阅读说明：本技术 环烯烃树脂装饰成型品的制造方法 (Method for producing cycloolefin resin decorative molded article ) 是由 竹内正基 于 2020-04-20 设计创作，主要内容包括：本发明提供了一种环烯烃树脂装饰成型品的制造方法,其具有如下工序：在使凝胶涂层组合物与包含自由基产生剂的环烯烃聚合性组合物接触的状态,使上述凝胶涂层组合物固化的同时,使上述环烯烃聚合性组合物聚合,由此得到凝胶涂层与环烯烃树脂层密合而成的环烯烃树脂装饰成型品。(The invention provides a method for manufacturing a cycloolefin resin decorative molded product, which comprises the following steps: the gel coating composition is solidified and the cycloolefin polymerizable composition is polymerized while the gel coating composition is brought into contact with the cycloolefin polymerizable composition containing the radical generating agent, thereby obtaining a cycloolefin resin decorative molded article in which the gel coating layer and the cycloolefin resin layer are adhered to each other.)

1. A method for producing a cycloolefin resin decorative molded product, comprising the steps of: the gel coating composition is solidified and the cycloolefin polymerizable composition is polymerized in a state of being in contact with the gel coating composition and the cycloolefin polymerizable composition containing the free radical generating agent, thereby obtaining the cycloolefin resin decorative molded product formed by closely adhering the gel coating and the cycloolefin resin layer.

2. The method for producing a cycloolefin resin decorative molded article according to claim 1, wherein a content of the curing accelerator contained in the gel coat composition is 1.5% by mass or less.

3. The method of manufacturing a cycloolefin resin decorative molded article according to claim 1 or 2, wherein the cycloolefin polymerizable composition contains a filler.

4. The method of manufacturing a cycloolefin resin decorative molded product according to claim 3, wherein the filler is in a fibrous and/or granular form.

Technical Field

The present invention relates to a method for producing a decorative molded article of cycloolefin resin.

Background

Conventionally, a cycloolefin resin molded product is generally coated with a coating.

Patent document 1 discloses a method of forming a coating on the surface of a cycloolefin resin molded product obtained by injecting a radical polymerizable coating material into a mold and curing the coating material in the mold.

Patent document 2 discloses a cycloolefin polymerizable composition in which a radical polymerizable monomer and a radical generating agent coexist, but does not disclose formation of a coating on the surface of a cycloolefin resin molded product.

Documents of the prior art

Patent document

Patent document 1: japanese re-table 2005/046958 publication;

patent document 2: japanese re-table 2015/098636 publication;

patent document 3: japanese patent laid-open publication No. 2005-271535;

patent document 4: japanese patent laid-open publication No. 2016-8243.

Disclosure of Invention

Problems to be solved by the invention

The invention provides a manufacturing method, which can manufacture a cycloolefin resin decorative molding product with a gel coating layer closely adhered to a cycloolefin resin layer.

Means for solving the problems

According to the present invention, there is provided a method for producing a cycloolefin resin decorative molded article, comprising the steps of: the gel coating composition is solidified and the cycloolefin polymerizable composition is polymerized in a state that the gel coating composition is contacted with the cycloolefin polymerizable composition containing the free radical generating agent, thereby obtaining the cycloolefin resin decorative molding product formed by closely adhering the gel coating layer and the cycloolefin resin layer.

In the production method of the present invention, the content of the curing accelerator contained in the gel coat composition is preferably 1.5% by mass or less.

In the production method of the present invention, it is preferable that the cycloolefin polymerizable composition contains a filler.

In the production method of the present invention, the filler is preferably in a fibrous and/or granular form.

Effects of the invention

According to the present invention, a production method capable of producing a cycloolefin resin decorative molded article in which a gel coat layer is in close contact with a cycloolefin resin layer can be provided.

Detailed Description

The manufacturing method of the present invention comprises the following steps: the gel coat composition is cured while polymerizing the cycloolefin polymerizable composition in a state where the gel coat composition is in contact with the cycloolefin polymerizable composition containing the radical generator. According to the production method of the present invention, a cycloolefin resin decorative molded article having a gel coat layer formed from the gel coat composition and a cycloolefin resin layer formed from the cycloolefin polymerizable composition and having the gel coat layer in close contact with the cycloolefin resin layer can be obtained.

In the present specification, "close adhesion" between the gel coat layer and the cycloolefin resin layer means that the gel coat layer and the cycloolefin resin layer are close adhesion to the extent that they can be classified into class 0 or class 1 in class 6 when the adhesion is evaluated in accordance with JIS K5600.

The cycloolefin resin molded product decorated by the production method of the present invention has a gel coat layer, and thus can provide a deep and high-grade decoration to the cycloolefin resin molded product.

In the present invention, the gel coat is formed using the gel coat composition. The gel coat composition is a liquid thermosetting resin composition or photocurable resin composition containing an unsaturated polyester resin, a vinyl ester resin, an acrylic resin, or the like as a base resin, alone or in combination, a curing agent component (polymerization initiator), and an optional additive such as a pigment. The gel coat composition can be applied to the surface of the mold to be used, for example, by spraying or brushing, to form a cycloolefin resin layer thereon, or conversely applied to the cycloolefin resin layer.

The gel coat composition may be in an uncured state or a semi-cured state if it is not in a cured state. The gel coat layer can be formed by curing the gel coat composition on the cycloolefin resin layer, and from the viewpoint of workability, it is preferable to form the gel coat layer by curing the gel coat composition in an uncured state. In addition, the gel coat composition in a semi-cured state means a gel coat composition in which the gel coat composition in an uncured state is partially cured, and the degree of curing is arbitrary as long as the desired effects exhibited by the present invention are not impaired.

As described below, the gel coat composition is preferably substantially free of a curing accelerator. Here, "substantially not containing a curing accelerator" means that the content of the curing accelerator contained in the gel coat composition is 1.5% by mass or less. The content of the curing accelerator is preferably 1.2% by mass or less, and more preferably 1% by mass or less. The gel coat formed from the gel coat composition is substantially free of a curing accelerator or a residue from a curing accelerator. Examples of the curing accelerator include metallic soaps such as manganese compounds and cobalt compounds, quaternary ammonium salts, and amines.

In view of the characteristics of the polymerization reaction of the cycloolefin resin layer and the gel coat layer, it is generally predicted that it is extremely difficult to bring the cycloolefin resin layer into close contact with the gel coat layer. As described in patent document 3, the cycloolefin resin layer is obtained by a metathesis polymerization reaction using a metathesis polymerization catalyst, whereas as described in patent document 4, the gel coat layer is obtained by a radical polymerization reaction using a polymerization initiator (curing agent component), a curing accelerator, and the like. Typical gel coats typically contain more than 1.5 mass% of a cure accelerator.

However, after intensive studies, it was found that the gel coat layer was closely adhered to the cycloolefin resin layer by performing curing of the gel coat composition and polymerization of the cycloolefin polymerizable composition in a state where the gel coat composition was brought into contact with the cycloolefin polymerizable composition.

It has also been found that by using a gel coat composition containing substantially no curing accelerator, the gel coat layer is more strongly adhered to the cycloolefin resin layer. For example, an uncured or semi-cured gel coat composition containing a curing agent component and no curing accelerator is applied to a mold, and then a cycloolefin polymerizable composition containing a radical generator is added to a coating film of the gel coat composition, and the cycloolefin polymerizable composition is polymerized while curing the gel coat composition in a state where the uncured or semi-cured gel coat composition is in contact with the cycloolefin polymerizable composition containing the radical generator, whereby both the cycloolefin polymerizable composition and the gel coat composition are cured and adhered to each other.

The reason why good adhesion can be obtained when the gel coat composition does not substantially contain a curing accelerator is presumed as follows. It is presumed that in the case where the gel coat composition contains a curing accelerator and the curing accelerator contributes to the curing reaction, the curing reaction rate of the gel coat composition is much higher than the polymerization reaction rate of the cycloolefin polymerizable composition, the active species derived from the radical initiator in the cycloolefin polymerizable composition do not efficiently react with the active species in the gel coat composition, and a crosslinked structure such as a covalent bond is not sufficiently formed between the base resin forming the gel coat and the cycloolefin resin forming the cycloolefin resin layer. On the other hand, it is presumed that when a gel coat composition containing a curing agent component and a cycloolefin polymerizable composition containing a radical generator and not containing a curing accelerator is used, a structure for improving adhesion is sufficiently formed between the base resin forming the gel coat and the cycloolefin resin forming the cycloolefin resin layer, and both are adhered to each other.

In the gel coat composition, as the base resin, an unsaturated polyester resin, a vinyl ester resin, an acrylic resin, or the like can be used alone or in combination.

The unsaturated polyester resin is obtained by condensation reaction of an unsaturated dibasic acid such as maleic acid or fumaric acid with a polyhydric alcohol such as ethylene glycol, propylene glycol or trimethylolpropane.

The vinyl ester resin is a resin obtained by adding an acryloyl group or a methacryloyl group to an epoxy resin, and is obtained by dissolving the resin in a vinyl monomer in the same manner as the unsaturated polyester resin.

The acrylic resin is formed from homopolymers or copolymers of acrylates or methacrylates.

Examples of the curing agent component (polymerization initiator) include a thermal curing agent and a light curing agent, and among them, a thermal curing agent is preferable in that the polymerization reaction and the curing reaction of the cycloolefin polymerizable composition are easily progressed.

Examples of the heat-curing agent include organic peroxides, and examples thereof include known heat-curing agents such as diacyl peroxides, peroxy esters, hydrogen peroxides, dialkyl peroxides, ketone peroxides, peroxy ketals, alkyl peroxy esters, and peroxy carbonate esters. The amount of the thermosetting agent to be added is not particularly limited as long as the object of the present invention can be achieved, and is usually 0.2 to 5 parts by mass, preferably 0.5 to 4 parts by mass, and more preferably 0.7 to 3 parts by mass, based on 100 parts by mass of the base resin. Further, by appropriately adjusting the curing temperature in accordance with the environmental temperature or the like, the adhesion between the gel coat layer and the cycloolefin resin layer can be improved.

Examples of the light-curing agent include benzoin ether systems such as benzoin alkyl ether, benzophenone systems such as benzophenone, benzil, and methyl benzoylbenzoate, acetophenone systems such as benzil dimethyl ketal, 2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, and 1, 1-dichloroacetophenone systems, and thioxanthone systems such as 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone. The addition amount of the light curing agent is usually 0.1 to 3 parts by mass with respect to 100 parts by mass of the base resin.

Further, in order to adjust the curing speed, a polymerization inhibitor or the like can be used in the gel coat composition. Examples of the polymerization inhibitor include trihydrobenzene, toluhydroquinone, 14-naphthoquinone, p-benzoquinone, hydroquinone, benzoquinone, hydroquinone monomethyl ether, p-tert-butylcatechol, and 2, 6-di-tert-butyl-4-methylphenol. The amount of the polymerization inhibitor added is usually 10 to 1000ppm, preferably 50 to 200ppm, in the gel coat composition. When the amount is in this range, the gel coat composition can be improved in storage stability, handling properties and strength development properties.

The gel coat composition used in the present invention may contain, as necessary, conventionally known pigments, extender pigments, dyes, colorants, thixotropic agents, ultraviolet absorbers, light stabilizers, antifoaming agents, leveling agents, internal release agents, waxes, antioxidants, fillers, dispersants, flame retardants, and the like.

The cycloolefin resin decorative molded article obtained by the production method of the present invention has a cycloolefin resin layer. The cycloolefin resin in the present specification means a homopolymer (homopolymer) obtained by polymerizing 1 monomer having a cycloolefin structure, or a copolymer (copolymer) obtained by polymerizing a plurality of monomers having a cycloolefin structure. Whether or not the polymer has a cycloolefin structure can be analyzed by, for example, Nuclear Magnetic Resonance (NMR).

The cycloolefin resin layer is obtained by polymerizing (preferably bulk polymerizing) the cycloolefin polymerizable composition. The cycloolefin polymerizable composition is prepared by appropriately mixing a cycloolefin monomer, a metathesis polymerization catalyst, a radical generator, and optional components such as an activator and a filler of the catalyst to be blended according to a desired method according to a known method.

First, each component contained in the cycloolefin polymerizable composition will be described.

Cycloolefin monomer

The cycloolefin monomer is a compound having an alicyclic structure and a carbon-carbon double bond in the molecule.

Examples of the alicyclic structure constituting the cycloolefin monomer include a monocyclic ring, a polycyclic ring, a condensed ring, a bridged ring, and a polycyclic ring in combination thereof. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, and more preferably 5 to 15.

Examples of the cycloolefin monomer include monocyclic cycloolefin monomers and norbornene monomers, and norbornene monomers are preferable. The norbornene-based monomer is a cycloolefin monomer having a norbornene ring structure in the molecule. These may be substituted with a hydrocarbon group such as an alkyl group, an alkenyl group, an alkylene group, or an aryl group, a polar group, or the like. The norbornene-based monomer may have a double bond other than the double bond of the norbornene ring.

Examples of the monocyclic cycloolefin monomer include cyclobutene, cyclopentene, cyclooctene, cyclododecene, cyclopentadiene, 1, 5-cyclooctadiene, and the like.

Specific examples of the norbornene-based monomer include: dicyclopentadiene compounds such as dicyclopentadiene and methyldicyclopentadiene;

tetracyclic [6.2.1.1^3,6.0^2,7]Dodec-4-ene, 9-ethylene tetracyclo [6.2.1.1^3,6.0^2,7]Dodec-4-ene, 9-phenyltetracyclo [6.2.1.1^3,6.0^2,7]Dodec-4-ene, tetracyclo [6.2.1.1^3,6.0^2,7]Dodec-9-ene-4-carboxylic acid, tetracyclo [6.2.1.1^3,6.0^2,7]Tetracyclodecadienes such as dodec-9-ene-4, 5-dicarboxylic anhydride;

norbornenes such as 2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-phenyl-2-norbornene, acrylic acid-5-norbornen-2-yl, methacrylic acid-5-norbornen-2-yl, 5-norbornene-2-carboxylic acid, 5-norbornene-2, 3-dicarboxylic acid, and 5-norbornene-2, 3-dicarboxylic anhydride;

oxanorbornenes such as 7-oxa-2-norbornene and 5-ethylidene-7-oxa-2-norbornene;

tetracyclic [9.2.1.0^2,10.0^3,8]Tetradeca-3, 5,7, 12-tetraene (also known as 1, 4-methano-1, 4,4a,9 a-tetrahydro-9H-fluorene), pentacyclic [6.5.1.1^3,6.0^2,7.0^9,13]Pentadecane-4, 10-diene, pentacyclic [9.2.1.0 ]^2,10.0^3,8]And cyclic olefins having four or more rings such as pentadeca-5, 12-diene and tricyclopentadiene.

Among these cycloolefin monomers, cycloolefin monomers having no polar group are preferable because a molded article having low water absorption can be obtained. In addition, when tetracyclic [9.2.1.0 ] is used^2,10.0^3,8]The viscosity of the cycloolefin polymer composition can be reduced by using a cycloolefin monomer having an aromatic condensed ring such as tetradeca-3, 5,7, 12-tetraene.

These cycloolefin monomers may be used alone or in combination of two or more. The physical properties of the cycloolefin resin obtained can be appropriately adjusted by the combination.

The cycloolefin polymerizable composition used in the present invention may contain any monomer copolymerizable with the cycloolefin monomer as long as the effect of the present invention is not hindered.

Metathesis polymerization catalyst

The metathesis polymerization catalyst used in the present invention is not particularly limited as long as it can ring-open polymerize a cyclic olefin monomer, and a known metathesis polymerization catalyst can be used.

The metathesis polymerization catalyst used in the present invention is a complex in which a transition metal atom is a central atom, a plurality of ions, an atom, a polyatomic ion and/or a compound are bonded. As the transition metal atom, atoms of groups 5, 6 and 8 (long form periodic table, the same applies hereinafter) are used. The atom of each group is not particularly limited, and tantalum is exemplified as the atom of group 5, molybdenum and tungsten are exemplified as the atom of group 6, and ruthenium and osmium are exemplified as the atom of group 8.

As the metathesis polymerization catalyst containing tungsten or molybdenum of group 6 as a central metal, a metal halide such as tungsten hexachloride; metal oxyhalides such as tungsten oxychloride; metal oxides such as tungsten oxide; and organic metal acid ammonium salts such as ammonium tridodecylmolybdate and ammonium tritridecyl molybdate.

As the metathesis polymerization catalyst containing ruthenium or osmium of group 8 as a central metal, a ruthenium carbene complex in which a carbene compound is coordinated to ruthenium is preferable. Here, the term "carbene compound" refers to a generic term for compounds having a methylene free group, and refers to compounds having a 2-valent carbon atom (carbene carbon) having no charge represented by (> C:).

Examples of the ruthenium carbene complex include compounds represented by the following general formula (1) or general formula (2).

[ chemical formula 1]

In the above general formulae (1) and (2), R¹And R²Each independently is a hydrogen atom; a halogen atom; or is thatAn organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; these groups may have a substituent, and may be bonded to each other to form a ring. As R¹And R²Examples of the ring bonded to each other include optionally substituted indenylene groups such as phenylindenylene.

Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, a carbonyloxy group, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, an alkylsulfinyl group having 1 to 20 carbon atoms, an alkylsulfonic group having 1 to 20 carbon atoms, an arylsulfonic group having 6 to 20 carbon atoms, a phosphonic acid group, an arylphosphonic acid group having 6 to 20 carbon atoms, an arylphosphonic acid group having 1 to 20 carbon atoms, a substituted aryl group, Alkyl ammonium groups having 1 to 20 carbon atoms, aryl ammonium groups having 6 to 20 carbon atoms, and the like. These organic groups having 1 to 20 carbon atoms, which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom, may have a substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

X¹And X²Each independently represents an arbitrary anionic ligand. The anionic ligand is a ligand having a negative charge when it is separated from the central metal atom, and examples thereof include a halogen atom, a diketonate group, a substituted cyclopentadienyl group, an alkoxy group, an aryloxy group, and a carboxyl group.

L¹And L²Represents a heteroatom-containing carbene compound or a neutral electron donor compound other than the heteroatom-containing carbene compound. Heteroatom-containing carbene compounds and compounds other than heteroatom-containing carbene compoundsThe neutral electron donor compound is a compound having a neutral charge when separated from the central metal. From the viewpoint of improving the catalyst activity, a heteroatom-containing carbene compound is preferable. The hetero atom means an atom of group 15 and group 16 of the periodic table of elements, and specifically includes a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, an arsenic atom, a selenium atom and the like. Among these, from the viewpoint of obtaining a stable carbene compound, a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom are preferable, and a nitrogen atom is more preferable.

The heteroatom-containing carbene compound is preferably a compound represented by the following general formula (3) or (4), and more preferably a compound represented by the following general formula (3) from the viewpoint of improving the catalytic activity.

[ chemical formula 2]

In the above general formulae (3) and (4), R³、R⁴、R⁵And R⁶Each independently represents a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms and containing a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom. Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom are the same as those in the above general formulae (1) and (2).

Furthermore, R³、R⁴、R⁵And R⁶The rings may be bonded to each other in any combination to form a ring.

In addition, from the viewpoint of further enhancing the effect of the present invention, R is preferably R⁵And R⁶Is a hydrogen atom. Furthermore, R³And R⁴The aryl group may preferably have a substituent, more preferably a phenyl group having an alkyl group having 1 to 10 carbon atoms as a substituent, and still more preferably a mesityl group.

Examples of the neutral electron donor compound include oxygen atoms, water, carbonyls, ethers, nitriles, esters, phosphines, phosphinates, sulfoxides, thioethers, amides, imines, aromatics, cyclic dienes, olefins, isocyanides, and isothiocyanates.

In the above general formulae (1) and (2), R¹、R²、X¹、X²、L¹And L²May be bonded to each other individually and/or in any combination to form a multidentate chelating ligand.

Further, as the ruthenium carbene complex used in the present invention, among the compounds represented by the above general formula (1) or (2), from the viewpoint of making the effect of the present invention more remarkable, the compounds represented by the above general formula (1) are preferable, and among them, the compounds represented by the following general formula (5) or (6) are more preferable.

The general formula (5) is shown below.

[ chemical formula 3]

In the above general formula (5), Z is an oxygen atom, a sulfur atom, a selenium atom, or NR¹²、PR¹²Or AsR¹²，R¹²Is a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; in order to further enhance the effect of the present invention, Z is preferably an oxygen atom.

In addition, R¹、R²、X¹And L¹As in the case of the above-mentioned general formulae (1) and (2), they may be bonded to each other individually and/or in any combination to form a polydentate chelate ligand, preferably X¹And L¹Do not form multidentate chelate ligands and R¹And R²Bonded to each other to form a ring, more preferably an indenylene group which may have a substituent, and still more preferably a phenylindenylene group.

Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom are the same as those in the above general formulae (1) and (2).

In the above general formula (5), R⁷And R⁸Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a heteroaryl group having 6 to 20 carbon atoms, and these groups may have a substituent or may be bonded to each other to form a ring. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and when a ring is formed, the ring may be any of an aromatic ring, an alicyclic ring, and a hetero ring, and preferably an aromatic ring, more preferably an aromatic ring having 6 to 20 carbon atoms, and still more preferably an aromatic ring having 6 to 10 carbon atoms.

In the above general formula (5), R⁹、R¹⁰And R¹¹Each independently is a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; these groups may have a substituent or may be bonded to each other to form a ring. Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom are the same as those in the above general formulae (1) and (2).

R⁹、R¹⁰And R¹¹Preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

Specific examples of the compound represented by the general formula (5) and a production method thereof include, for example, the compounds and production methods described in International publication No. 03/062253 (Japanese patent application laid-open No. 2005-515260).

The general formula (6) is shown below.

[ chemical formula 4]

In the above general formula (6), m is 0 or 1. m is preferably 1, in which case Q is an oxygen atom, nitrogen atom, sulfur atom, methylene group, ethylene group or carbonyl group, preferably methylene group.

In the above-mentioned general formula (6),

[ chemical formula 5]

Is a single bond or a double bond, preferably a single bond.

R¹、X¹、X²And L¹As in the case of the above-mentioned general formulae (1) and (2), the polydentate chelate ligands, preferably X, may be formed by bonding each alone and/or in any combination to each other¹、X²And L¹Do not form multidentate chelate ligands and R¹Is a hydrogen atom.

R¹³～R²¹Is a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; these groups may have a substituent or may be bonded to each other to form a ring. Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom are the same as those in the above general formulae (1) and (2).

R¹³Preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, R¹⁴～R¹⁷Preferably a hydrogen atom, R¹⁸～R²¹Preferably a hydrogen atom or a halogen atom.

Specific examples of the compound represented by the general formula (6) and a production method thereof include, for example, the compounds and production methods described in International publication No. 11/079799 (Japanese patent application laid-open No. 2013-516392).

Examples of the ruthenium carbene complex used in the present invention, which exhibits general performance, include compounds used in examples described later, and the following compound (7). In the compound (7), PCy₃Represents tricyclohexylphosphineAnd Mes represents mesitylene.

[ chemical formula 6]

The amount of the metathesis polymerization catalyst used is preferably 0.01 mmol or more, more preferably 0.1 to 50 mmol, and still more preferably 0.1 to 20 mmol, based on 1 mol of the total monomers used in the reaction. When the amount of the metathesis polymerization catalyst used is too small, the polymerization activity is too low and the reaction takes time, so that the productivity is poor, and when the amount is too large, the reaction is too vigorous, and the catalyst is likely to be solidified or precipitated before being sufficiently filled in a mold, and is difficult to store uniformly.

The metathesis polymerization catalyst may be used alone or in combination of two or more.

In order to control the polymerization activity, these metathesis polymerization catalysts preferably use an organoaluminum compound or an organotin compound in combination as an activator (co-catalyst).

As the activator in the case of using a compound of a transition metal of group 5 or 6 of the periodic table as a metathesis polymerization catalyst, there can be used, for example, alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride; alkoxyalkylaluminum chlorides in which a part of the alkyl groups of these alkylaluminum halides is substituted with an alkoxy group; organotin compounds, and the like. The amount of the activator used is not particularly limited, and is usually preferably 0.1 to 100 moles, and more preferably 1 to 10 moles, based on 1 mole of the total metathesis polymerization catalyst used in the cycloolefin polymerizable composition.

In the case of using a ruthenium carbene complex as a metathesis polymerization catalyst, an activator may be used or may not be used. Further, in the case of using a ruthenium carbene complex, since the activity of the catalyst is excellent at the time of bulk polymerization, the norbornene resin molded product obtained has an advantage of being less in odor derived from the unreacted norbornene monomer.

In addition, an activity modifier can be added as a component of the cycloolefin polymerizable composition. The activity modifier is used, for example, to prevent initiation of polymerization during injection into a mold when initiation of polymerization is performed.

Examples of the activity modifier in the case of using a compound of a transition metal of group 5 or 6 of the periodic table as a metathesis polymerization catalyst include compounds having an action of reducing the metathesis polymerization catalyst, and alcohols, halogenated alcohols, esters, ethers, nitriles and the like can be used. Among them, alcohols and halogenated alcohols are preferable, and halogenated alcohols are more preferable.

Specific examples of the alcohols include n-propanol, n-butanol, n-hexanol, 2-butanol, isobutanol, isopropanol, and tert-butanol. Specific examples of the halogenated alcohols include 1, 3-dichloro-2-propanol, 2-chloroethanol, 1-chlorobutanol and the like.

In particular, when a ruthenium carbene complex is used as a metathesis polymerization catalyst, a lewis base compound can be used as an activity regulator. Examples of the lewis base compound include lewis base compounds containing a phosphorus atom such as tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, triphenyl phosphite, and n-butylphosphine; and lewis base compounds containing a nitrogen atom such as N-butylamine, pyridine, 4-vinylpyridine, acetonitrile, ethylenediamine, N-benzylidenemethylamine, pyrazine, piperidine, and imidazole. Further, norbornene substituted with an alkenyl group such as vinylnorbornene, propenylnorbornene and isopropenylnorbornene functions as a monomer and also functions as an activity regulator. The amount of these activity regulators to be used may be appropriately adjusted depending on the compound to be used.

Free radical generator

The radical generator generates radicals by heating, thereby initiating a crosslinking reaction in the cycloolefin resin and also initiating a crosslinking reaction between the base resin contained in the gel coat composition and the cycloolefin resin, and has an effect of promoting adhesion between the gel coat and the cycloolefin resin layer. The sites where the radical generator initiates the crosslinking reaction are mainly carbon-carbon double bonds contained in the base resin of the gel coat and the cycloolefin resin, and crosslinking may occur in the saturated bond portion.

Examples of the radical generator include an organic peroxide, a diazo compound, and a nonpolar radical generator. Examples of the organic peroxide include: hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, and cumene hydroperoxide; dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide and t-butylcumyl peroxide; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; peroxyketals such as 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne, and 1, 3-bis (t-butylperoxyisopropyl) benzene; peroxy esters such as t-butyl peroxyacetate and t-butyl peroxybenzoate; peroxycarbonates such as t-butyl peroxyisopropyl carbonate and di (isopropyl peroxyl) dicarbonate; and a peroxidized alkylsilyl group such as t-butyltrimethylsilyl peroxide. Among them, in particular, in bulk polymerization, a dialkyl peroxide is preferable because it has little influence on the metathesis polymerization reaction.

Examples of the diazo compound include: 4,4 ' -bisazidobenzylidene (4-methyl) cyclohexanone, 4 ' -bisazidochalcone, 2, 6-bis (4 ' -azidobenzylidene) cyclohexanone, 2, 6-bis (4 ' -azidobenzylidene) -4-methylcyclohexanone, 4 ' -bisazidodiphenylsulfone, 4 ' -bisazidodiphenylmethane, 2 ' -bisazidostilbene and the like.

Examples of the nonpolar radical generator include: 2, 3-dimethyl-2, 3-diphenylbutane, 1, 4-diphenylbutane, 3, 4-dimethyl-3, 4-diphenylhexane, 1,2, 2-tetraphenylethane, 2,2,3, 3-tetraphenylbutane, 3,3,4, 4-tetraphenylhexane, 1, 2-triphenylpropane, 1, 2-triphenylethane, triphenylmethane, 1,1, 1-triphenylethane, 1,1, 1-triphenylpropane, 1,1, 1-triphenylbutane, 1,1, 1-triphenylpentane, 1,1, 1-triphenyl-2-propene, 1,1, 1-triphenyl-4-pentene, 1,1, 1-triphenyl-2-phenylethane and the like.

The amount of the radical generator in the cycloolefin polymerizable composition is usually 0.1 to 10 parts by mass, and preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total monomers used. When the content of the radical generator is in the above range, the crosslinking reaction proceeds sufficiently, the bending strength of the obtained molded article becomes good, and the reaction with the gel coat composition proceeds uniformly, and the adhesion between the cycloolefin resin layer and the gel coat layer is improved, which is preferable.

In the present invention, various additives may be added to the cycloolefin polymerizable composition in a range that does not impair the adhesion between the gel coat layer and the cycloolefin resin layer in order to improve or maintain the characteristics of the molded article obtained.

Examples of such additives include: reinforcing materials, antiaging agents, heat stabilizers, light stabilizers, ultraviolet absorbers, fillers, pigments, colorants, foaming agents, antistatic agents, flame retardants, lubricants, softeners, tackifiers, plasticizers, mold release agents, odor inhibitors, perfumes, elastomers, thermal cyclic olefin polymerization resins, hydrides thereof, and the like.

Various additives are added by the following method and the like in the method for producing a cycloolefin polymerizable composition described later: a method of adding the catalyst to a reaction liquid containing a catalyst and an activator; a method of preparing the reaction solution and mixing the reaction solution with a reaction solution containing a catalyst and an activator in reaction injection molding; and (3) filling in the mold in advance. The method of addition may be selected appropriately according to the type of additive.

Examples of the elastomer include: natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), ethylene-propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), and hydrogenated products thereof. The viscosity of the elastomer can be adjusted by dissolving the elastomer in the cycloolefin polymerizable composition and using the elastomer. Furthermore, the impact resistance of the resulting polymer can be improved by adding an elastomer. The amount of the elastomer used is preferably 0.5 to 20 parts by mass, and more preferably 2 to 10 parts by mass, based on 100 parts by mass of the total monomers in the cycloolefin polymerizable composition.

Examples of the antioxidant include various antioxidants for plastics and rubbers such as phenol type, phosphorus type, and amine type.

Preparation of cycloolefin polymerizable composition

The cycloolefin composition used in the present invention can be prepared by appropriately mixing the above-mentioned respective components according to a known method, or can be prepared by dividing the mixture into 2 parts or more of liquids and mixing the respective liquids at the time of the reaction. Each liquid was prepared using the above components so that only 1 part of the liquid did not undergo bulk polymerization, and when all the liquids were mixed, a cycloolefin polymerizable composition containing the components in a predetermined ratio was obtained. The combination of the 2 parts or more of the liquid includes the following two types (a) and (b) depending on the kind of the metathesis polymerization catalyst used.

(a) The method comprises the following steps The metathesis polymerization catalyst may be a metathesis polymerization catalyst which does not have a polymerization reaction activity by itself and exhibits a polymerization reaction activity by using an activator in combination. In this case, a cycloolefin polymerizable composition can be obtained by mixing a reaction raw liquid (a) containing a cycloolefin monomer and an activator and a reaction raw liquid (B) containing a cycloolefin monomer and a metathesis polymerization catalyst. Further, the reaction liquid (C) containing the cycloolefin monomer and not containing any of the metathesis polymerization catalyst and the activator may be used in combination.

(b) The method comprises the following steps In addition, when a metathesis polymerization catalyst having a polymerization reaction activity is used alone as the metathesis polymerization catalyst, a cycloolefin polymerizable composition can be obtained by mixing the reaction raw liquid (a) containing the cycloolefin monomer and the reaction raw liquid (b) containing the metathesis polymerization catalyst. In this case, as the reaction liquid (b), a reaction liquid obtained by dissolving or dispersing the metathesis polymerization catalyst in a small amount of an inert solvent is generally used. Examples of the solvent include: aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and trimethylbenzene; ketones such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and 4-hydroxy-4-methyl-2-pentanone; cyclic ethers such as tetrahydrofuran; diethyl ether, dichloromethane, dimethyl sulfoxide, ethyl acetate, etc., preferably an aromatic hydrocarbon, more preferably toluene.

The radical generator and any of various additives may be contained in any of the above-mentioned reaction liquids or may be added as a mixed liquid other than the above-mentioned reaction liquids.

As will be described later, the method for producing the cycloolefin resin decorative molded product of the present invention can be carried out by applying a known resin molding method, and it is preferable to mix the reaction liquid by selecting an appropriate mixing device according to the applied resin molding method and using the selected mixing device. Examples of the apparatus include a low-pressure mixer such as a dynamic mixer and a static mixer, in addition to a collision mixing apparatus generally used in the reaction injection molding method. The reaction liquids were immediately introduced into these apparatuses and mixed to form a cycloolefin polymerizable composition.

The cycloolefin polymerizable composition may contain a fibrous and/or particulate filler as appropriate. By polymerizing the cycloolefin composition containing the fibrous filler, a fiber-reinforced cycloolefin resin layer can be obtained, and as a result, a fiber-reinforced cycloolefin resin decorative molded article having a gel coat layer on the fiber-reinforced cycloolefin resin layer can be obtained.

In general, fiber-reinforced plastics have irregularities formed by fiber grains on the surface after molding due to differences in shrinkage and linear expansion coefficients between constituent reinforcing fibers and a matrix resin, and the fiber grains are transferred to the coating surface for decoration. Since the fiber pattern is generated even in the fiber-reinforced plastic using a cycloolefin resin as a matrix resin, the fiber pattern is transferred to the coating surface in the decoration by the usual coating, and it has been desired to laminate a gel coat decoration which is thicker and is difficult to transfer.

Since the cycloolefin resin decorative molded article obtained by the production method of the present invention is formed by bonding the gel coat layer and the fiber-reinforced cycloolefin resin layer, the gel coat layer has a smooth surface, and the irregularities corresponding to the irregularities of the reinforcing fibers are hardly visible on the surface.

The fibrous filler is not particularly limited as long as it is a fibrous filler used in the art. From the viewpoint of availability and usefulness, the long fiber is preferably 1 or more selected from carbon fiber and glass fiber. In the case of using both carbon fibers and glass fibers, the mixing ratio of the two is not limited, and from the viewpoint of the mixing effect, the glass fiber is preferably 0.1 to 10 parts by mass with respect to 1 part by mass of the carbon fibers.

The form of the fibrous filler is not particularly limited, and may be appropriately selected from unidirectional materials, woven fabrics, nonwoven fabrics, felts, knitted fabrics, rovings, staple fibers, and the like in which the fibrous filler is aligned in one direction. Among them, the form of continuous fibers such as unidirectional material, woven fabric, and roving is preferable. The fiber-reinforced cycloolefin resin obtained is preferably one having a high proportion of fibers and thus having a high mechanical strength.

As the form of the woven fabric, a conventionally known woven fabric can be used, and for example, a full weave structure in which fibers are interlaced such as a plain weave, a satin weave, a twill weave, and a triaxial weave can be used. As the form of the woven fabric, not only a two-dimensional woven fabric but also a stitched woven fabric, a three-dimensional woven fabric, or the like, which is fiber-reinforced in the thickness direction of the woven fabric, can be used.

When a fibrous filler is used for a woven fabric or the like, it is generally used as a fiber bundle. The number of filaments in 1 fiber bundle is not particularly limited, but is preferably in the range of 1000 to 100000 filaments, more preferably 5000 to 50000 filaments, and further preferably 10000 to 30000 filaments.

The carbon fiber is not particularly limited, and various carbon fibers produced by a conventionally known method such as acrylic, pitch, rayon, and the like can be used as desired. Among these, PAN-based carbon fibers produced from polyacrylonitrile fibers are preferably used because they do not cause inhibition of the metathesis polymerization reaction and can improve properties such as mechanical strength and heat resistance in the obtained fiber-reinforced cycloolefin resin.

Carbon fibers are preferable because they can maintain rigidity as their elastic modulus is higher, and therefore the thickness of the fiber-reinforced cycloolefin resin layer can be reduced. On the other hand, when the elastic modulus is too high, the tensile elongation may be lowered. The carbon fiber preferably has a tensile modulus of elasticity, as measured by the resin-impregnated strand tensile test (JIS R-7601), in the range of 200 to 400GPa, and more preferably in the range of 220 to 300 GPa. In addition, the carbon fiber is preferably high in tensile elongation. The tensile elongation is preferably 1.7% or more, more preferably 1.85% or more, and particularly preferably 2% or more. The tensile elongation is not particularly limited, but is usually 2.5% or less. The tensile elongation of the carbon fiber can be measured by the tensile test of the resin-impregnated strand. The higher the tensile elongation of the carbon fiber, the higher the fiber strength and the easier the handling, and the higher the mechanical strength of the obtained fiber-reinforced cycloolefin resin, the more preferable.

From the viewpoint of further improving the adhesion between the cycloolefin resin as the matrix resin and the carbon fibers, it is preferable that at least an appropriate amount of active hydrogen-containing groups such as carboxyl groups and hydroxyl groups are present on the surface of the carbon fibers. The amount of active hydrogen-containing groups of the carbon fiber can be quantified by the surface oxygen concentration (O/C) measured by X-ray photoelectron spectroscopy. The amount of active hydrogen-containing groups in the carbon fiber is preferably 0.02 to 0.2 in terms of O/C. Within this range, the active hydrogen-reactive groups (e.g., isocyanate groups and (meth) acrylate groups) contained in the cycloolefin monomer are preferably more effective in the carbon fibers, and the degree of oxidation of the carbon fiber surface is also appropriate. The amount of the active hydrogen-containing group in the carbon fiber is more preferably 0.04 to 0.15, and still more preferably 0.06 to 0.1 in terms of O/C.

The method for introducing the active hydrogen-containing group into the carbon fiber is not particularly limited, and a commonly used method may be appropriately employed. There are an ozone method, electrolytic oxidation in an acid solution, and the like, and an oxidation reaction in a solution which is economically excellent is preferable. In this case, the amount of the active hydrogen-containing group can be appropriately adjusted by the amount of current, temperature, residence time in the acid bath, the acid-alkali level, and the like.

The surface state of the carbon fiber is not particularly limited, and may be smooth or uneven. The unevenness is preferable in that an anchor effect can be expected. The degree of this unevenness can be appropriately selected. The introduction of the irregularities into the surface of the carbon fiber can be performed simultaneously with the oxidation reaction in the solution.

The cross-sectional shape of the carbon fiber is not particularly limited, and is preferably substantially circular. When the cross-sectional shape is circular, rearrangement of the filaments is likely to occur when the cycloolefin polymerizable composition is impregnated, and the polymerizable composition is likely to infiltrate between the fibers. In addition, there is an advantage that the thickness of the fiber bundle can be reduced and a fiber-reinforced cycloolefin resin excellent in covering property can be easily obtained. The fact that the cross-sectional shape is substantially circular means that the degree of deformation is 1.1 or less when the ratio (R/R) of the radius R of the circumscribed circle to the radius R of the inscribed circle of the cross-section is defined as the degree of deformation.

The length of the carbon fiber may be appropriately selected according to the application, and either short fiber or long fiber may be used. From the viewpoint of further improving the mechanical strength of the obtained fiber-reinforced cycloolefin resin, the length of the carbon fiber is usually 1cm or more, preferably 2cm or more, more preferably 3cm or more, and particularly, the carbon fiber as a continuous fiber is preferably used.

The carbon fiber used in the present invention does not require the sizing agent to be attached in advance, and is preferably a carbon fiber to which the sizing agent is attached in advance, from the viewpoint of further improving the adhesion between the cycloolefin resin as the matrix resin and the carbon fiber, because of the problem of the physical properties being lowered after molding due to fiber fuzzing.

The sizing agent is not particularly limited, and a known sizing agent can be used. Examples of the sizing agent include those selected from the group consisting of epoxy resins; a polyurethane resin; a vinyl ester resin; a polyamide resin; polyolefin resins such as nylon resin, polyethylene, and polypropylene; a polyester resin; and at least 1 of phenolic resins. The sizing agent is preferably at least 1 selected from the group consisting of epoxy resins, polyurethane resins, vinyl ester resins, and polyolefin resins, and more preferably an epoxy resin and/or a vinyl ester resin, from the viewpoint of easy availability.

Specific examples of such sizing agents include those made of epoxy resins such as KP-226, KP-0110, KP-136, KP-300, KP-752 and KP-1005, all of which are products of Songbu oil and fat pharmaceutical Co., Ltd; sizing agents formed by polyurethane resins such as KP-2816, KP-2817, KP-2807, KP-2820 and KP-2821; a sizing agent made of a vinyl ester resin such as KP-371 or KP-372; sizing agents made of nylon resins such as KP-1008; sizing agents made of polyethylene resins such as P-138; sizing agents formed by polypropylene resins such as TPE-100, TPE-102 and the like; and a sizing agent formed from a polyester resin such as KP-880 and KP-881.

The attachment of the sizing agent to the carbon fibers can be performed by bringing the sizing agent into contact with the carbon fibers. In this case, the sizing agent is preferably dispersed or dissolved in water or an organic solvent such as acetone, and used as a dispersion or solution. From the viewpoint of improving the dispersibility of the sizing agent and improving the liquid stability, it is preferable to add an appropriate surfactant to the dispersion or solution.

The amount of the sizing agent attached to the carbon fibers is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.5 to 2% by mass, based on 100% by mass of the total amount of the carbon fibers and the sizing agent. When the amount of the deposition is within this range, adequate carbon fiber astringency can be obtained, sufficient scratch resistance of the carbon fiber can be obtained, occurrence of fuzz due to mechanical friction or the like can be suppressed, impregnation of the cycloolefin polymerizable composition can be improved, and mechanical strength of the obtained fiber-reinforced cycloolefin resin can be improved.

The contact between the carbon fibers and the sizing agent can be suitably performed by a method generally used in industry, such as a roll impregnation method or a roll contact method. Since the carbon fibers are usually contacted with the sizing agent using a dispersion or solution of the sizing agent, the carbon fibers may be subjected to a drying step after the contact, and water or an organic solvent contained in the dispersion or solution of the sizing agent may be removed. The drying step can be performed by a method using hot air, a hot plate, a roller, various infrared heaters, or the like as a heat medium.

The carbon fibers are preferably attached with the sizing agent after the active hydrogen-containing groups are introduced to the surface of the carbon fibers and the irregularities are introduced.

The glass fiber used in the present invention is not particularly limited, and examples thereof include glass fibers having a shape of continuous fibers, woven fabrics, nonwoven fabrics, and the like, and glass fibers having various thicknesses are commercially available. The shape and thickness of the glass fiber can be appropriately selected depending on the application.

The mass per unit area of the glass fiber used in the present invention is appropriately selected depending on the purpose of use, and is preferably 600g/m²More preferably 600 to 2000g/m²More preferably 640 to 1800g/m². When the mass per unit area of the glass fibers is within the above range, the space between adjacent glass fibers is appropriate, the mechanical strength of the obtained fiber-reinforced cycloolefin resin becomes good, the flexibility is good, and the impregnation property of the cycloolefin polymerizable composition is improved, which is preferable.

The glass fibers are preferably surface-hydrophobized. By using the hydrophobized glass fiber, the glass fiber can be uniformly dispersed in the obtained fiber-reinforced cycloolefin resin, and the rigidity and the dimensional stability of the fiber-reinforced cycloolefin resin can be balanced and the anisotropy can be reduced. Examples of the treating agent used for the hydrophobization treatment include a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a fatty acid, an oil or fat, a surfactant, a wax, and other polymers. These treating agents also function as sizing agents.

Examples of the short fibers include short fibers obtained by cutting the above carbon fibers or glass fibers, wollastonite, potassium titanate, xonotlite, basic magnesium sulfate, aluminum borate, quadrangular pyramid-shaped zinc oxide, gypsum fibers, phosphate fibers, alumina fibers, needle-shaped calcium carbonate, and needle-shaped boehmite.

The relationship between the amount of the fibrous filler and the amount of the cycloolefin polymerizable composition impregnated into the fibrous filler is preferably 0.2 to 3 parts by volume, more preferably 0.5 to 2.5 parts by volume, and still more preferably 0.7 to 2 parts by volume, based on 1 part by volume of the cycloolefin polymerizable composition. When the amount is within this range, the bending strength of the resulting molded article can be favorably exhibited.

Specific examples of the particulate filler include: calcium carbonate, calcium hydroxide, calcium silicate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, titanium oxide, zinc oxide, barium titanate, silica, alumina, carbon black, graphite, antimony oxide, red phosphorus, various metal powders, clay, various ferrites, hydrotalcite, and the like.

The surface of the particulate filler is preferably subjected to a hydrophobic treatment. By using the particulate filler subjected to the hydrophobization treatment, aggregation and sedimentation of the particulate filler in the cycloolefin polymerizable composition can be prevented, and the particulate filler in the cycloolefin resin layer formed by polymerizing the cycloolefin polymerizable composition can be uniformly dispersed.

Examples of the treating agent used for the hydrophobization treatment include silane coupling agents such as vinyltrimethoxysilane, titanate coupling agents, aluminum coupling agents, fatty acids such as stearic acid, oils and fats, surfactants, and waxes. The hydrophobization of the particulate filler may be carried out by mixing a hydrophobizing agent at the same time when the cycloolefin polymerizable composition is produced, or the hydrophobization of the particulate filler may be carried out in advance with respect to the particulate filler used.

In order to improve the adhesion to the filler added to the cycloolefin polymerizable composition, a polar compound such as an isocyanate compound or a polyfunctional acrylate compound may be added as necessary.

Examples of the isocyanate compound include: aromatic diisocyanate compounds such as 4,4 '-methylene diphenyl diisocyanate (MDI), toluene-2, 4-diisocyanate, 4-methoxy-1, 3-phenylene diisocyanate, 4-isopropyl-1, 3-phenylene diisocyanate, 4-chloro-1, 3-phenylene diisocyanate, 4-butoxy-1, 3-phenylene diisocyanate, 2, 4-diisocyanate diphenyl ether, 1, 4-phenylene diisocyanate, toluene diisocyanate, Xylylene Diisocyanate (XDI), 1, 5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4, 4' -diisocyanate dibenzyl ester; aliphatic diisocyanate compounds such as methylene diisocyanate, 1, 4-tetramethylene diisocyanate, 1, 6-hexamethylene diisocyanate, and 1, 10-decamethylene diisocyanate; 4-cyclohexylene diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), 1, 5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, hydrogenated XDI and other alicyclic diisocyanate compounds, and polyurethane prepolymers obtained by reacting these diisocyanate compounds with low molecular weight polyols and polyamines so that the terminal groups become isocyanates.

The amount of the diisocyanate compound blended in the cycloolefin polymerizable composition is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and still more preferably 2 to 10 parts by mass, based on 100 parts by mass of all the monomers used.

The amount of the polyfunctional acrylate compound blended in the cycloolefin polymerizable composition is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and still more preferably 2 to 10 parts by mass, based on 100 parts by mass of all the monomers used. Examples of the polyfunctional acrylate compound include ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate (trimethylpropane trimethacrylate), neopentyl glycol dimethacrylate, and the like.

The content of the particulate filler in the cycloolefin polymerizable composition is preferably 10 to 1000 parts by mass, and more preferably 100 to 500 parts by mass, based on 100 parts by mass of the total monomers used. When the content is within this range, the strength of the resulting molded article can be improved, which is preferable.

The filler may be contained in the cycloolefin polymerizable composition in advance and injected into the mold together, or the filler may be provided in the mold in advance and the cycloolefin polymerizable composition may be injected thereinto, and may be selected as appropriate.

Forming method

In the production method of the present invention, the molding method for obtaining the cycloolefin resin decorative molded product is not particularly limited, and can be performed by using a known resin molding method as appropriate depending on the desired shape of the molded product. Examples of the resin molding method include: reaction injection molding (RIM process), resin transfer molding (RTM process), and infusion molding.

For example, when the cycloolefin resin decorative molded article obtained by the production method of the present invention has a gel coat layer and a fiber-reinforced cycloolefin resin layer, the cycloolefin resin decorative molded article can be produced by the following method: a gel coat composition is applied to the surface of a mold, a fibrous filler is laminated on the gel coat composition coating film in an uncured or semi-cured state, the cyclic olefin polymerizable composition is impregnated with the fibrous filler, and then the cyclic olefin polymerizable composition is polymerized while curing the gel coat composition in a state where the coating film is in contact with the impregnated cyclic olefin polymerizable composition. When the coating film of the gel coat composition is completely cured before polymerization of the cycloolefin polymerizable composition, sufficient adhesion cannot be obtained.

Further, by applying the gel coat composition to the surface of the mold and then charging the cycloolefin polymerizable composition into the coating film of the gel coat composition, a cycloolefin resin decorative molded article can be obtained in which the surface of the mold is transferred with high quality to the gel coat layer, the gel coat layer surface is smooth, and unevenness due to unevenness of the reinforcing fiber is hardly seen on the surface.

The temperature of the cycloolefin polymerizable composition before being supplied to the molding die is preferably 10 to 60 ℃, and the viscosity of the cycloolefin polymerizable composition is, for example, usually 5 to 3000 mPas, preferably about 50 to 1000 mPas at 30 ℃. The thickness of the gel coat obtained is preferably 10 to 500 μm, and more preferably 30 to 100 μm from the viewpoint of decorativeness and strength.

Forming die

The material of the mold to be used is not particularly limited, and specific examples thereof include steel, metal materials such as aluminum, zinc alloy, nickel, copper, and chromium, and resins, and the shape of the molded article to be processed by a processing method such as electroforming, thermal spraying, and plating, in addition to forging and casting, may be selected as appropriate depending on the structure of the mold and the resin molding method to be applied.

When the fibrous filler is placed in the mold in advance, the fibrous filler may be placed in the selected mold so as to be suitable for the resin molding method to be used. The gas in the mold may be replaced with an inert gas such as nitrogen gas or the pressure in the mold may be reduced as appropriate.

RIM method

The method is not particularly limited, and a molding die having a split-type die structure, that is, a male die and a female die is generally used. The male mold and the female mold are manufactured to form a void (cavity) suitable for the shape of a desired molded article. The fibrous filler is placed in the gap of the mold. The impregnation of the fibrous filler with the cycloolefin polymerizable composition is performed by injecting the cycloolefin polymerizable composition into a mold. The cycloolefin composition used in the present invention has a low viscosity and is excellent in impregnation into a base material, and can be uniformly impregnated into a fibrous filler.

In the molding of a two-component reaction type resin by the RIM method, the pressure at which the raw material (cycloolefin polymerizable composition) is injected into the mold during molding is about 1/30 to 1/500 of the pressure at which the resin is injected. Therefore, the filling property into the mold is very good, and the mold can be easily molded into various shapes. Since the injection pressure into the mold is very small, the internal pressure generated in the mold is also very small, and therefore, the strength required for the mold is greatly reduced as compared with a mold for injection molding, and the design of the mold becomes easy. Therefore, the mold for a large-sized molded product is also easy to design, and the large-diameter piping member, which is difficult to expand, is also easily expanded to the resin piping member. Further, the molding can be performed in a normal temperature range.

The filling pressure (injection pressure) at the time of filling the cyclic olefin polymerizable composition into the cavity of the molding die is usually 0.01 to 9.8MPa, preferably 0.02 to 5 MPa. In addition, the clamping pressure is usually in the range of 0.01 to 10 MPa.

RTM method

In the RTM (resin transfer molding) method, a cycloolefin polymerizable composition is injected into a mold filled with a fibrous filler, whereby the fibrous filler can be impregnated with the composition.

The molding by the RTM method not only generates a small pressure in the mold as in the RIM method, but also can simplify the mixing equipment because a mixing pressure as high as the RIM method is not required when mixing the cycloolefin polymerizable composition. In addition, since the polymerization rate is generally slower than that of the RIM method, it is generally advantageous in terms of impregnation.

The filling pressure (injection pressure) at the time of filling the cyclic olefin polymerizable composition into the cavity of the molding die is usually 0.01 to 9.8MPa, preferably 0.02 to 5 MPa. In addition, the clamping pressure is usually in the range of 0.01 to 10 MPa.

Injection molding method

In the injection molding method, the cyclic olefin polymerizable composition is filled into a mold by a vacuum pressure (about 0.1 to 100 Pa) and impregnated into a fibrous filler (e.g., glass fiber). Specifically, a fibrous filler is placed on a mold, and if desired, the fibrous filler is covered with an airtight film in a state where a release sheet and a resin diffusion material are arranged, and air in the airtight space is evacuated to be brought into a reduced pressure state. In this reduced pressure state, the cycloolefin polymerizable composition is injected into the airtight space, and the fibrous filler is impregnated with the cycloolefin polymerizable composition. The method is a method of forming a molded article free from stains and odor, and is suitable for forming a molded article having high strength such as a large-sized molded article, a thick article molded article, or the like.

In the method for manufacturing a cycloolefin resin decorative molded product of the present invention, in addition to the above-described method, a light resin transfer molding (L-RTM) method can be applied as an improved method. Basically, a molding method combining a pour molding method and an RTM method is a method in which a fibrous filler is placed on a female mold of a concave-convex mold, a male mold is closed, and pressure reduction is performed through an outer peripheral flange portion and a central portion of the mold. The inside of the mold is evacuated (about 0.1 to 100 Pa), the mold is closed, and the cycloolefin polymerizable composition is injected from the outer periphery thereof, thereby impregnating the fibrous filler with the composition. The excess cycloolefin polymerizable composition was accumulated in a pot at the center of the mold. The cycloolefin polymerizable composition is pressed from the outer periphery, and the composition is injected under reduced pressure and increased pressure. The filling pressure (injection pressure) at the time of filling the cyclic olefin polymerizable composition into the cavity of the molding die is usually 0.01 to 10MPa, preferably 0.02 to 5 MPa. In addition, the clamping pressure is usually in the range of 0.01 to 10 MPa.

Other impregnation methods

As another impregnation method, for example, the following method can be used: a method of preparing a material obtained by winding a fibrous filler in a dry state in an arbitrary cylinder by a filament winding method or the like, and impregnating the cyclic olefin polymerizable composition with the fibrous filler; a method of impregnating the fibrous filler with a cycloolefin polymerizable composition by spraying the composition; and a method of spraying each of the reaction liquids to the fibrous filler in combination of the above reaction liquids, and mixing the reaction liquids while spraying to impregnate the cycloolefin polymerizable composition.

The bulk polymerization is carried out by heating a mold such as injection of the cycloolefin polymerizable composition in advance or after the injection. The method of heating may be appropriately determined depending on the metathesis polymerization catalyst used in the cycloolefin polymerizable composition.

In the case where the cycloolefin polymerizable composition is supplied to the cavity formed in the molding die paired with the male die and the female die to perform bulk polymerization, in the case where the metathesis polymerization catalyst is a central atom of a group 6 transition metal such as molybdenum or tungsten, for example, in order to make the surface of the molded article formed with the gel coat a surface having a good appearance without pores or bubbles, the temperature of either the male die or the female die of the molding die is preferably 30 ℃ or higher and 80 ℃ or lower, preferably 40 ℃ or higher and 75 ℃ or lower, and more preferably 45 ℃ or higher and 70 ℃ or lower. The temperature of the other of the male mold and the female mold of the molding die is preferably 50 ℃ to 100 ℃, preferably 60 ℃ to 95 ℃, and more preferably 70 ℃ to 90 ℃. The temperature difference between the male mold and the female mold is preferably 10 ℃ to 50 ℃, more preferably 15 ℃ to 45 ℃, and still more preferably 20 ℃ to 40 ℃.

When the metathesis polymerization catalyst is a metathesis polymerization catalyst of group 8 containing ruthenium and osmium as the central metal, the maximum temperature of the molding die is preferably 90 ℃ to 300 ℃. The maximum temperature is more preferably 100 to 270 ℃, and still more preferably 120 to 250 ℃. The minimum temperature in the bulk polymerization is preferably 40 to 90 ℃ and more preferably 50 to 85 ℃. The initiation temperature of the bulk polymerization is usually in the range of 0 to 40 ℃ and preferably in the range of 10 to 30 ℃.

In the case where the metathesis polymerization catalyst is a metathesis polymerization catalyst of group 8 containing ruthenium or osmium as a central metal, the temperature difference between the male mold and the female mold is preferably 30 ℃ or less, more preferably 25 ℃ or less, and further more preferably 20 ℃ or less in order to form a surface having a beautiful appearance without pores or bubbles.

Examples of the method of adjusting the temperature of the mold include: adjusting the temperature of the forming die by using a heater; the temperature of a heat medium such as temperature-controlled water or oil circulating through a pipe embedded in the mold is adjusted.

After the operation of injecting the cycloolefin polymerizable composition into the mold or introducing the cycloolefin polymerizable composition into a predetermined mixing device, the bulk polymerization is completed preferably within a range of 20 seconds to 60 minutes, more preferably within a range of 20 seconds to 40 minutes, and may be maintained as it is for about 60 to 200 minutes. The heating may be performed in one stage, or may be performed in a plurality of stages including two or more stages.

After the completion of the bulk polymerization, the molded article can be obtained by, for example, opening the mold with a mold box and removing the mold. In the present specification, the term "mold release" refers to taking out a molded article obtained from a mold used. Since the molded article just produced is in a high-temperature state, the mold release is preferably performed after cooling to normal temperature.

The above-described process can produce a cycloolefin resin decorative molded article. The cycloolefin resin decorative molded article is a molded article in which a gel coat decorative surface (gel coat) is in close contact with a cycloolefin resin layer, and the close contact between the gel coat decorative surface and the cycloolefin resin layer is generally classified into 0 or 1, which is a standard of pass in an adhesion test conducted by a method according to JIS K5600.

Examples

The present invention will be described in further detail below with reference to examples, but the present invention is not limited to these examples. In the present example, an RTM method in which a carbon fiber is impregnated with a cycloolefin polymerizable composition using a mold will be described. In addition, the well-known RIM method and the infusion molding method can be similarly performed.

Example 1

AF7-EZ, made by Chem-Trend, is applied as a mold release agent to the inner surface of an aluminum mold having a side male-female opening into which a cycloolefin polymerizable composition can be injected and an inner dimension of 300mm in length, 200mm in width and 2mm in thickness. The master model side was heated to 50 ℃ and the gel coat composition 1 described below was sprayed onto the bottom surface of the inner surface using a spray coater to give a film thickness of about 50 μm.

The sprayed gel coat composition 1 was heated at 50 ℃ for 30 minutes to a degree that the surface thereof became sticky, semi-cured, and then a Toray carbon fiber felt CK6240E, made by Toray corporation, which was cut into fibers having a length of 290mm and a width of 190mm, was spread and 10 sheets were stacked inside the master model. The male mold was set on the female mold, and then the whole was heated to 50 ℃ to fill the mold with a cycloolefin polymerizable composition 1 described later.

After leaving at 50 ℃ for 10 minutes, the whole mold was heated at 90 ℃ for 30 minutes, and further heated at 120 ℃ for 1 hour, and then the male and female molds were separated, and the cycloolefin resin decorative molded article having the fiber-reinforced cycloolefin resin layer decorated with the gel coat was taken out from the inside.

The obtained fiber-reinforced cycloolefin resin layer was composed of 51 parts by volume of carbon fibers and 49 parts by volume of cycloolefin resin, and had a flexural strength of 640MPa as measured according to JIS K7017.

The adhesion of the gel coat decorative surface of the fiber-reinforced cycloolefin resin layer was confirmed by the method of JIS K5600, and the classification of the test result was 1. The classification of the test result as 0 or 1 is acceptable, and the adhesion between the gel coat layer and the cycloolefin resin layer of the obtained gel coat decorated cycloolefin resin decorated molded article is acceptable.

Preparation of gel coat composition 1

To 100 parts by mass of NR-AC0001P manufactured by TOMATEC corporation, 2 parts by mass of methyl ethyl ketone peroxide was added and mixed in a room at 23 ℃. The prepared gel coat composition 1 was used immediately after preparation. In the gel coat composition 1, the curing accelerator such as a cobalt compound or a manganese compound is 1 mass% or less.

Preparation of cycloolefin polymerizable composition 1

In a room at 23 ℃,5 parts by mass of trimethylpropane triacrylate, 5 parts by mass of hexamethylene diisocyanate, and 2 parts by mass of di-tert-butyl peroxide were mixed with a cycloolefin mixture containing 93 parts by mass of dicyclopentadiene and 7 parts by mass of tricyclopentadiene to prepare a mixed solution (a).

In a room at 23 ℃, 0.03 parts by mass of [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] dichloro (phenylmethylene) (trichlorohexylphosphine) ruthenium was dissolved in 1 part by mass of cyclopentanone to prepare a mixed solution (B).

Immediately after the mixed solutions (a) and (B) were prepared, the mixed solutions (a) and (B) were uniformly mixed to prepare a cycloolefin polymerizable composition 1. The prepared cycloolefin polymerizable composition 1 was immediately used.

Example 2

A cycloolefin resin decorative molded article having a fiber-reinforced cycloolefin resin layer with a gel coat decorated was obtained in the same manner as in example 1, except that the gel coat composition 1 was replaced by the spray of the gel coat composition 2. The obtained fiber-reinforced cycloolefin resin layer was composed of 51 parts by volume of carbon fibers and 49 parts by volume of cycloolefin resin, and had a flexural strength of 635MPa measured according to JIS K7017.

The adhesion of the gel coat decorative surface of the fiber-reinforced cycloolefin resin layer was confirmed by the method of JIS K5600, and the classification of the test result was 1. The classification of the test result as 0 or 1 is acceptable, and the adhesion between the gel coat layer and the cycloolefin resin layer of the obtained gel coat decorated cycloolefin resin decorated molded article is acceptable.

Preparation of gel coat composition 2

1 part by mass of bis (4-t-butylcyclohexyl) peroxydicarbonate and 1 part by mass of 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate were mixed in a room at 23 ℃ to prepare a paste, and the paste was added to 100 parts by mass of NR-AC0001P manufactured by TOMATEC corporation to mix them. The prepared gel coat composition 2 was used immediately after preparation. In the gel coat composition 2, the curing accelerator such as a cobalt compound or a manganese compound is 1 mass% or less.

Industrial applicability

The cycloolefin resin decorative molded product obtained by the production method of the present invention has the characteristics of the cycloolefin resin and also has high-grade decorative performance superior to that of a usual coating, and is an excellent molded product, and therefore, can be preferably used in fields where the cycloolefin resin is usually used, for example, a moving object, a housing of a moving object, a member of a housing facility, and the like.