JP2002120325A - Norbornene resin molding and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a norbornene resin molding in which a hydrogenated thermoplastic norbornene resin layer is formed at least on one surface of a crosslinked norbornene resin base material and which is excellent in weatherability and designability and almost odorless and a method for producing the molding. SOLUTION: The norbornene resin molding has the base material composed of the crosslinked norbornene resin and the hydrogenated thermoplastic norbornene resin layer which is formed to adhere at least to one surface of the base material. In the method for producing the norbornene resin molding, the crosslinked norbornene resin base material is formed by polymerizing a norbornene monomer, which is contacted with the surface of the hydrogenated thermoplastic norbornene resin layer, in the presence of a metathesis polymerization catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a norbornene-based resin molded product and a method for producing the same, and more particularly, to a hydrogenated thermoplastic norbornene-based resin layer formed on at least one surface of a crosslinked norbornene-based resin substrate. The present invention relates to a norbornene-based resin molded article having excellent weather resistance and design properties and low odor, and a method for producing the same.

[0002]

2. Description of the Related Art It has been known that a norbornene monomer gives a polymer by a metathesis polymerization reaction. Among them, a so-called reaction injection molding (RIM) method in which polymerization and molding are performed in a mold in a mold using a norbornene-based monomer such as dicyclopentadiene which is available at a low cost in the presence of a metathesis polymerization catalyst. Thus, a method for obtaining a norbornene-based resin molded article is generally adopted. According to this RIM method, not only can a large molded product be obtained using an inexpensive low-pressure mold, but also the obtained molded product has an excellent balance between rigidity and impact resistance, so that an attractive molded product can be obtained. It can be said that this is one of the practical forming means that can be used.

However, in the norbornene resin, the carbon-carbon double bond present in the repeating unit is easily oxidized, so that not only the color tone changes with time but also mechanical properties such as impact strength are deteriorated. In particular, there is a limit to outdoor use where the oxidation reaction is accelerated by sunlight.

[0004] Further, a molded article made of norbornene-based monomer obtained by the RIM method or the like has a peculiar odor because unreacted monomer tends to remain in the molded article. There were restrictions on their use in certain applications.

[0005] For this reason, studies have conventionally been made to solve the above-mentioned problems of norbornene-based resin molded articles, and methods of applying a coating on the surface of the molded article and laminating plastic sheets have been proposed. However, none of these methods is fully satisfactory, and the adhesion between the norbornene-based resin base material and other materials to be the surface layer is insufficient.
It has been difficult to efficiently produce a molded article having a surface layer firmly adhered, having excellent weather resistance and low odor.

[0006] For example, Japanese Patent Publication No. 6-24806 discloses that a norbornene monomer and a metathesis resin are placed in a mold provided with a specific olefin resin sheet such as polyethylene in order to solve the above-mentioned problem of adhesion. A method is disclosed in which a polymerizable resin composition containing a catalyst system is supplied, a norbornene-based resin base material is formed by polymerization, and an olefin resin sheet is coated on the base material surface.

However, according to the above method, the base material and the surface layer are fused and integrated by melting the olefin resin due to the heat generated by the polymerization of the norbornene monomer. Controlling the adhesive force between the substrate and the surface layer by the heat generated by the polymerization involves considerable difficulty, and it cannot be said that the adhesiveness between the substrate and the surface layer has been sufficiently improved. Further, when a thin olefin-based resin film is used for the surface layer, there is a problem that the olefin-based resin film generates wrinkles and pinholes due to heat generated by polymerization of the norbornene-based monomer.

As described above, the problems of the weather resistance and odor of the norbornene-based resin have not yet been sufficiently improved, and by solving this problem, it is possible to expand the applications of the norbornene-based resin molded article. It was strongly sought.

[0009]

SUMMARY OF THE INVENTION In view of the above-mentioned problems of the conventional method, an object of the present invention is to provide a crosslinked norbornene-based resin substrate having at least one surface on which a hydrogenated thermoplastic norbornene-based resin layer is formed. Another object of the present invention is to provide a norbornene-based resin molded article having excellent design properties and low odor, and a method for producing the same.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, it has been found that at least one surface of a crosslinked norbornene-based resin substrate has excellent bondability with the substrate. The present inventors have found that the above-mentioned object can be achieved by forming a hydrogenated thermoplastic norbornene-based resin layer, and have completed the present invention.

That is, according to the first aspect of the present invention, a substrate composed of a crosslinked norbornene-based resin and a hydrogenated thermoplastic norbornene-based resin layer adhered and formed on at least one surface thereof are provided. There is provided a norbornene-based resin molded product characterized by having the above.

According to the second aspect of the present invention, the first aspect is provided.
The present invention provides a norbornene-based resin molded product, wherein the crosslinked norbornene-based resin is a dicyclopentadiene-based resin.

Further, according to a third aspect of the present invention, in the first or second aspect, the crosslinked norbornene-based resin is formed by polymerizing a norbornene-based monomer in the presence of a ruthenium-based metathesis polymer complex. A norbornene-based resin molded article is provided.

On the other hand, according to the fourth invention of the present invention, the norbornene-based monomer is polymerized in the presence of a metathesis polymerization catalyst in contact with the surface of the hydrogenated thermoplastic norbornene-based resin layer to form a crosslinked norbornene-based resin substrate. And a method for producing a norbornene-based resin molded article, characterized in that:

Further, according to the fifth aspect of the present invention, the fourth aspect
The present invention provides a method for producing a norbornene-based resin molded product, wherein the norbornene-based monomer is dicyclopentadiene.

According to a sixth aspect of the present invention, there is provided the method for producing a norbornene-based resin molded article according to the fourth or fifth aspect, wherein the metathesis polymerization catalyst is a ruthenium-based metathesis polymer complex. Provided.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

1. Norbornene-based monomer The norbornene-based monomer used in the present invention is not particularly limited as long as it has a norbornene-based ring.
It is preferable to use a tricyclic or higher polycyclic norbornene-based monomer, since a molded article having excellent heat resistance and shape stability can be obtained.

Examples of the norbornene-based monomer include bicyclics such as 2-norbornene and norbornadiene, tricyclics such as dicyclopentadiene and dihydrodicyclopentadiene, tetracyclododecene, ethylidenetetracyclododecene, and phenyltetrane. Tetracyclics such as cyclododecene, pentacyclics such as tricyclopentadiene, heptacyclics such as tetracyclopentadiene, and their alkyl-substituted (for example, methyl-, ethyl-, propyl- and butyl-substituted), alkylidene-substituted (Eg, ethylidene-substituted), aryl-substituted (eg, phenyl, tolyl-substituted), epoxy group, methacrylic group, hydroxyl group,
Derivatives having a polar group such as an amino group, a carboxyl group, a cyano group, a halogen group, an ether group, and an ester bond-containing group are exemplified. These norbornene monomers may be used alone or in combination of two or more. Tricyclic, tetracyclic, and pentacyclic monomers are preferable because they are easily available, have excellent reactivity, and are excellent in heat resistance of the obtained resin molded product. Among them, dicyclopentadiene is most suitable. is there.

The term "dicyclopentadiene" as used herein means a dicyclopentadiene monomer alone or a mixture of a dicyclopentadiene monomer and another monomer capable of ring-opening copolymerization with the dicyclopentadiene monomer. The dicyclopentadiene monomer is particularly low in viscosity among the norbornene monomers, and the polymerizable resin composition using dicyclopentadiene is optimal because it has a very low viscosity. Moreover, since the crosslinked body of dicyclopentadiene is particularly tough and has high heat resistance among norbornene-based resins, this resin molded article is particularly excellent in strength, rigidity and heat resistance. Further, a dicyclopentadiene monomer is preferable because productivity is high because of high reactivity. In addition, dicyclopentadiene monomers are preferred because they are readily available at low cost.

As described above, the norbornene-based monomer may be copolymerized with another monomer capable of ring-opening copolymerization with the norbornene-based monomer, if necessary, as long as the achievement of the object of the present invention is not hindered. . Examples of other monomers capable of ring-opening copolymerization with the norbornene-based monomer include, for example, cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, monocyclic cycloolefins such as cyclododecene, or indene, cumarone, and coumarone-indene comonomer. Cyclic monomers having metathesis polymerization activity are exemplified, and are preferably used. These other monomers capable of ring-opening copolymerization with the norbornene-based monomer may be used alone or in combination of two or more.

2. Metathesis Polymerization Catalyst The metathesis polymerization catalyst used in the present invention is not particularly limited as long as it is capable of ring-opening polymerization of a norbornene-based monomer, and may be a known catalyst. For example, metal halides such as tungsten, molybdenum, tantalum, ruthenium, rhenium, osmium, titanium and the like, oxyhalides, oxides, organic ammonium salts and the like can be mentioned, and are preferably used. These metathesis polymerization catalysts may be used alone or in combination of two or more.

When it is necessary to carry out the ring-opening metathesis polymerization of the norbornene-based monomer in the air as a process, when the norbornene-based monomer contains a polar functional group, or when the polymerization system contains a highly polar substance. In this case, it is preferable to select a catalyst having excellent stability over time in the air or in the presence of a polar substance among the above metathesis polymerization catalysts. Specifically, a ruthenium carbene catalyst represented by the following general formula (a) or a general A ruthenium vinylidene catalyst of the formula (b) is preferably used. These ruthenium carbene catalysts and ruthenium vinylidene catalysts may be used alone or in combination of two or more.

[0024]

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[0025]

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[In the general formulas (a) and (b),
R1 and R2 independently of one another, hydrogen, C2-C20-
Alkenyl, C1-C20-alkyl, aryl, C1
-C20-carboxylate, C1-C20-alkoxy, C2-C20-alkenyloxy, aryloxy, C2-C20-alkoxycarbonyl, C1-C2
0 alkylthio, C1-C20-alkylsilyl, arylsilyl, thioalkyl, thioaryl (these are
Optionally substituted by C1-C5-alkyl, halogen, C1-C5-alkoxy or optionally phenyl substituted by C1-C5-alkyl, halogen, C1-C5-alkoxy) Or a ferrocene derivative, X1 and X
2 independently of one another means any desired anionic ligand; L1 and L2 independently of one another any desired neutral electron donor; and X1, X2, L1 and Two or three of L2 may also together form a multidentate chelating ligand. ]

Here, more preferred catalysts are those in which R1 and R2 in the general formulas (a) and (b) are
Independently of one another, hydrogen, methyl, ethyl, phenyl, ferrocenyl, alkylsilyl, arylsilyl or vinyl optionally substituted by methyl, ethyl, phenyl or ferrocenyl, X1 and X2
Are Cl and Br independently of each other, L1 and L2
Are catalysts, independently of one another, being trimethylphosphine, triethylphosphine, triisopropylphosphine, triphenylphosphine or tricyclohexylphosphine.

The amount of the metathesis polymerization catalyst used depends on the activity of the metathesis polymerization catalyst itself.
Although it cannot be said unambiguously, 1/5 to 1
/ 500,000 molar equivalents. If the amount of the metathesis polymerization catalyst used relative to all monomers is more than 1/5 equivalent, the molecular weight of the obtained resin will not be sufficiently increased.
If it is less than / 500,000 equivalents, the polymerization rate will be low.

Further, in the present invention, an activator, also called a metathesis cocatalyst, may be used together with a metathesis polymerization catalyst. The activator is not particularly limited as long as it can activate a metathesis polymerization catalyst capable of ring-opening polymerization of a norbornene monomer by bulk polymerization, and may be a known activator. For example, alkyl aluminum, alkyl aluminum halide, alkoxyalkyl aluminum halide, aryloxyalkyl aluminum halide, organic tin compound and the like can be mentioned.

The amount of the activator used is not particularly limited,
Usually, it is used in an amount of 0.1 mol or more, preferably 1 mol or more, and 100 mol or less, preferably 10 mol or less, per 1 mol of the metathesis polymerization catalyst used in the whole reaction solution. If the amount of the activator used is too small, the polymerization activity is too low and the reaction takes a long time, resulting in poor production efficiency.On the other hand, if the amount is too large, the reaction occurs violently. It may set before the object is fully filled. The activator is also dissolved in the monomer and used. However, as long as the properties of the molded article obtained by the bulk polymerization are not substantially impaired, the activator may be suspended or dissolved in a small amount of a solvent and then mixed with the monomer. Makes it difficult to precipitate,
You may use it, raising solubility.

Further, by using an activity regulator in combination, the reaction rate, the time from the mixing of the reaction solution to the start of the reaction, the reaction activity and the like can be adjusted. As the activity regulator, a compound having an action of reducing a metathesis polymerization catalyst or the like is used, and examples thereof include alcohols and halo alcohols. Specific examples of alcohols include n-propanol, n-butanol, n-hexanol, 2-butanol, isobutyl alcohol, isopropyl alcohol, t-butyl alcohol, and the like. Specific examples of halo alcohols include 1, 3-dichloro-2-propanol, 2-chloroethanol, 1-
Chlorobutanol and the like.

The amount of the activity modifier to be added is 1.0 or more, preferably 1.1 or more and 1.5 or less, preferably 1.4 or less in terms of the molar ratio of the activity modifier / activator. If the amount of the activity modifier is too small, the reaction will be too fast and the polymerizable resin composition will be less likely to flow between the reinforcing fibers and into the narrow part of the mold. Conversely, if the amount is too large, the reaction will occur even when heated. Is too slow and production efficiency decreases.

3. Other Ingredients The crosslinked norbornene-based resin serving as a base material of the molded article of the present invention may contain a filler, a reinforcing material, a dispersant, an antioxidant (if necessary) as long as the object of the present invention is not hindered. Anti-aging agent), foaming agent, antifoaming agent, thixotropic agent, antistatic agent, molecular weight modifier, polymer modifier, flame retardant, softener, plasticizer,
One or more of elastomers and the like may be added. Moreover, coloring with a dye, a pigment, a colorant, or the like may be performed, or a design such as a stone grain or a wood grain may be given by some method.

The crosslinked norbornene resin has sufficient strength, rigidity, heat resistance and the like even when used alone, but especially in applications where high strength, high rigidity, high heat resistance, etc. are required. The physical properties can be further enhanced by forming a composite with an inorganic filler or a reinforcing fiber. Crosslinked norbornene-based resin composited with inorganic fillers and reinforcing fibers has high rigidity, so it is not only effective in terms of strength design especially in applications requiring high rigidity, but also has a low coefficient of linear expansion. Therefore, it is also preferable in terms of the dimensional stability of the molded body.

Examples of the filler include calcium carbonate, aluminum hydroxide, magnesium carbonate, sodium hydrogencarbonate, clay, talc, mica, silica, kaolin, fly ash, montmorillonite, glass balloon, silica balloon, and heat-expandable chloride. Vinylidene particles and the like are mentioned, and are preferably used. Among these, calcium carbonate, fly ash, and aluminum hydroxide are particularly preferred because of their low cost and good physical properties of the molded article. In addition, by filling aluminum hydroxide, flame retardancy can be imparted to the crosslinked norbornene resin, and by filling a glass balloon or a silica balloon, the heat insulating property of the crosslinked norbornene resin can be improved. These fillers may be used alone or in combination of two or more. Further, if necessary, it can be used after being subjected to a surface treatment with a coupling agent, a surface treatment agent or the like.

The compounding amount of the filler is not particularly limited, and may be appropriately selected in consideration of required physical properties and cost. Preferably 1 to 500 parts by weight, more preferably 5 to 3 parts by weight, per 100 parts by weight of the norbornene monomer.
00 parts by weight. If the filling amount is too small, the effect of improving the physical properties by the filler is small. If the filling amount is too large, the viscosity of the polymerizable resin composition becomes high, making it difficult to flow. The average particle diameter of the particulate filler is usually 100 μm or less on average, preferably 0.01 to 50 μm, more preferably 0.1 to 30 μm, and still more preferably 1 to 30 μm.
It is in the range of 20 μm.

Examples of the reinforcing material include fibers such as glass fiber, carbon fiber, and aramid fiber, and are preferably used. The form of these fibers is not particularly limited, and may be short fibers or long fibers,
It may be processed into a cloth, mat, non-woven fabric, or the like. These fibers may be used alone,
Two or more kinds may be used in combination. Further, if necessary, it can be used after being subjected to a surface treatment with a coupling agent, a surface treatment agent or the like.

On the other hand, the dispersing agent is not particularly limited as long as it has a function of uniformly dispersing the filler in the norbornene-based monomer, keeping the state of the filler stable, and preventing aggregation and sedimentation of the filler. For example, a coupling agent and a surfactant may be used. The dispersant may be solid, liquid, or gas, but is preferably liquid from the viewpoint of handling properties. These dispersants are
They may be used alone or in combination of two or more. As coupling agents, silane-based, titanate-based, aluminate-based, and zircoaluminate-based coupling agents are known. Among them, silane-based coupling agents and titanate-based coupling agents are particularly preferable.

As the silane coupling agent, known compounds can be used, for example, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-
(2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropylmethoxysilane,
N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxy Silane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, cyclohexylmethyldimethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane,
Octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, trimethylmethoxysilane, trimethylethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane, n-decyltrimethoxysilane,
n-hexadecyltrimethoxysilane, 1.6 bis (trimethoxysilyl) hexane, γ-ureidopropyltriethoxysilane, γ-dibutylaminopropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, tetraethoxysilane, And perfluorooctylethyltriethoxysilane.

As the titanate coupling agent, known ones can be used, for example, triisostearoyl isopropyl titanate, di (dioctyl phosphate) diisopropyl titanate, didodecylbenzenesulfonyl diisopropyl titanate,
Diisostearyl diisopropyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl) (Phosphite) titanate and the like.

On the other hand, the surfactant is not particularly limited, and examples thereof include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. Examples of anionic surfactants include compounds such as carboxylate, nitrate ester, sulfonate and phosphate ester salts, and examples of cationic surfactants include primary, secondary, tertiary and tertiary surfactants. As compounds such as quaternary amine salts and amphoteric surfactants, compounds such as aminocarboxylic acid, phosphoric acid ester salts and betaine can be used. In addition, as the nonionic surfactant, ether-based, ester-based, ether-ester-based, and nitrogen-containing compounds, and various fatty acids such as stearic acid, oleic acid, linoleic acid, and linoleic acid can also be used. .

The amount of the dispersant is not particularly limited, and may be appropriately selected in consideration of required physical properties and cost. Preferably it is 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the filler. If the amount is too small, the effect of the dispersant is small, and if it is too large, the physical properties of the norbornene resin may be reduced.

Examples of the elastomers include natural rubber, polyisoprene, polybutadiene, styrene butadiene copolymer, acrylonitrile-butadiene copolymer, chloroprene, styrene-isoprene-styrene block co-aggregate, and styrene-butadiene-styrene. Block copolymers, ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, ethylene-vinyl acetate copolymers, and hydrides thereof are preferably used. These elastomers may be used alone or in combination of two or more.

Further, examples of the antioxidant include phenol-based, phosphorus-based, amine-based plastics and the like.
Antioxidants for rubber are used.

4. Crosslinked norbornene-based resin substrate In the norbornene-based resin molded article of the present invention, a crosslinked norbornene-based resin is used as a substrate. As described above, the crosslinked norbornene-based resin serving as a base material is not particularly limited, but may be a crosslinked norbornene-based resin obtained by subjecting one or more norbornene-based monomers to ring-opening polymerization in the presence of a metathesis polymerization catalyst. It is a norbornene resin. Among these, a dicyclopentadiene-based resin is particularly preferred because a molded article having excellent strength, rigidity and heat resistance can be obtained, and raw material monomers can be easily obtained at low cost.

5. Hydrogenated thermoplastic norbornene-based resin In the norbornene-based resin molded article of the present invention, a hydrogenated thermoplastic norbornene-based resin layer is formed on at least one surface of the crosslinked norbornene-based resin substrate. The hydrogenated thermoplastic norbornene-based resin used in the present invention is not particularly limited, and is a thermoplastic resin obtained by polymerizing one or more of the above-mentioned norbornene-based monomers and hydrogenating the same. Hydrogenated thermoplastic norbornene-based resin has good compatibility with crosslinked norbornene-based resin as base material, and can form a strong joint surface without special surface treatment such as primer treatment or sanding treatment. In addition, because of hydrogenation, the residual double bonds are small and the weather resistance is good.

The above-mentioned norbornene-based monomer may be optionally used within a range not to impair the achievement of the object of the present invention.
It may be copolymerized with another monomer capable of ring-opening copolymerization with the norbornene-based monomer. Other monomers capable of ring-opening copolymerization with the norbornene-based monomer include, for example, cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, monocyclic cycloolefins such as cyclododecene or indene, cumarone, and coumarone indene-based comonomers. Monomers and the like are mentioned, and are preferably used. These other monomers capable of ring-opening copolymerization with a norbornene-based monomer may be used alone,
Two or more kinds may be used in combination.

The hydrogenation rate of the hydrogenated thermoplastic norbornene resin is not particularly limited, but is preferably 90%.
%, More preferably 99% or more. If the hydrogenation rate is lower than 90%, the number of double bonds remaining in the resin increases, and the weather resistance required for the resin of the surface layer cannot be satisfied.

The hydrogenated thermoplastic norbornene-based resin layer may be colored with a dye, a pigment, a coloring agent, or the like, or may be provided with a design such as a stone grain or a wood grain by any method. . In addition, a filler, a reinforcing material, an antioxidant (an antioxidant), a foaming agent, an antifoaming agent, a thixotropic agent, an antistatic agent, if necessary, as long as the object of the present invention is not hindered. Molecular weight regulator, polymer modifier,
One or more of a flame retardant, a softener, a plasticizer, a surfactant, a pigment, a dye, a colorant, an elastomer and the like may be added.

Further, the shape of the hydrogenated thermoplastic norbornene resin is not particularly limited, and is not limited to a simple shape such as a film, a plate, a rod, and a tube.
Molded into any shape by a molding method such as injection molding, RIM molding, casting molding, pultrusion molding, RI, transfer molding, blow molding, press molding, vacuum molding, spray molding, hand lay-up, gel coating, etc. May be. The molded body does not need to be completely cured, but may be semi-cured formed by gel coating or the like.

6. Norbornene-based resin molded article The norbornene-based resin molded article of the present invention is provided on at least one surface of a base material composed of a crosslinked norbornene-based resin,
It is a molded article on which a hydrogenated thermoplastic norbornene-based resin layer is formed.

As described above, the hydrogenated thermoplastic norbornene resin used for the surface layer of the norbornene-based resin molded article has excellent bonding properties with the crosslinked norbornene-based resin as described above, and the residual hydrogenated thermoplastic norbornene-based resin is hydrogenated. It has few heavy bonds and good weather resistance. For this reason, the norbornene-based resin molded article of the present invention is a norbornene-based resin molded article having high weather resistance, in which the hydrogenated thermoplastic norbornene-based resin of the strongly bonded surface layer is hardly oxidized to block oxygen. be able to.

The hydrogenated thermoplastic norbornene-based resin in the surface layer can prevent the norbornene-based monomer contained in the crosslinked norbornene-based resin base material from scattering and suppress the generation of odor from the base material. .

Further, since the hydrogenated thermoplastic norbornene-based resin has high transparency, the norbornene-based resin molded article of the present invention using the hydrogenated thermoplastic norbornene-based resin as a surface layer is excellent in both deepness and surface gloss, and has very good design. Will be high. Further, since the hydrogenated thermoplastic norbornene-based resin has a high surface hardness, the norbornene-based resin molded article of the present invention using the hydrogenated thermoplastic norbornene-based resin as a surface layer is hardly damaged.

The hydrogenated thermoplastic norbornene-based resin layer is formed of at least one of the crosslinked norbornene-based resin base materials.
It may be provided on the entire surface or may be provided partially. That is, the region where the hydrogenated thermoplastic norbornene-based resin layer is provided may be appropriately selected in consideration of the physical properties and productivity required for the intended use. Also,
The thickness of the hydrogenated thermoplastic norbornene-based resin layer,
There is no particular limitation, and it may be appropriately selected according to the physical properties and productivity required for the intended use.

The norbornene-based resin molded article of the present invention can have a multilayer structure of three or more layers, if necessary. At this time, the layers other than the crosslinked norbornene-based resin and the hydrogenated thermoplastic norbornene-based resin are not particularly limited, and the material, shape, and lamination position can be arbitrarily selected. The third layer further increases the value of the norbornene-based resin molded article of the present invention, for example,
When laminated with a third layer made of a foam such as a urethane resin or a norbornene-based resin, the heat insulation of the molded body can be enhanced.

Further, the norbornene-based resin molded article of the present invention may be subjected to some kind of treatment in order to increase the bonding strength between the layers. For example, an intermediate layer may be provided, a primer treatment may be performed, or an anchor such as a sanding treatment may be performed. Bonding by the effect can also be performed.

The norbornene-based resin molded article of the present invention may be used by being joined and integrated with other members. The material, shape, and joining site of the other members to be used are not particularly limited, and an optimal member may be selected according to the intended use. Examples of such a member include steel and wood. By joining with such a member, the rigidity of the molded body can be increased, and a dimensional change due to a temperature change can be reduced.

The norbornene-based resin molded article of the present invention has a specific structure as described above, that is, a substrate formed of a crosslinked norbornene-based resin, and a hydrogen gas adhered and formed on at least one surface thereof. It may be produced by any method as long as the added thermoplastic norbornene-based resin layer can be obtained, and is not particularly limited.For example, for example, in contact with the surface of the hydrogenated thermoplastic norbornene-based resin layer, Then, a norbornene-based monomer is polymerized in the presence of a metathesis polymerization catalyst to form a crosslinked norbornene-based resin substrate.

The method of polymerizing the norbornene-based monomer on the hydrogenated thermoplastic norbornene-based resin layer is not particularly limited. For example, a mixed solution of the norbornene-based monomer is placed in a mold provided with the hydrogenated thermoplastic norbornene-based resin. A method of pouring and polymerizing and integrating, a method of coating or spraying a polymerizable resin composition on a hydrogenated thermoplastic norbornene-based resin, and the like are exemplified.

Since the above norbornene-based monomer has very good compatibility with the hydrogenated thermoplastic norbornene-based resin, it can swell or dissolve the hydrogenated thermoplastic norbornene-based resin in an extremely short time. Therefore, by polymerizing the norbornene-based monomer on the hydrogenated thermoplastic norbornene-based resin layer, the crosslinked norbornene-based resin formed by polymerization of the norbornene-based monomer is extremely strongly bonded to the hydrogenated thermoplastic norbornene-based resin layer. It will be. In the present invention, since there is no need to perform a special surface treatment such as a primer treatment or a sanding treatment, a complicated process is not required, and a norbornene-based resin molded article can be efficiently produced.

In the present invention, it is desirable to control the heat generated by the polymerization of the norbornene-based monomer so that the temperature of the hydrogenated thermoplastic norbornene-based resin is lower than the melting point. Due to the heat generated by the polymerization, the temperature of the hydrogenated thermoplastic norbornene resin becomes higher than the melting point, and when the resin is thin, wrinkles and pinholes may be generated in the hydrogenated thermoplastic norbornene resin. is there. In such a case, it is necessary to control the heat generation by some method. For example, a method of removing the heat of reaction by molding in a mold with cooling piping or a curing room controlled at a low temperature, a type of catalyst And a method of controlling the amount of addition to suppress heat generation.

7. Method for Producing Norbornene-Based Resin Molded Body Hereinafter, the production method of the present invention will be described in more detail with reference to FIGS. 1 to 3, but as described above, the production method of the present invention is not necessarily limited thereto. Not something.

First, as shown in FIG. 1, a hydrogenated thermoplastic norbornene-based resin sheet 31 is disposed on the surface of one casting mold 1. Next, as shown in FIG. 2, the hydrogenated thermoplastic norbornene-based resin sheet 3 is attached to the casting mold 1 with the hydrogenated thermoplastic norbornene-based resin sheet 31 attached.
The other casting mold 2 is set while maintaining a predetermined gap from the casting mold 2. It should be noted that the interval of the gap becomes the thickness of the crosslinked norbornene-based resin layer 32 after molding, and thus may be determined based on the physical properties required for the target product. Finally, as shown in FIG. 3, a polymerizable resin composition containing a norbornene-based monomer and a metathesis polymerization catalyst is filled into the gap from the injection hole 4 and cured, and hydrogenation is performed on the surface of the crosslinked norbornene-based resin 32. The norbornene-based resin molded body 3 integrated with the thermoplastic norbornene-based resin sheet 31 is removed from the mold.

In the present invention, the hydrogenated thermoplastic norbornene-based resin and the crosslinked norbornene-based resin are laminated and integrated by cast molding. However, cast molding can be performed at a low pressure. When the resin is poured into the mold, the hydrogenated thermoplastic norbornene-based resin is unlikely to be deformed or displaced from the disposition position, so that a molded article can be efficiently produced.

Further, the polymerizable resin composition containing the norbornene-based monomer and the metathesis polymerization catalyst can be made into an extremely low-viscosity compounding liquid, so that even at a low pressure, good permeability into narrow gaps is obtained. is there. Therefore, even in normal pressure molding or low pressure molding by cast molding, resin can be poured into every corner of a large product.

The obtained norbornene-based resin molded product has a low odor, and is excellent in weather resistance, mechanical strength, and design, so that, for example, a bathtub, a waterproof pan, a kitchen counter, a wash bowl, an exterior material, It can be suitably used for deck materials, wall materials, toilet bowls and the like.

[0068]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1 Dicyclopentadiene and (3,3-dimethylbutynylidene) bis (tricyclohexylphosphine) ruthenium dichloride of the following formula (1) were added to 200 parts of toluene.
The solution in which 0 parts are dissolved is mixed and stirred at 40 ° C. such that the molar ratio of (3,3-dimethylbutynylidene) bis (tricyclohexylphosphine) ruthenium dichloride to dicyclopentadiene becomes 1/10000. To obtain a polymerizable resin composition. Next, a hydrogenated thermoplastic norbornene-based resin sheet having a thickness of 0.06 mm (ZEONOR 160 manufactured by Zeon Corporation) is formed on both surfaces of the mold surface.
OR), the above polymerizable composition was poured. Thereafter, the mixture was cured by heating at 60 ° C. for 10 minutes to obtain a molded article (23 cm square, 4.0 mm thick) in which a hydrogenated thermoplastic norbornene-based resin sheet was integrated on both surfaces of a dicyclopentadiene resin plate. The time from cutting out the sheet to obtaining a molded body was 12 minutes. The bonding strength of the obtained molded body was evaluated based on whether or not the hydrogenated thermoplastic norbornene-based resin sheet could be peeled off from the base material by hand, and the odor was measured by dicyclopentadiene monomer on the molded body surface. The evaluation was based on whether or not there was a smell. Table 1 shows the evaluation results. Also, a test piece was cut out from the molded body and
An Izod impact test was performed according to SK7110 by applying an impact from a flatwise direction using a test piece without a notch. Table 1 shows the test results.

[0070]

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Comparative Example 1 Instead of the hydrogenated thermoplastic norbornene-based resin sheet,
A molded article in which a high-density polyethylene resin sheet was integrated on both surfaces of a dicyclopentadiene resin plate was carried out in the same manner as in Example 1, except that a high-density polyethylene sheet having a thickness of 0.08 mm was used as a surface layer. (23 cm square, thickness 4.0 mm). The time from cutting out the sheet to obtaining the molded article of the present invention was 12 minutes. As in Example 1, the bonding strength, odor, and impact strength of the molded body were evaluated. Table 1 shows the results.

Comparative Example 2 A polymerizable resin composition of dicyclopentadiene monomer prepared in the same manner as in Example 1 was poured into a flat mold.
By heating and curing at 0 ° C. for 10 minutes, a dicyclopentadiene resin plate (23 cm square, thickness 4.0 mm) was obtained. Next, both surfaces of the dicyclopentadiene resin plate were sanded with No. 180 sandpaper, and then a high-density polyethylene resin sheet was attached to both surfaces of the resin plate using a two-pack type epoxy resin. By heating and curing at 60 ° C. for 60 minutes, a molded article in which a high-density polyethylene resin sheet was integrated on both surfaces of a dicyclopentadiene resin plate was obtained. The time until a molded article was obtained was 87 minutes. As in Example 1, the bonding strength, odor, and impact strength of the molded body were evaluated. Table 1 shows the results.

COMPARATIVE EXAMPLE 3 A polymerizable resin composition of dicyclopentadiene monomer prepared in the same manner as in Example 1 was poured into a flat mold.
A dicyclopentadiene resin plate (23 cm square, thickness 4.0 mm) was obtained by heating and curing at 10 ° C. for 10 minutes. As in Example 1, the molded article was evaluated for odor and impact strength. Table 1 shows the results.

[0074]

[Table 1]

As is clear from Table 1, in the present invention, the hydrogenated norbornene-based resin layer can be provided on the surface of the crosslinked norbornene-based resin base material with high bonding strength in a very short time. The molded body is
It had low odor and excellent weather resistance.

[0076]

As described above, according to the present invention, the obtained norbornene-based resin molded product is hardly oxidized and degraded because the hydrogenated thermoplastic norbornene-based resin of the surface layer blocks oxygen, and has excellent weather resistance. Excellent, and the surface layer has a low odor to prevent the hydrogenated thermoplastic norbornene-based resin from scattering the norbornene-based monomer contained in the crosslinked norbornene-based resin. Since the transparency of the resin is high, the resin has a sense of depth, a glossy surface, and a high designability. in addition,
Since the crosslinked norbornene-based resin cures in a very short time, a norbornene-based resin molded body can be produced with higher working efficiency than conventional reinforcement by hand lay-up or spray-up. Therefore, the norbornene-based resin molded article of the present invention has low odor, excellent weather resistance, mechanical strength, and excellent design.For example, a bathtub, a waterproof pan, a kitchen counter, a wash bowl, an exterior material, and a deck It can be suitably used for materials, wall materials, toilets, and the like.

[Brief description of the drawings]

FIG. 1 is an explanatory view illustrating a first step in a manufacturing method of the present invention.

FIG. 2 is an explanatory view illustrating an intermediate step of the manufacturing method of the present invention.

FIG. 3 is an explanatory diagram illustrating a final step of the manufacturing method of the present invention.

[Explanation of symbols]

 Reference Signs List 1 Mold (lower mold) 2 Mold (upper mold) 3 Norbornene-based resin molded body 31 Hydrogenated thermoplastic norbornene-based resin molded body 32 Cross-linked norbornene-based resin molded body 4 Injection hole

Claims (6)

[Claims] 1. A norbornene-based resin molded article comprising: a base material composed of a crosslinked norbornene-based resin; and a hydrogenated thermoplastic norbornene-based resin layer adhered and formed on at least one surface thereof. . 2. The norbornene-based resin molded product according to claim 1, wherein the crosslinked norbornene-based resin is a dicyclopentadiene-based resin. 3. The crosslinked norbornene-based resin is formed by polymerizing a norbornene-based monomer in the presence of a ruthenium-based metathesis polymer complex.
Or the norbornene-based resin molded product according to 2. 4. A norbornene-based resin, wherein a norbornene-based monomer is polymerized in the presence of a metathesis polymerization catalyst in contact with the surface of a hydrogenated thermoplastic norbornene-based resin layer to form a crosslinked norbornene-based resin base material. A method for producing a molded article. 5. The method for producing a norbornene-based resin molded product according to claim 4, wherein the norbornene-based monomer is dicyclopentadiene. 6. The metathesis polymerization catalyst according to claim 4, wherein the metathesis polymerization catalyst is a ruthenium-based metathesis polymerization complex.
5. The method for producing a norbornene-based resin molded article according to the above.