JP2001278963A - Molding material capable of hardening, molding and their manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding material which is excellent in the low temperature stability, and the polymerization reaction at high temperature, and has little metal contents originating from a catalyst, while the molding material capable of hardening is the prehardening state which is obtained by the ring- opening metathesis polymerization of the norbornene monomer in the existence of the ruthenium complex catalyst. SOLUTION: The molding material is characterized by applying the ruthenium complex which the carbene compound containing at least one heteroatom in ruthenium coordinates as the ruthenium complex catalyst, while the molding material capable of hardening is the prehardenig state which is obtained by the ring-opening metathesis polymerization of the norbornene monomer in the existence of the ruthenium complex catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is capable of curing a norbornene-based monomer in a precured state (hereinafter sometimes referred to as "B stage") by ring-opening metathesis polymerization in the presence of a ruthenium complex catalyst. The present invention relates to a novel molding material, a molded product obtained from the molding material, and a method for producing them.

[0002]

2. Description of the Related Art Conventionally, elastomers, soft resins and hard resins at room temperature have been obtained by ring-opening metathesis polymerization of norbornene monomers, and these elastomers and resins have been used in the production of various molded articles. I have.

As a method for obtaining a molded article, there is a method in which a norbornene-based monomer is subjected to solution polymerization, and the polymer is formed into a molded article by a thermoforming method such as an injection molding method or a calendar molding method. Also, as in the case of the reaction injection molding (RIM) method, the norbornene-based monomer is lumped (bulk) in a mold.
A method of obtaining a molded article by polymerization is also known. The latter RI
In the M method, since a norbornene-based monomer is bulk-polymerized in a mold, it becomes a thermosetting resin having good heat resistance at once from a liquid material. ing.

Another method for obtaining a molded article of a polynorbornene resin has also been reported. For example, JP-A-2-2255
Japanese Patent Application Laid-Open No. 18-293124 and Japanese Patent Application Laid-Open No. 3-292124 describe a molding method of subjecting a polynorbornene-based resin, which is primarily molded by bulk polymerization in a mold, to a secondary molding by further applying an external force or heating. I have.

[0005] WO 99/54374 discloses that
There is described a curable molding material which is made into a semi-cured state by reacting a metathesis-polymerizable cycloolefin in the presence of a metathesis polymerization catalyst, and a method for producing various molded articles from the molding material.

[0006]

The above-mentioned WO 9
The molding material described in JP 9/54374 uses a ruthenium carbene complex in which two neutral electron donors (phosphine, amine, etc.) are coordinated to ruthenium as a metathesis polymerization catalyst, and uses a metathesis-polymerizable cycloolefin as a raw material. Thus, molded articles of various shapes can be easily and safely produced in the ordinary atmosphere.

However, the moldings obtained using the above-mentioned ruthenium catalysts have problems that storage stability is poor and that the catalyst activity during heat curing is low. Further, there is a problem that the ruthenium catalyst has a low catalytic activity, the amount of the catalyst used is relatively large, and the molding material becomes expensive. Furthermore, depending on the purpose of use of the finally obtained molded article, if the molded article contains a large amount of a metal compound or a halogen derived from a catalyst, for example, in a resin for electric / electronic parts, it is desirable. In some cases, there is no effect, and it is generally necessary to reduce the metal content in the resin as much as possible.

In view of such circumstances, the present invention firstly provides an industrially advantageous curable molding material in a pre-cured state obtained by ring-opening metathesis polymerization of a norbornene-based monomer in the presence of a ruthenium complex catalyst. It is another object of the present invention to provide a molded material having good storage stability at low temperatures (at ordinary temperatures) and easy to heat and cure. A second object of the present invention is to provide a molded material having a very small content of catalyst-derived metal, halogen and the like. Still another object of the present invention is to provide a molded product obtained by curing the obtained molding material and a method for producing the molded product.

[0009]

Means for Solving the Problems In order to achieve the above object, the present inventors have developed a precured molding material obtained by ring-opening metathesis polymerization of a norbornene monomer using various ruthenium complex catalysts. As a result of intensive studies, it has been found that a ruthenium complex catalyst having a specific structure has a very large temperature dependence of the polymerization reaction rate, and the precured molding material obtained by using this catalyst has storage stability at low temperature and high temperature. Was found to be excellent in polymerization reactivity. In addition, they have found that the ruthenium catalyst has extremely high catalytic activity, and that polymerization of this ruthenium catalyst can further reduce the metal content contained in the molding material. Further, a method for producing a molded article using this molding material has been established, and the present invention has been completed.

That is, the present invention relates to a curable molding material in a precured state obtained by subjecting a norbornene-based monomer to ring-opening metathesis polymerization in the presence of a ruthenium complex catalyst, wherein the ruthenium complex catalyst comprises A molding material characterized by using a ruthenium complex in which at least one heteroatom-containing carbene compound is coordinated.

The molding material can be molded with a ruthenium compound concentration in the molding material of 25 ppm or less.

Further, the present invention provides a method for producing a molded article and a molded article having a first step of obtaining the molded article, and a second step of shaping the molded article into a predetermined shape and heat-curing the molded article. I do.

[0013]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail by dividing them into items. (Metathesis polymerization catalyst) The catalyst used in the production of the molding material of the present invention is not particularly limited as long as it is a ruthenium complex in which ruthenium is coordinated with at least one heteroatom-containing carbene compound. A ruthenium carbene complex represented by the formula 1 or the general formula 2 is exemplified.

[0014]

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(Wherein R ¹ and R ² are each independently
C _1- which may contain hydrogen or (halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, silicon atom)
Represents a hydrocarbon group of C _20, X ^1, X ² represents an arbitrary anionic ligand independently of one another, L ¹ represents a hetero atom-containing carbene compounds, L ² is a hetero atom-containing carbene compound or Represents any neutral electron donating compound. In addition, two or three of R ¹ , R ² , X ¹ , X ² , L ¹ and L ² ,
Four, five or six may be linked together to form a polydentate ligand. )

In the general formulas 1 and 2, R
¹, R^TwoIs, for example, hydrogen, C _Two~ C₂₀Alkenyl
Group, C_Two~ C₂₀Alkynyl group, C₁~ C₂₀Alkyl group
Aryl group which may have a substituent, carboxyl group,
C_Two~ C₂₀Alkenyloxy group, C_Two~ C₂₀Alkynyluo
An xy group, an aryloxy group which may have a substituent,
C_Two~ C₂₀Alkoxycarbonyl group, C₁~ C₂₀Alkyl
A thio group, an arylthio group which may have a substituent,
₁~ C₂₀Alkylsulfonyl group, C₁~ C₂₀Alkylsul
And a finyl group.

The substituents for the allyl group, allyloxy group and arylthio group include halogen atoms such as nitro group, fluorine, chlorine and bromine, alkyl groups such as methyl group and ethyl group, methoxy group and ethoxy group. And an alkoxy group. Further, these groups may have a plurality of the same or different substituents.

L ¹ represents a carbene compound containing a hetero atom, and L ² represents a carbene compound containing a hetero atom or any neutral electron donating compound.

Here, as the hetero atom, for example,
Examples thereof include N, O, P, S, As, and Se atoms. Among them, N, O, P, S atoms and the like are preferable for obtaining a stable carbene compound, and N atoms are particularly preferable.

The carbene compound is a general term for a compound having a methylene free radical in a molecule and has an uncharged divalent carbon atom represented by (> C :). In general, carbene exists as an unstable intermediate generated during the reaction, but when it has a hetero atom, it becomes a relatively stable carbene compound.

Examples of such heteroatom-containing carbene compounds include compounds represented by the following formulas 3 and 4.

[0022]

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In the above formula, R ³ and R ⁴ are each independently hydrogen or C ₁ -C which may contain (halogen, oxygen, nitrogen, sulfur, phosphorus, silicon). It represents a _{2 0} hydrocarbon group.

The R ³ and R ⁴ are, for example, C ₁ -C
_{A 20} alkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₂ -C ₂₀ alkynyl group, a C ₃ -C ₈ cycloalkyl group optionally having a substituent, an aryl group optionally having a substituent, etc. Is mentioned.

Specific examples of the above formula 3 include 1,3-diisopropylimidazolidine-2-ylidene, 1,3-dicyclohexylimidazolidin-2-ylidene, 1,3
-Diphenylimidazolidine-2-ylidene, 1,3-
Di (methylphenyl) imidazole, 1,3-di (methylnaphthyl) imidazolidin-2-ylidene, 1,3-
Dimesityl imidazolidine-2-ylidene, 1,3-diadamantylimidazolidine-2-ylidene, 1,3,3
4,5-tetramethylimidazolidine-2-ylidene and the like.

Specific examples of the above formula 4 include 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3
-Dicyclohexyl-4-imidazoline-2-ylidene, 1,3-diphenyl-4-imidazoline-2-ylidene, 1,3-di (methylphenyl) -4-imidazoline-2-ylidene, 1,3-di (methyl Naphthyl) -4
-Imidazoline-2-ylidene, 1,3-dimesityl-
4-imidazoline-2-ylidene, 1,3-diadamantyl-4-imidazoline-2-ylidene, 1,3,4
5-tetramethyl-4-imidazoline-2-ylidene,
1,3,4,5-tetraphenyl-4-imidazoline-
2-ylidene and the like.

In addition to the compounds represented by the formulas 3 and 4, 1,3,4-triphenyl-2,3,4,4
5-tetrahydro-1H-1,2,4-triazole-
5-ylidene, 3- (2,6-diisopropylphenyl) -2,3,4,5-tetrahydrothiazole-2-
Ylidene, 1,3-dicyclohexylhexahydropyrimidine-2-ylidene, N, N, N ', N'-tetraisopropylformamidinylidene, 1,3,4-triphenyl-4,5-dihydro-1H-1 And heteroatom-containing carbene compounds such as 2,2,4-triazole-5-ylidene and 3- (2,6-diisopropylphenyl) -2,3-dihydrothiazole-2-ylidene.

As the hetero atom-containing carbene compound,
Cyclic compounds in which the heteroatom adjacent to the carbene has a bulky substituent are preferred. As a specific example, 1,3-
Diisopropylimidazolidine-2-ylidene, 1,3
-Dicyclohexylimidazolidin-2-ylidene,
1,3-di (methylphenyl) imidazolidine-2-ylidene, 1,3-di (methylnaphthyl) imidazolidin-2-ylidene, 1,3-dimesitylimidazolidine
2-ylidene, 1,3-diadamantyl imidazolidine-2-ylidene, 1,3-diphenylimidazolidine-
1,3-disubstituted imidazolidinylidenecarbene compounds such as 2-ylidene and 1,3,4,5-tetraphenylimidazolidin-2-ylidene;

1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-dicyclohexyl-4-imidazoline-2-ylidene, 1,3- (dimethylphenyl) -4-imidazoline-2-ylidene, 3-di (methylnaphthyl) -4-imidazoline-2-ylidene, 1,3-dimesityl-4-imidazoline-2-ylidene, 1,3-diadamantyl-4-imidazoline-2
-Ilidene, 1,3-diphenyl-4-imidazoline-
2-ylidene, 1,3,4,5-tetraphenyl-4-
1,3-disubstituted imidazolinylidenecarbene compounds such as imidazoline-2-ylidene.

The anionic (anionic) ligands X ¹ and X ² of the above formulas 1 and 2 may be any ligands as long as they have a negative charge when separated from the central metal. . Further, X ¹ and X ² may be combined to form a bidentate or more anionic ligand.

Specific examples of the above X ¹ and X ² include F and B
r, a halogen atom such as Cl, I, hydrogen, an OH group, a substituted allyl group, an alkenyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a carboxyl group, an alkyl or aryl sulfonate group, Examples thereof include an alkylthio group, an alkenylthio group, an arylthio group, an alkylsulfonyl group, an alkylsulfinyl group, an acetylacetonato group, a diketonate group, and a substituted cyclopentadienyl group. Of these, a halogen atom is preferable, and a chlorine atom is more preferable.

The neutral electron donating compound may be any ligand as long as it is a ligand having a neutral charge when separated from the central metal, that is, a Lewis base. Specific examples thereof include oxygen, water, carbonyl, amines, pyridines, ethers, nitriles, esters, phosphines, phosphinites, phosphites, stibines, sulfoxides, thioethers, and amides. , Aromatic compounds, cyclic diolefins, olefins, isocyanides, thiocyanates and the like.

Of these, phosphines are preferred.
Trialkylphosphines and triarylphosphines are more preferred. Examples of the trialkylphosphine include trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tributylphosphine, triisobutylphosphine, and tri (sec)
-Butyl) phosphine, tri (t-butyl) phosphine, tripentylphosphine, trihexylphosphine, tricyclopropylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, tri (2-methylcyclohexyl) phosphine, tri (3-
Examples thereof include methylcyclohexyl) phosphine, tri (3-methylcyclohexyl) phosphine, tri (2,4-dimethylcyclohexyl) phosphine, and tri (2,4,6-trimethylcyclohexyl) phosphine.

The triarylphosphine includes triphenylphosphine, tri (2-methylphenyl) phosphine, tri (4-chlorophenyl) phosphine, tri (3-methylphenylphosphine), tri (4-methylphenyl) phosphine, tri ( 2,4-dimethylphenyl) phosphine, tri (2,4,6-trimethylphenyl) phosphine, dimethylphenylphosphine, diethylphenylphosphine, diisopropylphenylphosphine, dibutylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, propyldiphenylphosphine And butyldiphenylphosphine.

The complex compound represented by the above formula 1 includes
For example, (1,3-dicyclohexylimidazolidin-
2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dicyclohexyl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dicyclohexylimidazolidin-2)
-Ylidene) (triphenylphosphine) benzylidene ruthenium dichloride, (1,3-dicyclohexyl-
4-imidazoline-2-ylidene) (triphenylphosphine) benzylideneruthenium dichloride, (1,3
-Dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dimesitylimidazolidine-2-ylidene) (triphenylphosphine) benzylideneruthenium dichloride, (1,3-dimesityl) -4-imidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-
Dimesityl-4-imidazolidin-2-ylidene) (triphenylphosphine) benzylidene ruthenium dichloride,

[1,3-di (2-methylphenyl) imidazolidine-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3
-Di (3-methylphenyl) imidazolidine-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (4-methylphenyl) imidazolidine-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium Dichloride, [1,3-di (2-methylphenyl) imidazolidine-2-ylidene] (triphenylphosphine) benzylidene ruthenium dichloride, [1,3-di (3-methylphenyl) imidazolidine-2-ylidene] ( Triphenylphosphine) benzylidene ruthenium dichloride, [1,3-di (4-methylphenyl) imidazolidine-2-ylidene] (triphenylphosphine) benzylidene ruthenium dichloride,

[1,3-di (2-methylphenyl) -4
-Imidazoline-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride,
[1,3-di (3-methylphenyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine)
Benzylidene ruthenium dichloride, [1,3-di (4
-Methylphenyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (2-methylphenyl) -4-imidazoline-2-ylidene] (triphenylphosphine) benzylidene ruthenium Dichloride,
[1,3-di (3-methylphenyl) -4-imidazoline-2-ylidene] (triphenylphosphine) benzylidene ruthenium dichloride, [1,3-di (4-methylphenyl) -4-imidazoline-2-ylidene ] (Triphenylphosphine) benzylidene ruthenium dichloride,

[1,3-di (2-methyl-1-naphthyl) imidazolidine-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride,
[1,3-di (4-methyl-1-naphthyl) imidazolidine-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (8-methyl-1-naphthyl) imidazolidine-2 -Ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (1-methyl-
2-naphthyl) imidazolidine-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (4-methyl-2-naphthyl)
Imidazolidine-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride,
[1,3-di (8-methyl-2-naphthyl) imidazolidine-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride,

[1,3-di (2-methyl-1-naphthyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (4-methyl-1-naphthyl) ) -4-
Imidazoline-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,
3-di (8-methyl-1-naphthyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine)
Benzylidene ruthenium dichloride, [1,3-di (1
-Methyl-2-naphthyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (4-methyl-
2-naphthyl) -4-imidazoline-2-ylidene]
(Tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (8-methyl-2-naphthyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3,4,5) Heteroatom-containing carbene compounds such as -tetraphenyl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dicyclohexylhexahydropyrimidine-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride A ruthenium complex compound coordinated with a neutral electron-donating compound;

Bis (1,3-diisopropylimidazolidine-2-ylidene) benzylidene ruthenium dichloride, bis (1,3-dicyclohexylimididazolidine)
2-ylidene) benzylidene ruthenium dichloride, bis (1,3-diisopropyl-4-imidazoline-2-
(Ylidene) benzylidene ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-
Ilidene) benzylidene ruthenium dichloride, bis (1,3-dimesitylimidazolidine-2-ylidene)
Ruthenium complex compounds in which two heteroatom-containing carbene compounds such as benzylidene ruthenium dichloride and bis (1,3-dimesityl-4-imidazoline-2-ylidene) benzylidene ruthenium dichloride are coordinated.

Examples of the complex compound represented by the above formula 2 include (1,3-dicyclohexylimidazolidine-2-ylidene) (tricyclohexylphosphine)
Phenylvinylidene ruthenium dichloride, (1,3-
Dimesityl imidazolidine-2-ylidene) (tricyclohexylphosphine) t-butylvinylidene ruthenium dichloride, 1,3-dicyclohexyl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) phenylvinylidene ruthenium dichloride,
3-dimesityl-4-imidazoline-2-ylidene)
(Tricyclohexylphosphine) phenylvinylidene ruthenium dichloride,

[1,3-di (methylphenyl) imidazolidine-2-ylidene] (tricyclohexylphosphine) t-butylvinylidene ruthenium dichloride,
[1,3-di (2-methyl-1-naphthyl) imidazolidine-2-ylidene] (tricyclohexylphosphine) phenylvinylidene ruthenium dichloride, [1,
3-di (4-methylphenyl) -4-imidazoline-2
-Ylidene] (tricyclohexylphosphine) t-butylvinylidene ruthenium dichloride, [1,3-di (4-methyl-1-naphthyl) -4-imidazoline-2
-Ylidene] (tricyclohexylphosphine) phenylvinylideneruthenium dichloride, (1,3,4,5
Heteroatoms such as -tetraphenylimidazolidine-2-ylidene) (tricyclohexylphosphine) t-butylvinylideneruthenium dichloride, (1,3-dicyclohexylhexahydropyrimidine-2-ylidene) (tricyclohexylphosphine) phenylvinylideneruthenium dichloride A ruthenium complex compound in which a carbene compound and a neutral electron donating compound are coordinated;

Bis (1,3-diisopropylimidazolidin-2-ylidene) phenylvinylidene ruthenium dichloride, bis (1,3-dicyclohexylimidazolidin-2-ylidene) t-butylvinylidene ruthenium dichloride, bis (1,3-diisopropyl) -4-imidazoline-2-ylidene) t-butylvinylidene ruthenium dichloride, bis (1,3-dicyclohexyl-4)
A ruthenium complex compound in which two heteroatom-containing carbene compounds such as (imidazoline-2-ylidene) phenylvinylidene ruthenium dichloride are coordinated; These ruthenium complex compounds can be used alone or in combination of two or more.

In the present invention, the ruthenium complex compound may be di-μ-chlorobis [(p-cymene) chlororuthenium], di-μ-chlorobis [(p-cymene)
[Chloroosmium] and a dinuclear ruthenium-carbene complex compound obtained by reacting with a dinuclear metal complex such as dichloro (pentamethylcyclopentadienyl) rhodium dimer.

These ruthenium complex compounds are described, for example, in Org. Lett. , 1999, Volume 1, 953
Page, Terahedron. Lett. , 1999,
It can be produced according to the method described in Vol.

The amount of the ruthenium complex compound used, that is, the ratio of the metathesis polymerization catalyst to the norbornene monomer, is usually 1: 2,000 to 1: 1, as the molar ratio of metal ruthenium / norbornene monomer in the catalyst.
2,000,000, preferably 1: 5,000 to 1,
1,000,000, more preferably 1: 10,000-
1: 500,000.

The ruthenium catalyst can be used by dissolving it in a small amount of an inert solvent, if necessary. Such solvents include, for example, chain aliphatic hydrocarbons such as pentane, hexane and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene,
Alicyclic hydrocarbons such as bicycloheptane, tricyclodecane, hexahydroindenecyclohexane, and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; diethyl ether; Solvents such as ethers such as tetrahydrofuran can be used. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons that are generally used industrially are preferable.

When additives such as an antioxidant and a plasticizer are in a liquid state, they can be used as a solvent for dissolving the catalyst. Examples of liquid antioxidants include:
2,6-di-t-butylphenol and 2,6-di-t-
Examples thereof include a mixture of butyl-4-methylphenol and 2,6-di-t-butyl-4-nonylphenol.

(Norbornene-Based Monomer) The monomer subjected to ring-opening metathesis polymerization in the presence of the above-mentioned catalyst is a norbornene-based monomer having a norbornene ring structure.
As such norbornene-based monomers, substituted and unsubstituted bicyclic or tricyclic or higher polycyclic norbornenes are used.

Specific examples thereof include norbornene, norbornadiene, methyl norbornene, dimethyl norbornene, ethyl norbornene, chlorinated norbornene, ethylidene norbornene, chloromethyl norbornene, trimethylsilyl norbornene, phenyl norbornene, cyano norbornene, dicyanorbornene, methoxycarbonyl norbornene, and pyridyl. Bicyclic norbornenes such as norbornene, nadic anhydride, nadimide;

Tricyclic norbornenes such as dicyclopentadiene, dihydrodicyclopentadiene and their alkyl, alkenyl, alkylidene and aryl substituents; dimethanohexahydronaphthalene, dimethanooctahydronaphthalene and their alkyl, alkenyl, alkylidene and aryl substitutions Pentacyclic norbornenes such as tricyclopentadiene; hexacyclic norbornenes such as hexacycloheptadecene; dinorbornene, a compound in which two norbornene rings are bonded by a hydrocarbon chain or an ester group, Compounds containing a norbornene ring such as an alkyl- or aryl-substituted product thereof may, for example, be mentioned.

Monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclooctene and cyclododecene and derivatives thereof having a substituent can also be copolymerized with the norbornene-based monomer.

The above norbornene monomers may be used alone or in combination of two or more, but the use of two or more is preferred. When two or more kinds are used, they become thermoplastic resins.
Resins having various physical properties can be obtained by appropriately combining a monomer having two double bonds and a monomer having a plurality of double bonds to be a thermosetting resin. Also,
Compared to the case where a monomer is used alone, when two or more kinds are used in combination, there is an advantage that a monomer having a high freezing point temperature can be handled as a liquid due to a drop in freezing point.

(Molding material in pre-cured state) Using the ruthenium complex compound (metathesis polymerization catalyst) and norbornene-based monomer as described above, reaction conditions, that is, the amount of the catalyst used, the reaction temperature, the use of a reaction regulator and the like are appropriately selected. By doing so, the rate of the metathesis polymerization reaction can be arbitrarily adjusted. Therefore, it is possible to obtain a molding material in the middle of the reaction in which the polymerization of the norbornene-based monomer as the raw material is not completed. Such a state is referred to as a “pre-cured state”. When the precured molding material is heated, the metathesis polymerization reaction resumes, and the curing can be completed.

The molding material in the pre-cured state of the present invention can be made into a liquid having fluidity or a solid having no fluidity by selecting conditions. In addition, the flow state can be appropriately selected according to the shaping method. When the pre-cured molding material is liquid, its viscosity is usually several tens c.
ps or more, and can be appropriately selected depending on the shaping method. When the pre-cured molding material is solid, its hardness (flexural rigidity) is not particularly limited, and can be appropriately selected according to the shaping method. The time from pre-curing to shaping into a predetermined shape may be appropriately selected according to the form of production of the molded article. Further, the time for maintaining the pre-curing time can be adjusted by the storage temperature.

The molding material of the present invention may contain, if necessary, an antioxidant, an ultraviolet absorber, an elastomer, a polymer modifier,
Fillers, flame retardants, crosslinking agents, sliding agents, coloring agents, odorants,
By blending various additives such as fillers for weight reduction, foaming agents, whiskers for surface smoothing,
The properties of the molded article described later can be modified. Normal,
These additives are used by dissolving or dispersing them in the norbornene-based monomer in advance.

Examples of the antioxidant include various antioxidants for plastics and rubbers such as hindered phenol, phosphorus and amine. These antioxidants may be used alone, but are preferably used in combination. The mixing ratio of the antioxidant is usually 0.5 parts by weight or more, preferably 1 to 3 parts by weight, based on the norbornene-based monomer. The antioxidant may be copolymerizable with the monomer, and specific examples thereof include 5- (3,5-di-t).
Examples thereof include norbornenylphenol compounds such as tert-butyl-4-hydroxy) benzyl-2-norbornene and the like (for example, JP-A-57-83522).
Reference).

The elastomer is not particularly limited as long as it is soluble in the norbornene monomer. Examples of such an elastomer include natural rubber, butyl rubber, polybutadiene, polyisoprene, polyisobutylene, ethylene-propylene copolymer, ethylene-propylene-diene terpolymer (EPDM), and styrene-based block copolymer. EPDM and styrene block copolymers are preferred. These elastomers can be used in a wide range from liquids having an average molecular weight of 500 to several thousand to solids having an average molecular weight of several hundred thousand to several hundred thousand. Moreover, you may use individually and may use 2 or more types together.

Examples of the filler include inorganic fillers such as glass powder, talc, calcium carbonate, mica, and aluminum hydroxide. Such fillers are preferably surface-treated with a silane coupling agent or the like. When sulfur or peroxide is used as a crosslinking agent, heat resistance is improved.

As the reinforcing material, inorganic reinforcing materials such as glass and carbon, PAN, pitch, rayon carbon fiber, PE
Organic fibers such as T, polyethylene, and Kepler can be used. These reinforcing materials may be in any form such as chopped strand, mat, roving, cloth and the like. These reinforcing materials can be mixed with the material, or may be set in a molding die in advance.

The molding material of the present invention has a large temperature dependency, that is, it is stable at a low temperature, but is produced using a ruthenium complex catalyst having excellent reactivity at a high temperature. Excellent (the curing reaction does not proceed), and the amount of ruthenium compound (ruthenium complex compound or its decomposition product) contained in the molding material can be suppressed to 25 ppm or less. Therefore, the finally obtained molded article can be suitably used as a material of a molded article in which it is desirable that the content of a metal compound derived from a catalyst such as an electric or electronic component, halogen, or the like be as small as possible.

(Method of Manufacturing Molded Article and Molded Article) A molded article in a pre-cured state is cured by heating to obtain a molded article. The heating operation is usually performed in two stages. The first-stage heating is performed to make the above-described pre-cured state. The temperature is usually 0 to 100 ° C., preferably 20 to 50 ° C., and the time can be appropriately set depending on the amount of the catalyst and the reaction temperature. The second stage of heating is performed for shaping into a predetermined shape and completing the curing. The temperature at that time is usually 50 to 250 ° C, preferably 60 to 200 ° C, and the reaction time can be appropriately set depending on the amount of the catalyst used and the reaction temperature.
As described above, in the present invention, since a ruthenium complex catalyst having high temperature dependence is used, the curing time of the molding material can be set to a short time, which is advantageous for industrial production.

In the present invention, after the molding material in the pre-cured state is formed into a predetermined shape, the formed molding material may be heat-cured. It can also be done. Further, the molding material of the present invention can be used in a solvent-free composition, and a solvent can be used if necessary.

The molded product obtained by heating and curing the precured molding material of the present invention includes pipes, semicircular tubes,
Any of a planar object and a three-dimensional object such as a laminate may be used. When a molding die is used for shaping into a predetermined shape, a compression molding die, an ordinary SMC (Sh
eet Mold Compound) and BMC (Bu
lk Mold Compound) molds can be used. Various molding methods such as compression, injection compression, matched metal die, and prepreg molding can be used. The molding method can be appropriately selected and the shape and material of the mold can be selected according to the use and the production amount of the molded article.

(Printed Wiring Board) The method for manufacturing a molded article of the present invention can be suitably applied to the manufacture of a printed wiring board. Such a printed wiring board is manufactured by first preparing a prepreg or sheet-like (sheet or film) pre-cured molding material impregnated in a base material, laminating this, and heating and curing.

The method for producing the prepreg is not particularly limited, but usually, a reaction solution in which the above-mentioned monomer, catalyst and various compounding agents are uniformly dissolved or dispersed is impregnated into a reinforcing base material and precured. It is manufactured by subjecting it to a heat treatment. Generally, prepreg is 50-500
It is preferable that the thickness be about μm.

Examples of the reinforcing base material include paper base materials (such as linter paper and kraft paper), glass base materials (such as glass cloth, glass mat, and glass paper quartz fiber) and synthetic resin-impregnated base materials (such as polyester resin and aramid). Fiber). Further, these reinforcing base materials may be surface-treated with a treating agent such as a silane coupling agent. These reinforcing substrates can be used alone or in combination of two or more. The amount of the polynorbornene-based resin used in the reinforcing substrate is appropriately selected depending on the purpose of use, but is in the range of 1 to 90% by weight, preferably 10 to 60% by weight based on the reinforcing substrate.

The method for producing the sheet is not particularly limited, but generally, a casting method is used. For example,
The reaction solution obtained by uniformly dissolving or dispersing the monomer, catalyst and various compounding agents as described above is cast or applied on a smooth surface, and subjected to a heat treatment for pre-curing, and then peeled off from the smooth surface. To get a sheet. As the smooth surface, a mirror-finished metal plate or a resin carrier film can be used. The sheet obtained by the casting method generally has a thickness of about 10 μm to 1 mm.

The printed wiring board (laminated board) is obtained by stacking the above-mentioned prepregs and / or sheets, heating and compressing and curing the prepreg to obtain a required thickness. On this substrate, for example, a circuit is formed by laminating a wiring conductive layer made of a metal foil or the like, or by etching the surface. The conductive layer for wiring is not only laminated on the outer surface of the substrate, but may be laminated inside the substrate as needed. In order to prevent warpage at the time of secondary processing such as an etching process, it is preferable to stack the layers in a vertically symmetric combination. For example, the laminated prepreg and / or sheet is heated to a thermosetting temperature or higher, usually 60 to 250 ° C., preferably 80 to 250 ° C., and 10 to 80 gf / c
The laminate can be obtained by pressing to about m ² .

Other methods of applying metal to these insulating layers or substrates include vapor deposition, electroplating, sputtering, ion plating, spraying and layering. Commonly used metals are copper, nickel, tin, silver,
Gold, aluminum, platinum, titanium, zinc and chromium. Copper is most frequently used in wiring boards.

The printed circuit board can be mounted with an electric element or the like as follows. First, a resin obtained by the method for producing a molding material of the present invention, and a composition to which a filler or the like is added as required are sufficiently mixed by a known means such as a kneader or a three-roll mill, and this is then rolled and extruded. The sheet is formed into a sheet by an injection method, a doctor blade method, or the like, and heat-treated as necessary to obtain a pre-cured curable insulating sheet. Next, through-holes are formed in the insulating sheet as desired in the thickness direction, and the through-holes are filled with a conductive metal paste to form via-hole conductors.

Further, a space for accommodating an electric element is formed at a predetermined position of the insulating sheet. Next, a wiring circuit layer is formed on the surface of the insulating sheet, and an electric element is mounted in the gap. The wiring circuit layer is, for example, a method of forming a metal layer by plating on the surface of an insulating sheet and forming a circuit pattern by etching, or a method of forming a resist pattern on the surface of the insulating sheet and forming a circuit pattern by plating. Can be formed by a known method.

The transfer film on which the electric element is mounted is laminated and pressed on the insulating sheet so that the electric element is accommodated in the gap of the insulating sheet. Then, the transfer film is peeled off, and the electric element is separated from the insulating sheet. To form a single wiring layer in which the electric element is mounted and accommodated in the gap. In this case, the structure on which the wiring circuit layer and the electric element are mounted can be transferred from the transfer film to the insulating sheet.

Thereafter, the second and third insulating sheets in the pre-cured state obtained by the present invention are laminated and pressed on the upper and lower surfaces of the insulating sheet in which the electric elements are stored, and the insulating sheet is cured. Heat to a sufficient temperature and cure it all at once.

The wiring board thus obtained has a low dielectric constant, excellent electrical properties, excellent mechanical strength, and excellent adhesion.

[0076]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the scope of the present invention is not limited to these examples. In these examples, the percentages and ratios are based on weight. The methods for measuring various physical properties are as follows.

(1) Viscosity: Using a B-type viscometer (manufactured by Tokimec), The measurement was performed by rotating the rotor No. 4 at 12 rpm. (2) Glass transition temperature (Tg): glass transition temperature (T
g) The measurement was performed by measuring Tig according to JIS K7121 to obtain Tg. (3) Peel strength: measured in accordance with JIS C6481.

Example 1 Preparation of Molded Material in Precured State
And benzylidene (1,3-dimesitylimidazolidine-2-ylidene) in a 300 ml separable flask
(Tricyclohexylphosphine) ruthenium dichloride (synthesized based on the description in Org. Lett., 1999, vol. 1, p. 953) 42 mg (concentration in a polymerization system: 0.5 mmol / l) and a stirrer were placed. .

After adding 0.5 ml of toluene and stirring with a magnetic stirrer to dissolve the ruthenium catalyst, dicyclopentadiene (containing 10% of 5-ethylidenebicyclo [2.2.1] hept-2-ene) 99 .
5 ml was added and stirred. The stirrer was taken out, placed in a water bath at 30 ° C., stirred for 50 minutes with a mechanical stirrer, and immediately cooled with ice to obtain a fluid, high-viscosity liquid (molding material 1). All of the above operations were performed in a nitrogen atmosphere. The viscosity of the molded material 1 at 0 ° C. was measured and found to be 12.2 Pas.

In order to examine the storage stability of the molding material 1 at a low temperature, it was stored in a refrigerator at −10 ° C. under a nitrogen atmosphere for one week, and a fluid and highly viscous liquid state was maintained. When the viscosity at 0 ° C. was measured, it was 18.2 Pa
s.

Comparative Example 1 Preparation of Molded Material in Precured State
Preparation and Low Temperature Stability Test A 300 ml separable flask was charged with dicyclopentadiene (5-ethylidenebicyclo [2.2.1] hept-
100 ml of 2-ene (containing 10% of 2-ene) and 78 mg of triphenylphosphine (concentration in the polymerization system: 3 mmol / l) were added, and the mixture was stirred and dissolved with a mechanical stirrer. To this, benzylidenebis (tricyclohexylphosphine) ruthenium dichloride (Strem Che)
41 mg (concentration in a polymerization system: 0.5 mmol / l) was added thereto, followed by stirring to dissolve. This is 3
After being placed in a water bath at 0 ° C. and stirred for 50 minutes, the mixture was immediately cooled with ice, and became a fluid high-viscosity liquid (molding material 2). All of the above operations were performed in a nitrogen atmosphere.

The viscosity of the molded material 2 at 0 ° C. was measured and found to be 10.3 Pas. In order to examine the storage stability of the molding material 2 at a low temperature, it was stored in a refrigerator at −10 ° C. under a nitrogen atmosphere, and after 1 day, it had become a solid without fluidity. As described above, in Comparative Example 1, the curing reaction proceeded even at a low temperature, and storage stability was found to be poor.

Example 2 Curing reaction of the molding material 1 at high temperature
Flat molding press die for 4 × 10 × 10 with a response temperature control pipe (manufactured SUS420j2), placed in a press molding apparatus having a vertically movable hydraulic press, the mold temperature is, the upper mold 80 ° C., The lower mold was set to 60 ° C. With the mold open, 40 g of the molding material 1 was introduced into the lower mold, and then the mold was closed by operating a hydraulic press to mold. The pressure at this time was 10 kg per 1 cm 2 of the area of the flat plate. Three
After a lapse of minutes, the mold was opened and the molded product was taken out. The above molding operation was performed in air. The obtained molded product was sufficiently cured, and had a Tg of 130 ° C.

Comparative Example 2 Curing of the molding material 2 at high temperature
Addition to using the response forming material 2 was operated in the same manner as in Example 2.
The obtained molded product was not sufficiently cured and had a Tg of 45.
° C. This molded product is placed in a 150 ° C. oven for 30 minutes.
After post-curing for minutes, the curing progressed and the Tg reached 131 ° C. As described above, in Comparative Example 2, the reactivity at a high temperature was poor, so that the curing was insufficient in the mold, and a post-curing at a higher temperature was required to sufficiently cure.

Example 3 Benzylidene (1,3-dimethyl)
Tyl-4-imidazoline-2-ylidene) (tricyclo
Hexylphosphine) using ruthenium dichloride
Preparation of molding material and curing reaction As a ruthenium catalyst, benzylidene (1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride (Tetr)
ahedron Lett. , 1999, 40, 2
Synthesized based on the description on page 247), 42 mg
(Concentration of 0.5 mmol / l in the polymerization system)
The operation was performed in the same manner as in Example 1 except that the temperature of the water bath was set to 46 ° C and the storage temperature of the semi-cured molding material in the refrigerator was set to 0 ° C. The molded material obtained here is referred to as molded material 3.

The viscosity at 0 ° C. of the molding material 3 immediately after preparation was 11.5 Pas. The viscosity at 0 ° C. after storage at 0 ° C. for 1 week is 12.9 Pas,
It was found that the storage stability at low temperatures was excellent. When a flat plate was formed using the molding material 3 immediately after preparation in the same manner as in Example 2, the Tg of the flat plate was 131 ° C. From this, it was found that the polymerization reactivity at high temperatures was also excellent.

Example 4 Preparation of Reinforced Molded Material and
In a separable flask having a curing reaction of 500 ml, dicyclopentadiene (containing 10% of a trimer of cyclopentadiene) 10
0g, glass fiber chopped strand (product number:
60 g of CS3E227, manufactured by Nitto Boseki Co., Ltd., dried at 120 ° C. for 30 minutes and then returned to room temperature) and 60 g of calcium carbonate powder (trade name: Shiraishi A, Shiraishi Industry Co., Ltd.)
After drying at 120 ° C. for 30 minutes and returning to room temperature) 6
After adding 0 g, degassing and degassing while stirring with a mechanical stirrer, the atmosphere was replaced with nitrogen.

Liquid antioxidants (2,6-di-tert-
Butylphenol and 2,6-di-tert-butyl-4
Benzylidene (1,3-dimesitylimidazolidine-2) to methyl phenol in a ratio of 2: 1.
2.1 g of a catalyst solution in which 1% of -ylidene) (tricyclohexylphosphine) ruthenium dichloride (the same as in Example 1) was dissolved was added to a separable flask while vigorously stirring with a mechanical stirrer. The separable flask was placed in a water bath at 34 ° C., and after stirring was continued for 50 minutes, the mixture was immediately cooled with ice. As a result, a fluid high-viscosity mixture (molding material 4) was obtained.

The molding material 4 was placed in a refrigerator at −10 ° C.
When stored for a week, it remained in a fluid state.
Using 65 g of the molding material 4 after storage, the mold temperature was set to 120
When a flat plate was formed in the same manner as in Example 2 except that the temperature was set at 80 ° C. and the lower mold was set at 80 ° C., a glass fiber reinforced molded product was obtained.

Example 5 Prepreg (resin impregnated base material) method
Preparation of Copper-Clad Laminate by Tetracyclo [7.
4.0.1 ^10,13 . 0 ^2,7 ] Trideca-2,4,6,11
98 ml of tetraene (Diels-Alder adduct of indene and cyclopentadiene) and a stirrer were placed. There, a liquid antioxidant (a mixture of 2,6-di-tert-butylphenol and 2,6-di-tert-butyl-4-methylphenol at a ratio of 2: 1) was mixed with benzylidene (1,3- 2.1 g of a catalyst solution obtained by dissolving 2% of dimesityl imidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride (the same as in Example 1) was added thereto, followed by stirring to obtain a mixture 1. The ruthenium concentration in the liquid is 0.5 mmol / liter).
All of the above operations were performed in a nitrogen atmosphere.

A Teflon sheet is laid in a dry box under a nitrogen atmosphere, and a 0.19-mm-thick glass cloth (product number: WE 19 105, manufactured by Nitto Boseki Co., Ltd.) is impregnated with the mixed solution 1 thereon. Was laid, and a Teflon (registered trademark) sheet was laid thereon, and was placed at room temperature (23 ° C.) for 2 hours to obtain a prepreg in a semi-cured state. The prepreg was wound into a roll with the Teflon sheet attached, and stored at −10 ° C. for 2 days in a nitrogen atmosphere. After returning the prepreg after storage to room temperature, the prepreg was taken out into the air and the Teflon sheet was peeled off. The four prepregs were stacked, 18 μm electrolytic copper foil was laminated on both sides of the outer layer, sandwiched between two stainless steel end plates by a press molding apparatus, and heated and pressed at 190 ° C. for 10 minutes at a load of 30 kg per 1 cm 2, A 0.8 mm copper-clad laminate was obtained. When the copper foil peel strength of the obtained copper-clad laminate was measured,
It was 300 gf / cm.

Comparative Example 3 Prepreg (resin impregnated base material) method
Preparation of Copper-Clad Laminate by Tetracyclo [7.
4.0.1 ^10,13 . 0 ^2,7 ] Trideca-2,4,6,11
-Add 99.5 ml of tetraene (Diels-Alder adduct of indene and cyclopentadiene) and a stirrer,
78 mg of triphenylphosphine (concentration of 3 mmol / liter in the polymerization system) was added, and the mixture was stirred and dissolved.

Liquid anti-aging agent (2,6-di-tert-
Butylphenol and 2,6-di-tert-butyl-4
-Methylphenol mixed at a ratio of 2: 1) and 2.1 g of a catalyst solution obtained by dissolving 2% of benzylidenebis (tricyclohexylphosphine) ruthenium dichloride (manufactured by Strem Chemical Co.) were added, followed by stirring. (The ruthenium concentration in the formulation is
0.5 mmol / l). All of the above operations were performed in a nitrogen atmosphere.

The subsequent operations were the same as in Example 5 to obtain a copper-clad laminate. However, the peel strength of this copper-clad laminate was 200 gf / cm. The small peel strength indicates that sufficient adhesion was not achieved when laminated with a copper foil due to the progress of curing during storage.

Example 6 In a 300-ml separable flask, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) was added.
8.5 mg (concentration 0.1 mmol / liter in a polymerization system, ruthenium concentration 10) (tricyclohexylphosphine) ruthenium dichloride (synthesized based on the description in Org. Lett., 1999, vol. 1, p. 953)
ppm) and a stirrer. To this, toluene 0.2m
After adding l, stirring with a magnetic stirrer to dissolve the ruthenium catalyst, 99.8 ml of dicyclopentadiene (containing 10% of a trimer of cyclopentadiene) was added and stirred. The stirrer was taken out, placed in a 45 ° C. water bath, stirred with a mechanical stirrer for 50 minutes, and immediately cooled with ice to obtain a fluid high-viscosity liquid (molding material 5). All of the above operations were performed in a nitrogen atmosphere.

Next, the molding material 5 was molded in the same manner as in Example 2 to obtain a flat plate. The obtained molded product was sufficiently cured, and had a Tg of 143 ° C. Thus, it was found that sufficient reactivity was obtained even when the amount of the catalyst was reduced.

Comparative Example 4 Dicyclopentadiene (containing 10% of a trimer of cyclopentadiene) 10 was placed in a 300 ml separable flask.
Then, 0 ml and 5.2 mg of triphenylphosphine (concentration in the polymerization system: 0.2 mmol / liter) were added, and dissolved by stirring with a mechanical stirrer. Then, benzylidenebis (tricyclohexylphosphine) ruthenium dichloride (manufactured by Strem Chemical) was added to 8.2.
mg (concentration in the polymerization system: 0.1 mmol / liter, ruthenium concentration: 10 ppm), and stirred to dissolve. Put this in a 45 ° C water bath and stir for 50 minutes.
Immediately on ice cooling, it became a fluid, high-viscosity liquid (molding material 6). All of the above operations were performed in a nitrogen atmosphere.

Next, the molding material 6 was molded in the same manner as in Example 2 to obtain a flat plate. The obtained molded product was not sufficiently cured and was rubbery. This molded article was placed in an oven at 150 ° C. for 30 minutes and post-cured.
Curing was insufficient and Tg was 65 ° C. As described above, in Comparative Example 4, by reducing the amount of the catalyst, the reactivity at a high temperature became worse as compared with Comparative Example 2, and the curing was insufficient even after the post cure.

[0099]

According to the present invention, a ruthenium catalyst having a greater temperature dependency than a conventionally used metathesis polymerization catalyst is used. The ruthenium catalyst used in the present invention has the advantages of excellent stability at low temperatures and excellent reactivity at high temperatures. Therefore, the molding material in the semi-cured state of the present invention is:
Excellent low-temperature stability and high-temperature polymerization reactivity.

In the production method of the present invention, since a catalyst having excellent reactivity at high temperatures is used, the curing time can be shortened and the amount of the catalyst can be reduced. Can be industrially advantageously produced.

Further, according to the present invention, a molding material having extremely small contents of catalyst-derived metal, halogen and the like can be obtained.
Therefore, it is particularly suitable for the production of a molded article in which the metal content in the finally obtained molded article is required to be reduced as much as possible, such as an electric / electronic part application.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B29K 105: 06 B29K 105: 06 C08L 65:00 C08L 65:00 (72) Inventor Naoki Kanda Kawasaki, Kanagawa Prefecture 1-2-1 Yoko, Kawasaki Ward F-term in the Zeon Corporation Development Center (reference) 4F071 AA69 AF13 AF36 AF40 AF58 AH13 BA02 BB01 BB12 BC01 BC03 4F204 AA12 EA03 EB01 EE03 EE10 EE23 EF27 EK13 EK17 4J032 CA23 CA24 CA27 CA28 CA35 CA36 CA38 CA43 CA45 CA46 CA68 CB01 CB03 CD02 CE06 CE07 CF01 CG07

Claims (4)

[Claims] A curable molding material in a pre-cured state obtained by subjecting a norbornene-based monomer to ring-opening metathesis polymerization in the presence of a ruthenium complex catalyst, wherein at least one ruthenium complex catalyst is used as the ruthenium complex catalyst. A molding material characterized by using a ruthenium complex in which a heteroatom-containing carbene compound is coordinated. 2. The molding material according to claim 1, wherein the concentration of the ruthenium compound contained in the molding material is 25 ppm or less. 3. A method for producing a molded product, comprising: a first step of obtaining the molded material according to claim 1 or 2; and a second step of shaping the molded material into a predetermined shape and curing by heating. Method. 4. A molded article formed by using the molding material according to claim 1 or 2.