preparation method

 The above molding material is cast into a mold capable of forming a flat plate with a thickness of 3 mm.Then, the mold is heated in an oven at 40 ° C for 5 hours and at 130 ° C for 2 hours to form a flat plate. A cured product was obtained.

 (b) Bending test

 A bending test piece having a width of 25 mm and a length of 80 mm was cut out from a flat plate, and a bending test (test speed: 2 mm / min) was performed in accordance with JISK7203. At this time, the bending deflection rate was obtained by the following equation.

Deflection rate (%) = 6 d V / L ²

 d Deflection at break (mm) v Specimen thickness (mm)

 L Distance between fulcrums (mm)

 II. Water resistance

 The retention was determined from the strength of the dielectric breakdown before and after the pleat cooker test (PCT).

 (a) Test specimen preparation method

Casting the above molding material into a mold that can make a flat plate with a thickness of 2 mm Thereafter, the mold was heated in an oven at 40 ° C. for 5 hours and at 130 ° C. for 2 hours to obtain a flat cured product.

 (b) Dielectric breakdown strength

 The measurement was performed according to JISK6911. The conditions of PCT were as follows: temperature: 121 ° C., pressure: 222 kPa, and time: 50 hours. Table 1 shows the evaluation results. As can be seen from the table, the molded articles obtained from the compounds of the respective examples using the reactive polysiloxane have a larger deflection rate and higher toughness than the respective comparative examples. Further, in each of the examples, there is no decrease in the dielectric breakdown strength after PCT and the water resistance is excellent.

 table 1

<Example 1>

100 parts of DCPD with a purity of about 98% was added to Sumireiza-BHT (trade name, manufactured by Sumitomo Chemical Co., Ltd., antioxidant) 2 parts, and triphenylphosphine (made by Wako Pure Chemical Industries, Ltd.) Reagent grade) 0.05 parts, FZ 3 7 7 8 (Nippon Rikiichi Co., Ltd., trade name, ethoxymethylhydroxide polysiloxane) 2.0 parts, OO / 01113

The dispersion was dispersed to prepare a D CPD resin solution. Thereafter, 150 parts of molten silica (average particle size 5 ^ m) was added and mixed to obtain a compound.

 <Example 2>

 Example 2 Example 1 was repeated except that 2.0 parts of MAC—2101 (trade name, manufactured by Nippon Tunica Co., Ltd., epoxy and polysiloxane having a condensable silylalkyl group) was used instead of FZ3778. A companion was obtained in the same manner.

<Example 3>

 Same as Example 1 except that 2.0 parts of polymer type silane coupling agent FZ 3704 (trade name, manufactured by Nippon Tunicer KK, polyethoxymethylsiloxane) was used instead of FZ 3778 Then the compound was obtained.

<Comparative Example 1>

 A DCPD resin solution was prepared by adding 2 parts of Sumilyzer-BHT and 0.06 parts of triphenylphosphine (special grade) to 100 parts of DCPD having a purity of about 98% and dispersing them. . Thereafter, a molten silica (manufactured by Tatsumori Co., Ltd., about 150 parts in average diameter) was added and mixed to obtain a compound.

<Comparative Example 2>

100 parts of DCPD with a purity of about 98%, 2 parts of Sumilyzer-BHT, 0.06 parts of triphenylphosphine (special grade), 0.6 parts of silane coupling agent A—171 (Nippon Tunicar) 2.0 parts of vinyl trimethoxysilane (trade name, manufactured by Co., Ltd.) were added and dispersed to prepare a DCPD resin solution. Thereafter, 150 parts of molten silica (average particle size of about 5 / m) was added and mixed to obtain a compound. <Comparative Example 3>

 As a silane coupling agent, use 2.0 parts of A-187 (trade name, manufactured by Nippon Rikiichi Co., Ltd., glycidoxypropyltrimethoxysilane) instead of A-171. A compound was obtained in the same manner as in Comparative Example 2 except for the above.

Comparative Example 4>

 Comparative Example 2 except that 2.0 parts of A—163 (trade name, manufactured by Nippon Tunicer Co., Ltd., methyltrimethoxysilane) was used instead of A—171 as the silane coupling agent. A compound was obtained in the same manner as described above.

<Comparative Example 5>

 A-137 (N-octyl triethoxysilane) (N-octyl triethoxysilane) was used in place of A-171 as the silane agent. A compound was obtained in the same manner as in Comparative Example 2.

Comparative Example 6>

 Comparative Example 2 except that 2.0 parts of A—153 (Nippon Rikiichi Co., Ltd., phenyl triethoxysilane) was used instead of A—171 as the silane coupling agent. A compound was obtained in the same manner as.

B. Example 4, Comparative Examples 7-8

In these examples and comparative examples, a DCPD resin solution was prepared using DCPD and cyclohexane as a cycloolefin monomer, a filler was added thereto, and the mixture was stirred and mixed in the same manner as in Example 1. Pounds were prepared. The obtained compound was heated at 60 ° C for 4 hours, and then cooled to about 35 ° C for use. First, 0.15 parts of a metathesis polymerization catalyst was added to this compound and mixed, and then the compound was depressurized and defoamed to obtain a molding material.

 A test piece was molded using the obtained molding material, and various characteristics were evaluated by the following methods. The method for preparing the test pieces and the method for evaluating various characteristics were the same as those in Examples 1 to 3 described above. Table 2 shows the evaluation results.

 Table 2

<Example 4>

 Same as in Example 1 except that 100 parts of DCPD was replaced with 50 parts of DCPD having a purity of about 98% and 50 parts of Cyclo-Yugen (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) Then we got the comp.

 <Comparative Example 7>

 A compound was obtained in the same manner as in Comparative Example 1, except that 100 parts of DCPD and 50 parts of cyclooctane (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) were used as the cycloolefin monomers. .

 <Comparative Example 8>

As a cycloolefin monomer, in addition to DCPD 100 parts, A compound was obtained in the same manner as in Comparative Example 2 except that 50 parts of cycloxene was used.

C. Examples 5 to: L0, Comparative Examples 9 to; L2

 In each of these examples, a DCPD resin solution was prepared using a metal-containing coupling agent as a coupling agent, a filler was added thereto, and the mixture was stirred and compounded as in Example 1. Was prepared.

 To this compound was added 0.12 parts of a polymerization catalyst, and after mixing, the compound was degassed under reduced pressure to obtain a molding material. A test piece was molded using the obtained molding material, and various characteristics were evaluated by the following methods. The method for preparing the test pieces and the method for evaluating the bending characteristics were the same as those in Examples 1 to 3 described above.

 In addition, the reactivity between the capping agent and the filler was evaluated based on the decrease in the viscosity of the compound. The viscosity was evaluated in accordance with JIS 6901 for the viscosity of the compound for 1 hour after preparation and the viscosity of the compound after standing at 35 ° C. for 20 hours. The measurement conditions were as follows: temperature: 35 ° C, viscometer: B L-type rotational viscometer, rotation speed: 60 rpm.

Table 3 shows the results of the evaluation. As can be seen from Table 3, the bending characteristics of the product containing the metal-containing coupling agent are superior to those of the product containing no metal-coupling agent, and are equivalent to those of the silane coupling agent. In addition, since the viscosity of the product containing the metal-containing coupling agent decreases faster than that of the product containing the silane-based coupling agent, it can be seen that the reaction between the coupling agent and the filler is faster. Table 3

<Example 5>

 As a coupling agent, instead of FZ3778, PLANK KR55 (trade name of Ajinomoto Co., Inc., a titanium-based coupling agent having an aryl group, tetra (2,2-dithiol) Melting using 1.5 parts of aryloxymethyl — 1 -butyl) bis {di (tridecyl)} phosphite titanate and bis (dioctylpyrophosphate) oxyacetate A compound was obtained in the same manner as in Example 1 except that the amount of silica added was 100 parts. <Example 6>

 In the same manner as in Example 5 except that 1.5 parts of Preacut AL-M (trade name, manufactured by Ajinomoto Co., Ltd., acetoxyalkoxyaluminum diisopropylate) was used instead of Preacut KR 55, I got the compound.

 <Example 7>

Olgatics ZC—570 instead of KR55 (Zirconium acetyl acetate bisacetyl acetate, trade name, manufactured by Matsumoto Pharmaceutical Co., Ltd.) A compound was obtained in the same manner as in Example 5 except that 1.0 part was used.

<Example 8>

 As a coupling agent, instead of FZ3778, use Plankt KR55 (0.5 parts) and A-163 (1.5 parts), and adjust the amount of added melting force. A compound was obtained in the same manner as in Example 1 except that the amount was 100 parts.

<Example 9>

 Implemented except that the addition amount of Pre-Ract KR55 was 1.0 part, the addition amount of A-163 was 3.0 parts, and the addition amount of molten silica was 200 parts. A compound was obtained in the same manner as in Example 8.

<Example 10>

 As a coupling agent, 1.0 parts of Plankt KRTTS (trade name, manufactured by Ajinomoto Co., Inc., Isoprovir Tris Soy Steoil Oil) was used instead of FZ37778, and molten silica was used. A compound was obtained in the same manner as in Example 1, except that the amount of addition was 100 parts.

Comparative Example 9>

 A compound was obtained in the same manner as in Comparative Example 1, except that the addition amount of triphenylphosphine was 0.05 part, and the addition amount of the molten silicon force was 100 parts.

Comparative Example 10>

The addition amount of triphenylphosphine is 0.05 parts, the addition amount of silane coupling agent A-171 is 1.5 parts, and the addition amount of molten silica is 100 parts. Other than that described in Comparative Example 2, I got a compendium.

<Comparative Example 1 1>

 A compound was obtained in the same manner as in Comparative Example 5, except that the addition amount of triphenylphosphine was 0.05 parts and the addition amount of molten silica was 100 parts.

<Comparative Example 1 2>

 In the same manner as in Comparative Example 2 except that 3.0 parts of A-163 was used instead of A-171 as the silane coupling agent and the amount of molten silica added was 200 parts. I got the compound.

D. Examples 11-1: L2, Comparative Examples 13-14

 In these examples and comparative examples, compounds were prepared using calcium carbonate as a filler. In addition, stirring at the time of compound preparation was performed at 260 rpm for 60 minutes using a evening bottle.

 To this compound was added 0.12 parts of a polymerization catalyst, and after mixing, the compound was degassed under reduced pressure to obtain a molding material. A test piece was molded using the obtained molding material, and various characteristics were evaluated by the following methods. The method for preparing the test pieces and the method for evaluating the bending characteristics were the same as those in Examples 1 to 3 described above.

Table 4 shows the results of the evaluation. As can be seen from Table 4, the product containing the metal-containing adhesive has superior flexural strength compared to the product without the additive, and is superior to the product containing the silane coupling agent. Table 4

<Example 11>

 The addition amount of Preact KR 55 was 1.6 parts, and NS 400 (calcium carbonate, trade name of Nitto Powder Chemical Co., Ltd.) was used instead of molten silica. Then, a compound was obtained in the same manner as in Example 5.

 <Example 1 2>

 A compound was obtained in the same manner as in Example 11 except that 0.8 parts of the plan KRTTSS was used instead of the plan KR55.

 Comparative Example 1 3>

 A compound was obtained in the same manner as in Comparative Example 9 except that 100 parts of NS400 (calcium carbonate, trade name, manufactured by Nitto Powder Chemical Co., Ltd.) was used instead of molten silica.

 Comparative Example 1 4>

A compound was obtained in the same manner as in Comparative Example 10, except that 100 parts of NS400 (calcium carbonate, trade name, manufactured by Nitto Powder Co., Ltd.) was used instead of molten silica. INDUSTRIAL APPLICABILITY According to the cycloolefin composition and the molding material of the present invention, the toughness (particularly the bending rate during a bending test) is maintained without deteriorating the water resistance, electrical insulation, and mechanical properties. Can be suppressed. The molded product obtained from the cyclorefin composition and the molding material of the present invention can make use of the excellent water resistance, boiling resistance, mechanical properties, and electrical properties of the cycloolefin polymer. , Bathtubs, kitchen tops, tanks, unit baths, wall panels, pleasure boats, sewers, water pipes, corrugated boards, wiring boards, molded products such as insulating materials, electrical components, electronic components, etc. It is possible.

Claims

The scope of the claims

1. A cycloolefin composition comprising a cycloolefin monomer capable of polymerizing the polymerization, a coupling agent, and a polymerization catalyst for a polymerization,

 A cycloolefin composition comprising, as the above-mentioned coupling agent, at least one of a metal-containing coupling agent and a reactive polysiloxane.

2. The above-mentioned force-printing agent

 2. The cycloolefin composition according to claim 1, comprising at least one metal-containing coupling agent selected from the group consisting of titanium, aluminum, zirconium, iron, calcium, magnesium, and zinc.

3. The above coupling agent is

 Tetra (2,2—diaryloxymethyl-1—butyl) bis {di (tridecyl)} phosphite, isoprovir trisostearoyl cyanate, acetate alkoxy aluminum 2. The cycloolefin composition according to claim 1, which comprises at least one of mujisopropylate, zirconium acetyl acetate and bisethyl acetate.

4. The above-mentioned power-printing agent

3. The cycloolefin composition according to claim 1, comprising a reactive polysiloxane represented by the following general formula (1). RRRRR

M ^J (SiO) _a — (SiO) _b — (SiO) _d- (SiO) _e — Si-M ¹ ··· (1)

R Y z Q R wherein each R represents a hydrogen atom, a monovalent hydrocarbon group or a halogenated alkyl group independently selected from each other;

 Y represents an organic reactive functional group represented by the following general formula (4), and —R represents X… (4)

(However, R ¹ represents a direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and X represents a functional group having organic reactivity.)

 Z represents a hydrolyzable group or a condensable silylalkyl group represented by the following general formula (5),

-R ² -S i-(OR ⁴ )

 ( Five )

(R ³ ) 3-r

(However, R ² represents an alkylene group having 2 to 5 carbon atoms, R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and r represents 2 or 3 Is.)

 Q represents a polyoxyalkylene group represented by the following general formula (6),

-(CH ₂ ) _p -0- (C ₂ H ₄₀ ) _m- (C ₃ H ₆₀ ) _n -R ⁵ (6)

(However, R ⁵ represents a hydrogen atom, an acyl group or a monovalent hydrocarbon group, p is 0 or a positive integer, m and n are 0 or a positive integer of 150 or less, m + n is an integer of 1 to 150.)

M ¹ independently represents a group selected from the above R, Y, Ζ and Q; a is Ri integer der of 0 to 5 0 0, b is in the case of 0-2 0 0 integer der of Ri (where b is 0, M ¹ is Ri Y der, and also d and e Yes shift D is an integer of 0 to 200 (when d is 0, M ¹ is Z, and b and are both integers of 1 or more) , E is an integer of 0 to 200 (when e is 0, M ¹ is Q, and both b and d are integers of 1 or more).

5. The above-mentioned force printing agent

 3. The cycloolefin composition according to claim 1, comprising a reactive polysiloxane represented by the following general formula (2).

K K ix x \

M ^2- (SiO) _f- (SiO) _g- (SiO) _h -Si- M ² … (2)

R Y Z R wherein each R represents a hydrogen atom, a monovalent hydrocarbon group or a halogenated alkyl group selected independently of each other;

 Y represents an organic reactive functional group represented by the following general formula (4),

^-1 -X… (4)

(However, R ¹ represents a direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and X represents a functional group having organic reactivity.)

Z represents a hydrolyzable group or a condensable silylalkyl group represented by the following general formula (5), -R ² -S i-(OR ⁴ ) _r

 I… (5)

 3) 3-r

(However, R ² represents an alkylene group having 2 to 5 carbon atoms, R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and r represents 2 or 3 Is.)

M ² independently represents a group selected from the above R, Y and Z,

f is an integer of 0 to 500, g is an integer of 0 to 200 (when is 0, M ² is Y and h is an integer of 1 or more ), H is an integer of 0 to 200 (when h is 0, M ² is Z, and: f is an integer of 1 or more).

6. The above-mentioned force-printing agent

 4. The cycloolefin composition according to claim 1, comprising a reactive polysiloxane represented by the following general formula (3).

K K XV XV

M ³ — Si—O-(SiO) j— (SiO) _k — Si— M ³ … (3)

Κ ν Ζ 、 wherein each R represents a hydrogen atom, a monovalent hydrocarbon group or a halogenated alkyl group selected independently of each other;

Z represents a hydrolyzable group or a condensable silylalkyl group represented by the following general formula (5), RS i-(OR ⁴ )

 ( Five )

(R ³ ) 3

(However, R ² represents an alkylene group having 2 to 5 carbon atoms, R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and r represents 2 or 3 Is.)

M ³ independently represents a group selected from the above R and Y, j is an integer of 0 to 500, k is an integer of 0 to 500 (when k is 0, M ³ is Z).

7. The above-mentioned polymerization catalyst is

 2. The cycloolefin composition according to claim 1, which is a ruthenium compound.

8. The above-mentioned polymerization catalyst is

 3. The cycloolefin composition according to claim 1, which is a compound represented by the following general formula (7) or (8).

X ¹ L ¹ Q ¹

M = C 7)

X 2 'τ L 2 Q

X ¹ L ¹ Q ¹

 \ I

 M = C = C (8)

X ² L ² Q ^ώ

(However, Μ indicates ruthenium or osmium X ¹ and X ^{2 each} represent an anionic ligand,

1 and ^{2 each} represent a neutral ligand,

Q ¹ and Q ² are each independently selected from hydrogen, an alkyl group, an alkyl group having a substituent, an alkenyl group, an alkenyl group having a substituent, an aromatic group, and an aromatic group having a substituent. Indicates the selected group. )

9. The cycloolefin composition according to claim 8, wherein the catalyst is a compound represented by the following general formula (9).

X ¹ L ¹ R ⁷

 \ I /

M = CR ⁵

 / I \ /… (9)

X ² L ² C = C

 / \

HR ⁶

(Wherein, R ⁵ and R ^6, which it, alkylene Le group with carbon number 1-1 8, an alkenyl group of carbon number 2-1 8 Al Kiniru group having 2 to 1 8 carbon atoms, Ariru group, carbon atoms Carboxylate group having 1 to 18 carbon atoms, alkoxyl group having 1 to 18 carbon atoms, alkenyloxy group having 2 to 18 carbon atoms, alkynyloxy group having 2 to 18 carbon atoms, 2 to 18 carbon atoms Independently from an alkoxy group having 2 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, an alkylsulfonyl group having 1 to 18 carbon atoms and an alkylsulfinyl group having 1 to 18 carbon atoms Represents a group selected as

R ⁷ represents a group selected from hydrogen, aryl group and alkyl group having 1 to 18 carbon atoms. )

10. Includes additional filler,

 2. The cycloolefin composition according to claim 1, wherein the filler is at least one selected from glass, silica, alumina, magnesium hydroxide, aluminum hydroxide and silica sand.

1 1. The above cycloolefin monomers are

 2. The cycloolefin composition according to claim 1, comprising dicyclopentene.

12. A process for producing a cycloolefin composition, comprising a step of mixing a cycloolefin monomer capable of polymerization by polymerization, a coupling agent, and a metathesis polymerization catalyst.

 A method for producing a cycloolefin composition, wherein the coupling agent comprises at least one of a metal-containing coupling agent and a reactive polysiloxane.

13. A molding material comprising the cycloolefin composition according to claim 1.

14. A molded product which is a cured product obtained by curing the molding material according to claim 13.