JP2001278962A - Resin composition and method of producing hardened product by applying the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that overcomes the shortness of application time and the deterioration due to the heat of high activity metathesis polymerization catalyst which is one component type and to provide a method of manufacturing for a hardening material applying it. SOLUTION: The resin composition contains at least a kind of component from (a) the metathesis polymerization cycloolefin compound and/or its compound, (b) the metathesis polymerization catalyst shown by formula (1), (c) the filling material or the additive. [M shows ruthenium or osmium. X or X1 shows an anionic lignd independently, respectively. L shows a neutral electron- donating group. R to R5 show each hydrogen or a specific organic group having the carbon number of 1 to 20].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for metathesis polymerization and a method for producing a cured product using the same. These resin compositions or cured products can be used
It is useful as an insulating material for electricity, a coating material, a molding material for housing equipment such as a septic tank / bath tub, and an industrial material such as a corrugated sheet / pipe.

[0002]

2. Description of the Related Art It is known that cycloolefins undergo ring-opening polymerization using a metathesis polymerization catalyst system. For example, J. Am. Chem. Soc. , 196
0, Vol. 82, 2337 describes that ring-opening polymerization of norbornene is carried out by a metathesis catalyst system.
ngew. Chem. Int. Edn. , 1964, V
No. 3,723, describes that cyclopentene undergoes ring-opening polymerization with a metathesis catalyst system [MoCl5 / Al (C2H5) 3]. Further, a method of producing a polymer by ring-opening polymerization of a cycloolefin is also known. For example, JP-A-50-130900 and JP-A-52-130900
No. 33000 discloses a method for producing a ring-opening polymer using a metathesis catalyst system comprising a halide such as tungsten or molybdenum and an organoaluminum compound.

[0003] JP-A-3-205409 discloses a two-component type in which a catalyst component selected from tungsten hexachloride and tungsten oxytetrachloride is combined with an activator selected from diethylaluminum chloride and ethylaluminum dichloride. A method for producing a dicyclopentadiene polymer crosslinked by a reaction injection molding method using the metathesis catalyst system described above is disclosed. In these metathesis catalyst systems,
It has been found that the catalyst component is activated by the activator and causes ring-opening polymerization of the norbornene-type monomer. When the above reaction injection molding is performed, the solution A and the solution B
Are impinged and mixed, and the mixture is immediately poured into a mold in a liquid state, and is subjected to ring-opening polymerization in a lump.

[0004] It is known that cured products obtained by ring-opening polymerization of these cycloolefin compounds with a metathesis catalyst system are excellent in mechanical properties, electrical properties, water resistance and the like. However, in conventional metathesis catalyst systems, poor curing is likely to occur due to the effects of oxygen in the air, moisture attached to the filler, and functional groups such as hydroxyl groups and epoxy groups contained in the additives. For this reason, since the usual filler cannot be added, the use of the molded article has been limited. Also, in order to eliminate the influence of moisture and oxygen in the air, the working environment at the time of molding has been significantly restricted, such as setting the molding environment to a nitrogen atmosphere or limiting the molding to molding in a mold.

On the other hand, a one-component type high-activity metathesis polymerization catalyst which is hardly affected by oxygen and moisture in the air and the material is disclosed in Japanese Patent Publication No. Hei 9-512828.

[0006]

The above-mentioned highly active metathesis polymerization catalyst is deteriorated by heat due to heating and heat generated during the polymerization process. There is a problem that the amount used is large. In addition, there is a problem that the viscosity increases immediately after the addition of the catalyst, the usable time required for molding is short, and the workability is poor. SUMMARY OF THE INVENTION The present invention provides a resin composition which overcomes the deterioration of a one-component type high activity metathesis polymerization catalyst due to heat and short pot life, and a method for producing a cured product using the same.

[0007]

Means for Solving the Problems The present inventors have studied various types of resin compositions which are polymerized and molded from cycloolefin compounds using a metathesis polymerization catalyst, and as a result, by using a specific metathesis polymerization catalyst, Equivalent curability can be obtained with a much smaller amount than conventional metathesis catalysts, and sufficient pot life can be ensured without adding a polymerization rate regulator, resulting in significant economic and workability. Was found to be improved. In addition, we found that the cured product obtained by polymerization has properties equivalent to or better than the water resistance, tough mechanical properties, and electrical properties of the cured product obtained by the conventional metathesis polymerization system. Thus, the present invention has been completed.

That is, the present invention provides (a) a metathesis polymerizable cycloolefin compound and / or a polymer thereof,
A resin composition comprising (b) a metathesis polymerization catalyst represented by the general formula (1) and (c) at least one component selected from a filler, a reinforcing material, and an additive.

Embedded image (M represents ruthenium or osmium, X and X ¹ each independently represent an anionic ligand, L represents a neutral electron donating group, R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ is each independently hydrogen, an alkyl group having 1 to 20 carbon atoms,
Alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, aryl group, carboxylate group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkenyloxy group having 2 to 20 carbon atoms, 2 carbon atoms An alkynyloxy group, an aryloxy group, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, and an alkylsulfinyl group having 1 to 20 carbon atoms. Show. )

In the above resin composition, the preferable content of the component is 0.0001 to 20 parts by weight of the component (b) and 100 parts by weight (based on the component) of the component (a). 0.001 to 700 parts by weight.

[0010] The present invention also provides a method for producing a cured product, characterized by heating and curing the above resin composition.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION As the metathesis polymerizable cycloolefin compound in the component (a) used in the present invention, any compounds useful in metathesis polymerization may be used. Among them, norbornene-based monomers such as substituted or unsubstituted norbornene, dicyclopentadiene, and dihydrodicyclopentadiene are preferably used.

Examples of the norbornene compounds include bicyclic norbornenes such as norbornene, methyl norbornene, dimethyl norbornene, ethyl norbornene, ethylidene norbornene, butyl norbornene, dicyclopentadiene (a dimer of cyclopentadiene), dihydrodicyclopentadiene, methyl Tricyclic norbornenes such as dicyclopentadiene, dimethyldicyclopentadiene,
Tetracyclododecene, methyltetracyclododecene,
Examples include tetracyclic norbornenes such as dimethylcyclotetradodecene, and pentacyclic or higher norbornenes such as tricyclopentadiene (trimer of cyclopentadiene) and tetracyclopentadiene (tetramer of cyclopentadiene). A compound having two or more norbornene groups,
For example, norbornadiene, tetracyclododecadiene,
Symmetric tricyclopentadiene or the like can also be used as a polyfunctional crosslinking agent.

Of these, dicyclopentadiene, methyltetracyclododecene, ethylidene norbornene, tricyclopentadiene, and tetracyclopentadiene are preferred, and dicyclopentadiene is particularly preferred, in terms of availability and economy.

These norbornene compounds are used alone,
Although it can be used as a mixture of a plurality of monomers, it is preferably a mixture containing 50% by weight or more of dicyclopentadiene and, in addition, tricyclopentadiene and / or tetracyclopentadiene.

Cyclobutene (other than norbornene), cyclopentene, cyclooctene, cyclooctadiene, which is capable of ring-opening copolymerization with the norbornene-based compound,
Cycloolefins such as cyclododecene, tetrahydroindene, methyltetrahydroindene, and cyclododecatriene can be mixed and used as long as the object of the present invention is not impaired. Incidentally, normal commercially available dicyclopentadiene may contain vinylnorbornene, tetrahydroindene, methylvinylnorbornene, methyltetrahydroindene, methyldicyclopentadiene, dimethyldicyclopentadiene, tricyclopentadiene, and the like as impurities. Dicyclopentadiene of various purity is commercially available. The dicyclopentadiene used in the present invention has a purity of 80% by weight or more, preferably 90% by weight or more, although it varies depending on the intended use of the obtained polymer.

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

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

Component (a) contained in the resin composition of the present invention
Contains, in addition to the metathesis-polymerizable cycloolefin-based compound, a polymer obtained by partially polymerizing the metathesis-polymerizable cycloolefin-based compound (including what is called semi-cured or B-stage). You may. If the metathesis polymerizable cycloolefin-based compound and the metathesis polymerization catalyst of the general formula (1) are mixed, a polymer is generated with the lapse of time, although the degree varies, and the component (a) in the composition after mixing has the metathesis polymerizability. It becomes a mixture of a cycloolefin compound and its polymer. Here, the production rate of the polymer can be appropriately adjusted by changing the conditions (such as the amount, type, temperature, and time of the metathesis polymerization catalyst).

The component (b) used in the present invention is a metathesis polymerization catalyst represented by the general formula (1) as described above. This catalyst is different from a conventionally known two-component metathesis catalyst system in which a catalyst component and an activator are combined, unlike a cycloolefin-based catalyst without easily losing catalytic activity due to oxygen or moisture in the air. It is a catalyst capable of subjecting a compound to ring-opening polymerization by a metathesis reaction.

In the general formula (1), R, R ¹ , R ² , R ³ , R ⁴
And R ⁵ are an alkyl group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms.
They may be substituted with 0 alkoxy groups or aryl groups, and these groups may be further substituted with halogen, alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, or phenyl groups. In addition, these ligands include aryl or hydroxyl groups, thiol groups, thioether groups,
Ketone group, aldehyde group, ester group, ether group, amine group, imine group, amide group, nitro group, carboxylic acid group, disulfide group, carbonate group, isocyanate group, carbodiimide group, carboalkoxy group, carbamate group, halogen etc. It may contain a functional group. Preferably, R is hydrogen, R ¹ is an alkyl group of 1 to 20 carbon atoms,
It is an alkenyl group or an aryl group having 2 to 20 carbon atoms. More preferably, R ¹ is a phenyl group or a vinyl group, and these groups may be partially substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group or a functional group. . Particularly preferred R ¹ is chlorine, bromine,
Iodine, _{fluorine, -NO 2, -N (CH 3} ) 2, a methyl group, partially substituted phenyl group or a vinyl group in a methoxy group and a phenyl group. Most preferred R ¹ is a phenyl group or —C ＝ C (CH ₃ ) ₂ .

R ² , R ³ , R ⁴ and R ⁵ are each independently halogen, an alkyl group having 1 to 20 carbon atoms,
Alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, aryl group, carboxylate group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkenyloxy group having 2 to 20 carbon atoms, 2 carbon atoms Alkynyloxy group, aryloxy group, alkoxycarbonyl group having 2 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms, alkylsulfonyl group having 1 to 20 carbon atoms and 1 to 20 carbon atoms
Alkylsulfinyl group. Imidazolidine ligands are also referred to as 4,5-dihydro-imidazole-2-ylidene ligands.

R ² and R ³ may together form a cycloalkyl group or an aryl group. R ² and R ³ are preferably halogen, a phenyl group or a cycloalkyl group formed by combining R ² and R ³ . R ⁴ and R
⁵ is a saturated or unsaturated aryl group, respectively.

As R ⁴ and R ⁵ , a bulky group is preferable in terms of thermal stability, and R ⁴ and / or R ⁵ are each preferably a compound represented by the general formula (2).

Embedded image Here, R ⁹ , R ¹⁰ and R ¹¹ are each independently a halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group or a hydroxyl group, a thiol group, a thioether group, a ketone group. , Aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carbalkoxy, carbamate, halogen and other functional groups It is. R ⁹ , R ¹⁰ and R ¹¹ are particularly preferably each a methyl group.

In the general formula (1), X and X ¹ each independently represent hydrogen, halogen or an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxide group having 1 to 20 carbon atoms, an aryloxide group, 3-20 alkyl diketonate group, aryl diketonate group, carboxylate group having 1-20 carbon atoms, aryl sulfonate group, alkyl sulfonate having 1-20 carbon atoms, alkylthio group having 1-20 carbon atoms, carbon number It is an alkylsulfonyl group having 1 to 20 carbon atoms or an alkylsulfinyl group having 1 to 20 carbon atoms. X and X1 may be partially substituted by an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group. May be substituted with an alkyl group, an alkoxy group having 1 to 5 carbon atoms and a phenyl group. More preferably, X and X 1 are halogen, benzoate, a carboxylate group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a phenoxy group, an alkoxy group having 1 to 5 carbon atoms,
Alkylthio group having 1 to 5 carbon atoms, aryl group, 1 carbon atom
To 5 alkylsulfonate groups. More preferably, halogen, CF ₃ CO ₂ , CH ₃ CO ₂ , CFH ₂ C
O ₂ , (CH ₃ ) ₃ CO, (CF ₃ ) ₂ (CH ₃ ) CO, (C
F ₃ ) (CH ₃ ) ₂ CO, PhO (phenoxy), MeO
(Methoxy), EtO (ethoxy), a tosylate group, a mesylate group or a trifluoromethanesulfonate group. Most preferably, X and X ¹ are each chlorine.

L represents a neutral electron donating group. The neutral electron donating group is a group having a neutral charge when the coordination to the central metal is removed. Preferably, phosphine, sulfonated phosphine, phosphite, phosphinite,
Examples include phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine and thioether compounds.
More preferably, it is a compound represented by PR ⁶ R ⁷ R ⁸ , wherein R ⁶ , R ⁷ and R ⁸ are each independently an aryl group,
It is an alkyl group having 1 to 10 carbon atoms, a primary alkyl group, a secondary alkyl group or a cycloalkyl group. Particularly preferably, -P (cyclohexyl) ₃ , -P (cyclopentyl) ₃ , -P (isopropyl) ₃ and -P (phenyl) ₃
It is.

Examples of the structure of the catalyst of the present invention include the following chemical formulas (3) to (8).

Embedded image

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

Here, Mes is known as a so-called “mesityl” group represented by the formula (9). Also, i-Pr
Is an isopropyl group.

A method for synthesizing the above compound (catalyst) is already known. For example, Organic Letters Volume 1, Issue 1, 953
-956 (1999), the ligand L
As the compound to be 1, 1,3-dimesityl-4,5-
It uses dihydroimidazolium tetrafluoroborate.

The amount of the metathesis polymerization catalyst, ie, component (b), used is 0.0001 to 20 parts by weight (based on 100 parts by weight of the metathesis-polymerizable cycloolefin compound of component (a) and / or a polymer thereof). Parts by weight, preferably 0.001 to 5 parts by weight. If the amount is less than 0.0001 parts by weight, curing will be poor, and if it exceeds 20 parts by weight, it is uneconomical.

The resin composition of the present invention comprises at least one kind of a filler, a reinforcing material, or an additive (other than the filler and the reinforcing material) in addition to the component (a) and the component (b). It contains three components (component c).

Here, the filler is used for the purpose of improving mechanical properties such as shrinkage and elasticity of the obtained cured product, and powdered or granular inorganic filler and organic filler are used. is there.

As the inorganic filler, for example, crystalline silica,
There are fused silica, synthetic silica, silica sand, calcium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium oxide, clay, expanded graphite, aluminum fluoride, alumina, etc., and wood powder, polyester, silicone, polyacrylonitrile as an organic filler. Butadiene-styrene (A
BS). Further, a foamable organic filler (Expancel, manufactured by Nippon Ferrite Co., Ltd.) in which isobutane gas is sealed in a core in a vinylidene chloride-polyacrylonitrile cell is also included. The grade such as the particle size, shape, and quality can be appropriately determined depending on the use, physical properties, and the like of the cured product. As the inorganic filler, silica, aluminum hydroxide, and aluminum fluoride are preferable from the viewpoint of electrical properties and thermal conductivity. Commercially available products include CRT-AA, CRT
-D, RD-8, SO-R series, SO-H series (trade name, manufactured by Tatsumori), COX-31 (trade name, manufactured by Micro Corporation), C-303H, C-315H, C- 30
8 (trade name, manufactured by Sumitomo Chemical Co., Ltd.) and SL-700 (trade name, manufactured by Takehara Chemical Co., Ltd.). The amount (content) of the filler may be appropriately determined depending on the use, physical properties, and the like of the cured product, but may be 1 to 100 parts by weight of the metathesis polymerizable cycloolefin-based compound of the component (a) and / or 100 parts by weight of the polymer. ７００700 parts by weight, preferably 5 to 500 parts by weight. If the amount is less than 1 part by weight or exceeds 700 parts by weight, improvement in mechanical properties such as shrinkage and elasticity of the cured product cannot be expected.

The reinforcing material is contained for the purpose of improving the mechanical properties of the cured product, and a typical one is a fiber reinforcing material. Examples of the fiber reinforcing material include glass fiber, carbon fiber, inorganic reinforcing material such as metal fiber and aramid fiber, polyester fiber, olefin fiber such as polyethylene and polypropylene, preferably glass fiber,
It is a carbon fiber reinforcing material or an aramid fiber. These reinforcing materials may be long fibers or short fibers. Roving in which the strands are aligned to form a bundle, roving cloth weaving the roving, continuous strand mat in which random coil-shaped long fibers are molded into a mat shape, chopped strands in which long fibers are cut, and gluing of chopped strands with a binder Chopped strand mat, surfacing mat, twill weave mat or cloth and strand combination 3
Dimensional glass mat (Chori Co., Ltd., trade name: Parabeam),
Non-woven fabrics, continuous strands, and preforms in which strands are three-dimensionally formed can be used.

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

The amount (content) of these reinforcing materials used is 1 to 700 parts by weight, preferably 5 parts by weight, per 100 parts by weight of the metathesis polymerizable cycloolefin compound of component (a) and / or its polymer. ５００500 parts by weight. If the amount is less than 1 part by weight, improvement in mechanical strength cannot be expected, and if it exceeds 700 parts by weight, the mechanical properties of the cured product and the workability during molding deteriorate.

As the component (c), in addition to the above-mentioned filler and reinforcing material, various additives can be contained for the purpose of improving the physical properties, appearance, and workability of the cured product. Such additives include modifiers, polymerization rate regulators, defoamers, foaming agents, mold release agents, colorants, stabilizers (ultraviolet absorbers, light stabilizers, antioxidants), adhesive properties There are imparting agents, flame retardants, wetting agents, dispersants, thixotropic materials, and organic peroxides.

Examples of the modifying agent include elastomer, natural rubber, butadiene rubber, styrene butadiene copolymer (SBR), styrene butadiene-styrene block copolymer (SBS), styrene-maleic acid copolymer, ethylene -Copolymers such as vinyl acetate copolymers,
Thermoplastic resins such as polymethyl methacrylate, polyvinyl acetate, and polystyrene are exemplified. In addition, these copolymers and thermoplastic resins may be esterified, or a polar group may be grafted. In addition, physical properties can be improved by blending epoxy resin, urethane resin, polyester resin, silicone resin, phenol resin, polyimide resin, polyamide resin, polyamideimide resin and derivatives thereof. Further, for example, a compound obtained by reacting an epoxy with norbornene monocarboxylic acid, a compound obtained by reacting an isocyanate compound with norbornene-ol, a hymic acid-modified polyester, a petroleum resin, and the like are also included. Examples of the petroleum resin include those produced using a known C5 or C9 fraction purified from an ethylene plant as a raw material. For example, Quinton (trade name, manufactured by Zeon Corporation), Norsolex (trade name, manufactured by Zeon Corporation, thermoplastic polynorbornene resin) and the like can be mentioned. These petroleum resins preferably have a number average molecular weight (converted by a gel permeation chromatography method using a standard polystyrene calibration curve) of 500 or more, and have a functional group such as a hydroxyl group or an ester group in the resin skeleton. Is more desirable.

Further, a Defensor MCF-300 or Megafac F-178RM (Dai Nippon Ink Chemical Industry Co., Ltd.)
(Product name) The copolymer containing a perfluoroalkyl group precipitates on the surface during the polymerization of the resin composition of the present invention, and is therefore effective for modifying the surface state, particularly for improving heat resistance.

An ion scavenger may be used to modify the resin by adsorbing ionic impurities in the resin composition. The ion trapping agent is roughly classified into an ion-adsorbing substance that performs ion exchange with an ion-adsorbing substance that simply adsorbs ions. Examples of the ion-adsorbing substance include activated carbon, zeolite, silica gel, activated alumina, and activated clay.
Ion exchangers are further divided into organic ion exchangers and inorganic ion exchangers.Examples of organic ion exchangers include cation-exchange sulfonic acid groups, phenolic hydroxyl groups,
Polystyrenesulfonic acid having a carboxyl group, phenolsulfonic acid resin, polymethacrylic acid, etc., an anion-exchangeable amino group, substituted amino group, styrene-based polymer having a quaternary ammonium base, or a chelate resin, or a chelate resin thereof Mixtures and the like can be mentioned.

Inorganic ion exchangers can be broadly classified into those which adsorb anions and cations, cations and anions. Examples of inorganic ion exchangers that adsorb anions and cations include beryllium oxide hydrate, gallium oxide hydrate, lanthanum oxide hydrate, iron oxide hydrate, aluminum oxide hydrate, and titanium oxide hydrate. Metal hydrates such as iron oxide hydrate, zirconium oxide hydrate, tin oxide hydrate, germanium oxide hydrate and thorium oxide hydrate. Further, both ion exchangers IX-1100 (calcium-based) and IX-1 which are marketed by Toa Gosei Co., Ltd.
320 (antimony-magnesium-aluminum system), IXE-600, IXE-633, IXE-68
0 (antimony-bismuth-based) can also be used. The IX series is preferred from the viewpoint of effect vs. cost.

Examples of the inorganic ion exchanger that adsorbs cations include antimony pentoxide hydrate, manganese oxide hydrate, silicon oxide hydrate, niobium oxide hydrate, tantalum oxide hydrate, and molybdenum oxide water. Metal hydrates such as hydrates and tungsten oxide hydrates, zirconium phosphate, zirconium tungstate, ammonium phosphomolybdate, phosphoantimonic acid, zirconium molybdate, titanium molybdate, zirconium tungstate, titanium tungstate, molybdate Tin, tin tungstate, zirconium antimonate, titanium antimonate,
Examples include zirconium selenate, zirconium tellurate, zirconium silicate, zirconium phosphosilicate, zirconium polyphosphate, chromium tripolyphosphate, and antimony triphosphate. Cation exchangers IX-100 (zirconium-based), IX-150 (zirconium-based),
XE-200 (tin-based), IXE-300 (antimony-based), IXE-400 (titanium-based) and the like can also be used.

Examples of the inorganic ion exchanger that adsorbs anions include antimony trioxide hydrate, bismuth oxide hydrate, and hydrotalcites. Further, anion exchangers IX-500, IX-550 (bismuth-based) marketed by Toa Gosei Co., Ltd.,
IXE-700 (magnesium-aluminum system), I
XE-702 (aluminum-based), IXE-800 (zirconium-based), IXE-1000 (lead-based) and the like can also be used.

Among these inorganic ion exchangers, a bismuth oxyacid-based compound represented by the following general formula (11) disclosed in JP-A-2-294354 is preferable.

Embedded image Bix (M) yOz (OH) p (X) q (Y) r · nH2O (11) (In the general formula (11), M is a metal such as Sb or Si, X and Y are carbonate groups, Oxyacid residues such as nitric acid group, sulfonic acid group and silicate group, x, y, z, p, q, r and n are 0
Represents a number that includes the above decimals. )

The ion scavenger is preferably finely dispersed, and is preferably made porous and atomized to increase the specific surface area in order to enhance the adsorption capacity and exchange capacity. The particle size is usually 50 μm or less, preferably 25 μm or less. The addition amount is usually 0.01 to 100 parts by weight, preferably 0.1 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight. However, the amount and type of these ion scavengers vary depending on the use and the target trapped ion, and two or more types can be used in combination, and the method of use is not limited.

The amount (content) of these modifiers depends on the physical properties of the desired cured product, but is usually 0.5 to 100 parts by weight based on 100 parts by weight of the component (a). If the amount exceeds 100 parts by weight, inconveniences such as a decrease in curability and an increase in viscosity occur.

Examples of the polymerization rate regulator include phosphorus compounds such as triisopropylphosphine, triphenylphosphine and dicyclohexylphenylphosphine, 1-hexene and allyl compounds. This amount (content) is 0.005 to 20 parts by weight per 100 parts by weight of the component (a).
Parts by weight. Since this polymerization rate regulator is for the purpose of controlling the usable time (pot life) of the resin composition,
When the time is short, the amount used is small, and when the time is long, the amount is large.

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

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

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

The stabilizer includes an ultraviolet absorber, a light stabilizer and an antioxidant. Here, as the ultraviolet absorber, for example, phenyl salicylate, para-t-
Salicylic acid-based ultraviolet absorbers such as butylphenyl salicylate, benzophenone-based ultraviolet absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, -(2'-hydroxy-5'-methylphenyl) benzotriazole, 2-
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole-2- (2'-hydroxy-
Benzotriazole ultraviolet absorbers such as 3 ', 5'-di-t-amylphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3,3' -Cyanoacrylate-based ultraviolet absorbers such as diphenylacrylate. These may be used alone or in combination of two or more.
The amount (content) of these ultraviolet absorbers may be appropriately determined depending on the use environment and required characteristics of the cured product.
Usually, the amount is 0.05 to 20 parts by weight based on 100 parts by weight.

As the light stabilizer, bis (2,2,6,6)
-Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl)
Hindered amine light stabilizers such as sebacate and dimethyl succinate / 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate are exemplified. The amount (content) of this light stabilizer is
Usually, 0.05 to 20 parts by weight per 100 parts by weight of component (a)
Parts by weight are added.

As antioxidants, parabenzoquinone,
Quinones such as tolquinone and naphthoquinone; hydroquinones such as hydroquinone and para-t-butylcatechol; 2,5-di-t-butylhydroquinone; and di-t-butyl.
Paracresol, hydroquinone monomethyl ether,
Pyrogallol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, stearyl-β- (3′5-di-tert-butyl-4-methylphenol)
(Hydroxyphenyl) propionate, tetrakis-
[Methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 2,2'-
Methylene bis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol) 1,3,5-trimethyl-
2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′,
5'-di-t-butyl-4'-hydroxybenzyl) -S
Reaction product of triazine-2,4,6- (1H, 3H, 5H) trione and p-cresol / dicyclopentadiene / isobutylene (trade name W manufactured by Goodyear Chemical)
Phenols such as INGSTAY L-HLS);
Copper salts such as copper naphthenate and copper octenoate; quaternary ammonium salts such as trimethylbenzylammonium chloride, trimethylbenzylammonium maleate and phenyltrimethylammonium chloride; oximes such as quinone dioxime and methyl ethyl ketoxime; triethylamine hydrochloride; Amine hydrochlorides such as dibutylamine hydrochloride; sulfur-based compounds such as 1,11- (3,6,9-trioxaundecyl) -bis (3-dodecylthiopropionate); triphenylphosphite; tris Phosphorus-based compounds such as nonylphenyl phosphite can be used. The type and amount of these antioxidants are appropriately selected depending on conditions such as compatibility with the filler, intended molding workability, and resin storage stability. Use amount (content)
Usually, from 0.001 to 1 based on 100 parts by weight of the component (a).
0 parts by weight.

Examples of the adhesion-imparting agent include silane coupling agents. Here, as the silane coupling agent, usually, a compound represented by the formula Y _n SiX _4-n (where Y has a functional group,
X is a monovalent group bonded to Si, X is a monovalent group which has hydrolyzability and is bonded to Si, and n is an integer of 1 to 3). Examples of the functional group in Y include groups such as vinyl, amino, epoxy, chloro, mercapto, methacryloxy, cyano, carbamate, pyridine, sulfonyl azide, urea, styryl, chloromethyl, ammonium salt, and alcohol. X includes, for example, chloro, methoxy, ethoxy, methoxyethoxy and the like. Specific examples include vinyltrimethoxysilane, vinyltris (2-
Methoxyethoxy) silane, γ- (2-aminoethyl)
-Aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N, N-dimethylaminophenyltriethoxysilane, mercaptoethyltriethoxysilane , Methacryloxyethyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, 3-
(N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane hydrochloride and the like, and these can be used in combination. The silane coupling agent is usually used in an amount of 0.1 part by weight based on 100 parts by weight of the component (a).
001 to 5 parts by weight.

As the flame retardant, hexabromobenzene,
Tetrabromobisphenol A, decabromodiphenyl oxide, tribromophenol, dibromophenyl glycidyl ether, perchloropentacyclodecane,
Halogen compounds such as heptate derivatives may be used alone or in combination of two or more. Further, a phosphate compound such as tris (dichloropropyl) phosphate and tris (dibromopropyl) phosphate, a boric acid compound and the like can also be used in combination. Further, examples of the auxiliary flame retardant include antimony trioxide, iron oxide, aluminum hydride and the like. When these are used in combination with the flame retardant, the flame retardant effect is further enhanced. Usually, the halogen-based flame retardant is used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the cycloolefin-based compound, and the auxiliary flame retardant such as antimony trioxide is used in an amount of 1 to 15 parts by weight. Hydrates such as commercially available aluminum hydroxide and magnesium hydroxide can also be used as fillers for flame retardancy as plastic fillers.
The amount (content) of these used is usually 10 to 300 parts by weight based on 100 parts by weight of the component (a).

In addition, a commercially available wetting agent or dispersant such as BYK series manufactured by BYK-Chemie can be added to improve the wettability between the filler and the cycloolefin-based compound. In order to improve molding workability, a release agent such as a silicone oil or zinc stearate can be added. In addition, an inorganic or organic thixotropic material can be added. As inorganic thixotropic materials,
For example, silica fume (trade name: # 200, R972, RX200, etc., manufactured by Nippon Aerosil Co., Ltd.), bentonite, special silica balloon (trade name, Ba, manufactured by DuPont)
omasil). As organic thixotropic materials,
For example, Dispalon 6600 (trade name, manufactured by Kusumoto Kasei Co., Ltd.), BYK-410 (BYK, trade name), and the like can be given.

As the organic peroxide, for example, cumene hydroperoxide, tert-butylperoxy-
2-ethyl hexanate, methyl ethyl ketone peroxide, benzoyl peroxide, acetylacetone peroxide, bis-4-tert-butylcyclohexanedicarbonate, 2,5-dimethyl-2,5-bis (t
Known ones such as -butylperoxy) hexyne-3 are exemplified. These may be used in combination of two or more. The used amount (content) is usually 0.1 to 10 parts by weight based on 100 parts by weight of the component (a).

The resin composition of the present invention is prepared by dissolving a metathesis polymerization catalyst of the general formula (1) in a metathesis polymerizable cycloolefin compound, and adding at least one type of filler, reinforcing material or additive. It is obtained by adding a third component (component c). At this time, the temperature at which the catalyst is added to and dissolved in the cycloolefin compound and the temperature at which the third component is added are usually -10 to 70C, preferably 5 to 50C.

The resin composition of the present invention is cured by heating to obtain a molded product. The heating operation may be one-stage heating or two-stage heating. In the case of one-stage heating, the temperature is usually 0 to 250 ° C, preferably 20 to 200 ° C. In the case of two-stage heating, the temperature of the first stage is usually 0 to 150 ° C, preferably Is 10 to 100 ° C.,
The temperature of the second stage is usually 20 to 200 ° C, preferably 30 to 180 ° C. The heating and curing time can be appropriately determined depending on the amount of the catalyst, the heating temperature, and other conditions.

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

[0066]

The present invention will be specifically described below with reference to examples. In the examples, “parts” means “parts by weight” unless otherwise specified. (DCPD resin liquid 1) 92.5 parts by weight of high-purity dicyclopentadiene (trade name: H-DCP, manufactured by Maruzen Petrochemical Co., Ltd.) was added to ethylidene norbornene (Nippon Petrochemical Co., Ltd.)
(EBH), 7.5 parts by weight was added to prepare a DCPD resin solution. (DCPD resin solution 2) To 25 parts by weight of high-purity dicyclopentadiene (trade name: H-DCP, manufactured by Maruzen Petrochemical Co., Ltd.), 75 parts by weight of 1,5-cyclooctadiene (made by Degussa-Hüls) are added Thus, a DCPD resin solution 2 was prepared. (DCPD resin liquid 3 and DCPD resin liquid 4) In a dry box in which DCPD resin liquid 1 was purged with diethylaluminum chloride at 40 mM, n-propyl alcohol at 52 mM, and silicon tetrachloride at 20 mM, respectively. To obtain DCPD resin solution 3. Further, tridecyl ammonium molybdate was added to DCPD resin solution 1 at a concentration of 10 mmol, and
CPD resin liquid 4 was prepared.

(Unsaturated polyester resin solution) 2 equipped with a stirrer, condenser, nitrogen gas inlet tube and thermometer
Propylene glycol 38 in a 4-liter four-neck flask
0 parts, 624 parts of neopentyl glycol and 747 parts of isophthalic acid, and heated to 150 ° C. for 1 hour using a mantle heater while slowly flowing nitrogen gas.
The temperature was raised to 220 ° C. over a period of h. Keep it at that temperature for 5h,
An intermediate having an acid value of 8 was obtained. After cooling, add maleic anhydride 5
39 parts were charged and the temperature was raised to 150 ° C. in 1 hour, and further 4 hours
Then, the temperature was raised to 210 ° C. The reaction proceeded while keeping the temperature at that temperature to obtain an unsaturated polyester having an acid value of 25. Into this, 0.01% by weight of hydroquinone was dissolved in a styrene monomer in which the unsaturated polyester content was 60% by weight, and then a 0.5% by weight of a 6% by weight cobalt naphthenate solution as an accelerator was added. 0.4P viscosity at 25 ° C
An unsaturated polyester resin liquid containing an a · s accelerator was prepared.

<Examples 1 to 6> The Ru carbene catalyst A shown in FIG. 1 was added to the DCPD resin solution 1 or 2 in a room at 25 ° C. and stirred for 5 minutes to completely dissolve the catalyst. did. In the case of the composition in which the filler was added, the filler was added after the resin liquid containing the catalyst, and the mixture was stirred for 5 minutes using a stirrer. After defoaming under vacuum, the resin liquid was coated with a release agent on an iron plate (300 x 300 x 6 mm thick)
The resin composition having the composition shown in Table 3 was injected into a mold having two sheets and a mold having a thickness of 3 mm. The filler used is shown in Table 1. In addition, the fiber reinforced test piece was hand laid up on a glass plate. After leaving each at room temperature for 1 hour, they were heated according to the prescribed curing conditions shown in Table 2 to obtain cured products.

<Comparative Example 1> Unsaturated polyester resin liquid 1
To 100 parts by weight, 1 part by weight of 55% by weight methyl ethyl ketone peroxide was added, mixed, vacuum degassed, poured into the same mold as that used in the examples, and the cured product was cured under the curing conditions shown in Table 2. Produced. <Comparative Example 2 and Comparative Example 3> DCPD resin liquid 3 and DCP
The D resin liquid 4 was mixed in equal amounts in a dry box purged with nitrogen, poured into the same mold as that used in the examples during a pot life of 20 ° C. for 20 minutes, and cured under the conditions shown in Table 2. To prepare a cured product. Comparative Example 2 was molded in a nitrogen molding atmosphere, and Comparative Example 3 was molded in an air atmosphere. <Comparative Example 4> DCPD resin liquid 3 and DCPD resin liquid 4
Was mixed at room temperature in an air atmosphere, and injected into the same mold as that used in the examples to prepare cured products under the curing conditions shown in Table 2. <Comparative Example 5> To the DCPD resin liquid 1, the Ru carbene catalyst B shown in FIG. 1 was added in the composition shown in Table 3, mixed, stirred, vacuum degassed, and injected into the same mold as used in the examples. And Table 2
A cured product was prepared under the curing conditions shown in Table 1.

The evaluation method of the obtained cured product is as follows. <Pot life> 25 in accordance with JIS-K-6901
The usable time (pot life) at ° C was measured.

<Mechanical Properties> Bending test: The bending strength and the flexural modulus were measured under the following conditions in accordance with JIS-K-7203. Test specimen shape: 120 × 12 × 3 mm thickness Test speed: 5 mm / min Test span: 80 mm Number of tests: n = 5

<Hardening degree> TGD-9600 manufactured by Vacuum Riko
(Thermal balance analyzer), room temperature (25 ° C) to 400 ° C
The temperature was raised at a rate of 10 ° C./min, the loss on heating at 250 ° C. was measured, and the degree of cure of the test sample was calculated by the following formula. Curing degree (%) = weight of test piece at 250 ° C. (g) / R
Weight of test piece at T (25 ° C) (g)

<Glass Transition Temperature> The glass transition temperature was measured at a heating rate of 5 ° C./min using a DSC-7 model manufactured by PerkinElmer.

<Boiling resistance> The cured product having the shape described in the above mechanical properties was immersed in hot water of about 95 ° C. for 300 hours, and the bending strength of the test piece after the boiling test was measured in the same manner as in the above bending test. The retention of the bending strength was calculated as the boiling resistance by the following formula. Flexural strength retention (%) = (Bending strength after boiling test / Bending strength before boiling test) × 100

<Electrical Characteristics> The electrical characteristics of the cast material were measured using an LCR meter HP42 manufactured by Hewlett-Packard Japan.
The dielectric loss tangent (tan δ) was measured using 75A. Temperature 2
The test was performed at 5 ° C., a humidity of 60%, and a frequency of 10 kHz.

Tables 3 and 4 show the measurement results of the examples and comparative examples. The degree of cure of the resin composition of the present invention was high without being affected by moisture attached to the filler or oxygen in the air even with a very small amount of catalyst used. Each property was equal to or higher than that of a cured product obtained by a conventional metathesis polymerization catalyst system or a cured product of an unsaturated polyester resin.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

[Table 4]

[0081]

According to the present invention, the use of the resin composition of claim 1 or 2 makes it possible to use a filler or an air even with a very small amount of catalyst compared to a two-component metathesis polymerization catalyst system or a conventional one-component metathesis polymerization catalyst. A cured product with a very high degree of curing can be obtained without being affected by the water and oxygen inside, so that it is economical. In addition, since a sufficient usable time can be secured without adding a polymerization rate regulator, the working margin is large. The cured product produced by the production method of claim 3 is water-resistant,
Applications that require strong mechanical and electrical properties,
For example, it can be applied to many applications such as coils, wiring boards, semiconductors and other electronic and electrical insulating materials, septic tanks, bathtubs, wall panels, molding materials for housing equipment such as pleasure boats, and industrial materials such as corrugated plates and pipes. It is possible.

[Brief description of the drawings]

FIG. 1 shows Ru carbene catalysts A and B used in Examples of the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Norio Honda 48 Wadai, Tsukuba, Ibaraki Prefecture Within Hitachi Chemical Co., Ltd. Research Institute (72) Inventor Masahiro Suzuki 4-3-1 Higashicho, Hitachi City, Ibaraki (72) Inventor Takuya Sugishita 4-3-1 Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Office F-term (reference) 4J032 CA34 CA35 CA36 CA38 CA68 CD01 CE06 CE16 CG07

Claims (3)

[Claims] 1. A metathesis polymerizable cycloolefin compound and / or a polymer thereof, and (b) a general formula (1)
And a resin composition comprising (c) at least one component selected from fillers, reinforcing materials and additives. Embedded image (M represents ruthenium or osmium, X and X ¹ each independently represent an anionic ligand, L represents a neutral electron donating group, R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ is each independently hydrogen, an alkyl group having 1 to 20 carbon atoms,
Alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, aryl group, carboxylate group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkenyloxy group having 2 to 20 carbon atoms, 2 carbon atoms An alkynyloxy group, an aryloxy group, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, and an alkylsulfinyl group having 1 to 20 carbon atoms. Show. ) 2. The resin composition according to claim 1, wherein the component (b) is 0.0001 with respect to 100 parts by weight of the component (a).
A resin composition comprising 〜20 parts by weight and 0.001 to 700 parts by weight of component (c). 3. A method for producing a cured product wherein the resin composition according to claim 1 or 2 is cured by heating.