JP2001164201A - Primer composition, cycloolefin polymer complex using the same, and method of producing the complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a primer composition capable of well adhering a metathesis polymer from a cycloolefin to the surface of a substrate, such as plastics and metals, to provide a cycloolefin polymer complex obtained by using the composition, and to provide a method of producing the complex. SOLUTION: This primer composition contains a metathesis polymerization catalyst and a resin. The composition preferably contains a thermoplastic resin as the resin, and more preferably contains an epoxy resin or a urethane resin. The method of producing cycloolefin polymer complex comprises treating a surface of the substrate with the primer composition, applying a molding material containing the cycloolefin and the metathesis polymerization catalyst to the treated surface and curing the material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a primer composition capable of favorably adhering a metathesis polymer of cycloolefin to the surface of a substrate such as plastics and metals, a cycloolefin polymer composite using the same, and The present invention relates to a method for producing the composite.

[0002]

BACKGROUND OF THE INVENTION It is known that cycloolefins undergo ring-opening polymerization with metathesis polymerization catalyst systems. For example, J. Am. Chem. Soc. , 196
0, Vol. 82, 2337 describes that ring-opening polymerization of norbornene is carried out by a metathesis catalyst system.
ew. Chem. Int. Edn. , 1964, Vol.
3,723 contains cyclopentene as a metathesis catalyst system [MoC
1 ₅ / Al (C ₂ H ₅ ) ₃ ]. A method for producing a polymer by ring-opening polymerization of a cycloolefin is also known. For example, JP-A-50-130900 and JP-A-52-33000
Japanese Patent Application Laid-Open Publication No. H11-163,086 discloses a method for producing a ring-opening polymer using a metathesis catalyst system comprising a halide such as tungsten or molybdenum and an organoaluminum compound.

On the other hand, there is also known a method in which a norbornene-type monomer such as dicyclopentadiene or tricyclopentadiene is subjected to bulk polymerization by reaction injection molding (RIM) to obtain a crosslinked polymer molded product. For example, JP-A-58-12
No. 7728 and JP-A-58-129003 disclose a solution A comprising a mixture of a catalytic component of a metathesis catalyst system and a monomer, and a solution B comprising a mixture of an activator of a metathesis catalyst system and a monomer. Reaction injection molding (RIM)
To obtain a crosslinked polymer molded product.

JP-A-59-51911 discloses a metathesis catalyst in which a catalyst component selected from organic ammonium salts of tungsten and molybdenum is combined with an activator selected from alkoxyalkylaluminum halides and aryloxyaluminum halides. A method for producing a crosslinked polymer molded article by reaction injection molding of a norbornene-type monomer using the system is disclosed.

[0005] Japanese Patent Application Laid-Open No. 3-205409 discloses a double decomposition in which a catalyst component selected from tungsten hexachloride and tungsten oxytetrachloride is combined with an activator selected from diethyl aluminum chloride and ethyl aluminum dichloride. A method for producing a dicyclopentadiene polymer crosslinked by a reaction injection molding method using a catalyst system is disclosed. It has been found that in these metathesis catalyst systems, the catalyst component is activated by an activator and causes ring-opening polymerization of the norbornene-type monomer. In the case of performing the reaction injection molding, the solution A and the solution B are collision-mixed, and the mixed solution is immediately poured into a mold in a liquid state,
Ring-opening polymerization is performed in bulk. In the metathesis catalyst system described above, it has been found that the catalyst component is activated by a cocatalyst (activator) component and causes ring-opening polymerization of norbornene-type cycloolefins. When the above reaction injection molding is performed, the solution A and the solution B are collision-mixed, and the mixed solution is immediately poured into a mold in a liquid state, and is subjected to ring-opening polymerization in a lump. It is also known that the cured product obtained in this way has excellent mechanical properties, electrical properties, water resistance and the like.

[0006]

However, the polymers of cycloolefins using these metathesis polymerization catalysts are:
Since there is no polar group in the molecule, adhesion to plastics and metals serving as substrates is extremely low. Therefore, as it is, it cannot be used for applications that are combined with plastic, metal, or the like. Therefore, a method of treating the surface of a substrate in advance with a silane coupling agent (for example,
263124, JP-A-2-6525, JP-A2-1
85558, JP-A-2-276852, JP-A-10
-17676 publication) is known. However, this method is effective for bonding with inorganic substances such as glass and metal, but has little effect on plastic. Also, JP-A-3-106939 and JP-A-3-147.
No. 822 and JP-A-5-247241 propose a method of applying a hydrocarbon resin-based primer to the surface of a base material. These primers have excellent adhesiveness to an olefin-based resin, but have a high polarity. Poor adhesion to large plastics and metals. In addition, a method of improving the adhesiveness by copolymerizing monomers having a polar group such as a hydroxyl group or a carboxyl group is considered, but these polar groups are known to cause curing inhibition. Further, Japanese Patent Application Laid-Open No. Hei 7-26
6434, JP-A-8-266434, JP-A-10-
JP-A-130577 discloses a method using a polyurethane resin as a primer. However, although the adhesion between the substrate and the primer is good, the primer is easily separated between the primer and the cycloolefin polymer. The present invention relates to a primer composition capable of satisfactorily adhering a cycloolefin metathesis polymer to the surface of a substrate such as plastics and metals, a cycloolefin polymer composite using the same, and a method for producing the composite. Is provided.

[0007]

Means for Solving the Problems In order to form a cycloolefin polymer composite by integrally molding a cycloolefin polymer with a base material such as plastics and metals, the present inventors have proposed a method for forming a cycloolefin polymer composite. As a result of examining a primer that enhances the adhesive force at the olefin polymer interface, the use of a primer composition containing a metathesis polymerization catalyst as a primer significantly improves the adhesion between the substrate and the cycloolefin polymer. And completed the present invention.

That is, the present invention provides a primer composition capable of favorably adhering a metathesis polymer of cycloolefin to the surface of a base material such as plastics and metals, a cycloolefin polymer composite using the same, and a composite thereof. And a method for producing the same. That is, the present invention is a primer composition containing a metathesis polymerization catalyst and a resin. The resin is preferably a thermosetting resin, the thermosetting resin is preferably an epoxy resin or a urethane resin, and a hydroxyl group-containing norbornene-based resin is preferably used as one of the polyol components of the urethane resin. In the present invention, a component that becomes a resin by reacting as a resin is also referred to as a resin. For example, a urethane resin is referred to as an isocyanate component and a polyol component, and an epoxy resin is referred to as a resin containing an epoxy resin component and a curing agent component. The metathesis polymerization catalyst is preferably a ruthenium compound, and the metathesis polymerization catalyst is preferably a catalyst represented by the general formula (A).

Embedded image (M represents ruthenium or osmium, X and X1 each independently represent an anionic ligand, L and L1 each independently represent a neutral electron donating group, Q and Q1 each independently represent hydrogen, alkyl Group, alkenyl group or aromatic group, and the alkyl group, alkenyl group or aromatic group may have a substituent.) Further, the metathesis polymerization catalyst is a catalyst represented by the general formula (B). It is preferred that there is.

Embedded image (M represents ruthenium or osmium, X and X1 each independently represent an anionic ligand, L and L1 each independently represent a neutral electron donating group, R1 and R2
Are each independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group, a carboxylate group having 1 to 18 carbon atoms, An alkoxy group, an alkenyloxy group having 2 to 18 carbon atoms, an alkynyloxy group having 2 to 18 carbon atoms, an allyloxy group having 2 to 18 carbon atoms, and having 2 to 1 carbon atoms
An alkoxycarbonyl group having 8 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, an alkylsulfonyl group having 1 to 18 carbon atoms or an alkylsulfinyl group having 1 to 18 carbon atoms;
Represents hydrogen, an aryl group or an alkyl group having 1 to 18 carbon atoms. Furthermore, it is preferable that the metathesis polymerization catalyst is a catalyst represented by the general formula (C).

Embedded image (M represents ruthenium or osmium, X and X1 each independently represent an anionic ligand, L and L1 each independently represent a neutral electron donating group, Q and Q1 each independently represent hydrogen, alkyl Represents an alkyl group, an alkenyl group or an aromatic group, and the alkyl group, the alkenyl group or the aromatic group may have a substituent.) In the present invention, the surface of the substrate is treated with the above primer composition. And a cycloolefin polymer composite obtained by curing a molding material containing a cycloolefin and a metathesis polymerization catalyst on the treated surface. Further, the present invention provides a method for producing a cycloolefin polymer composite, in which a substrate surface is treated with the above primer composition, and a molding material containing a cycloolefin and a metathesis polymerization catalyst is cured on the treated surface.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the method for producing a cycloolefin polymer composite of the present invention, a base material is treated with a primer composition containing a metathesis polymerization catalyst and a resin, and a molding containing a cycloolefin and a metathesis polymerization catalyst on the treated surface. This is to cure the material.

The substrate used in the present invention is not particularly limited, and may be, for example, polyethylene, polypropylene, poly-4-methylpentene, ionomer, polyvinyl chloride, polyvinylidene chloride, polystyrene, AS as plastic.
Resin, ABS resin, (meth) acrylic resin, polyvinyl alcohol, EVA, cellulosic plastic, polyamide resin, polyacetal, polyphenylene ether, modified polyphenylene ether, PET, PBT, P
EN, polyphenylene sulfide, polysulfone, polyacrylate, polyetherimide, thermoplastic resin such as polyethersulfone, polyetherketone, polyamideimide, polyimide, etc., unsaturated polyester resin, phenol resin, epoxy resin, urethane resin, silicone resin, urea Thermosetting resins such as resin and melamine resin are exemplified. In addition, various rubbers and elastomers can be used. Various metals such as iron, carbon steel, and stainless steel, galvanized steel, and nitrided steel, metals such as aluminum, copper, and titanium, and various alloys as metals. Further, in order to improve the weather resistance and appearance on the outer surface of the base material, various synthetic resin paints such as urethane resin, acrylic resin and polyester resin are applied or plated.

The primer composition used in the present invention comprises a resin and a metathesis polymerization catalyst. The resin is not particularly limited, but various thermoplastic resins and thermosetting resins can be used. These can be used alone or in combination of two or more. Further, a thermosetting resin and a thermoplastic resin may be used in combination.

The thermoplastic resin is not particularly restricted but includes polyolefins such as polyethylene, polypropylene, chlorinated polyethylene and chlorinated polypropylene;
Methylpentene, ionomer, polyvinyl chloride, polyvinylidene chloride, polystyrene, AS resin, ABS resin, (meth) acrylic resin, polyvinyl alcohol, E
VA, cellulose-based plastic, polyamide resin, polyacetal, polyphenylene ether, modified polyphenylene ether, polyester, polydiallyl phthalate, polyacrylate, polyetherimide, polyethersulfone, polyetherketone, polyamideimide, polyimide, etc., and rubbers such as SBR , BR, I
R, EPM, EPDM, NBR, chloroprene rubber, I
IR, urethane rubber, silicone rubber, and various elastomers are used. These can be used alone or in combination of two or more.

Although there is no particular limitation on the thermosetting resin, these resins include unsaturated polyester resins,
Phenol resin, epoxy resin, urethane resin, silicone resin, urea resin, melamine resin, and the like can be given. These resins are more preferably epoxy resins or urethane resins because of their high adhesiveness.

The epoxy resin is not particularly limited,
Glycidyl ether-based bisphenol A type, bisphenol F type, bisphenol S type, phenol novolak type, cresol novolak type and the like can be mentioned. These are used together with a curing agent.As the curing agent, polyamines such as diethylenetriamine, isophoronediamine, diaminodiphenylmethane and modified products thereof, polyaminoamides, and acid anhydrides such as hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, and dicyandiamide, Polymer captan, phenolic resin, urea resin, melamine resin and the like can be mentioned. These epoxy resins and curing agents can be used alone or in combination of two or more. If necessary, a curing accelerator such as a tertiary amine, imidazole, or a phosphorus compound may be used in combination.

The urethane resin used in the present invention is not particularly limited, but generally comprises an isocyanate and a polyol.

The isocyanate for the urethane resin used in the present invention is not particularly limited. Examples thereof include toluene diisocyanate (hereinafter abbreviated as TDI), diphenylmethane diisocyanate (hereinafter abbreviated as MDI), paraphenylene diisocyanate, and metaphenylene diisocyanate.
Aromatic isocyanates such as naphthalene-1,5-diisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate, polyphenylenepolymethylene polyisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), 1,10-decane Diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,
Aliphatic and alicyclic diisocyanates such as 3 and 1,4-diisocyanate, isophorone diisocyanate,
Alicyclic diisocyanates such as hydrogenated TDI and hydrogenated MDI;
Alternatively, some of these isocyanates are prepolymerized into urethane, burette, allohanate, uretdione, uretonimine, carbodiimide, oxazolidone, amide, imide, and the like.
They can be used alone or in combination of two or more.

The polyol for the urethane resin used in the present invention is not particularly limited, and includes polyester polyols, graft polyols, polylactone polyols, castor oil polyols, polyether polyols, and hydroxyl group-containing thermoplastic resins. . These compounds can be used alone or in combination of two or more.

The polyester polyols include polycarboxylic acids (aliphatic saturated or unsaturated polycarboxylic acids, adipic acid, azelaic acid, dodecanoic acid, maleic acid, fumaric acid, itaconic acid, dimerized linoleic acid and / or
Or an aromatic polycarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid and a low molecular weight glycol such as ethylene glycol, diethylene glycol, propylene glycol, 1,2-, 1,3- or 1,4-butanediol, 1, 5-pentanediol, 3-methyl-
By condensation polymerization with 1,5-pentanediol, 1,6-hexane glycol, 1,8-octanediol, 1,10-decanediol, neopentyl glycol, hydrogenated bisphenol A, glycerin, trimethylolpropane, hexanetriol The resulting polyol is exemplified.

Examples of the graft polyol include compounds in which at least one selected from polystyrene, polyacrylonitrile and polymethyl methacrylate is graft-bonded to the main chain of a divalent glycol having 2 to 10 carbon atoms.

As the polylactone-based polyol, ε-caprolactone, α-methyl-ε-caprolactone, ε-methyl-ε-caprolactone, β-methyl-δ-valerolactone, etc. are used as polymerization initiators for glycols and triols. Examples of the polyol include addition-polymerized polyols in the presence of a catalyst such as an organic metal compound, a metal chelate compound, or a fatty acid metal acyl compound.

Examples of castor oil-based polyols include linear or branched polyesters of castor oil and castor oil fatty acid and a polyol (the aforementioned low molecular weight polyol and / or polyether polyol), for example, diglyceride, monoglyceride and castor oil of castor oil fatty acid. Mono-, di-, or triesters of fatty acids and trimethylolpropane, mono-, di-, or triesters of castor oil fatty acids and polypropylene glycol, and the like can be mentioned.

Examples of the polyether polyol include ethylene glycol, propanediol, butanediol,
Diethylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol toluenediamine, glycerin, trimethylolpropane, shoe rose, ethylenediamine, Propylenediamine, diethylenetriamine, aniline, toluenediamine, metaphenylenediamine, diphenylmethanediamine, xylylenediamine or the like having one or more compounds having two or more active hydrogen groups as initiators, ethylene oxide, propylene oxide, butylene oxide, Amylene oxide, glycidyl ether, methyl glycidyl ether, t-butyl glycidyl ether, phenylglycidyl Polyether polyols obtained by addition polymerization by a known method monomers one or more of such Jill ether.

As other polyols, a hydroxyl group-containing thermoplastic resin or a liquid resin can be used. As the hydroxyl group-containing thermoplastic resin, there is a hydroxyl group-containing norbornene-based resin, and among the norbornene-based resins, dicyclopentadiene-based resin is more preferable. As a hydroxyl group-containing dicyclopentadiene resin, Quinton 1 manufactured by Zeon Corporation
700 and Neolesin PH-10 manufactured by Nippon Petrochemical Co., Ltd.
5 and Neolesin NB-90.

For the purpose of modifying these polyols, short molecular weight polyols can be used in combination. Examples include ethylene glycol, diethylene glycol, propylene glycol, 1,2-, 1,3- or 1,4-
Butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexane glycol, 1,8-octanediol, 1,10-decanediol, neopentyl glycol, bisphenol A
Propylene oxide adduct, hydrogenated bisphenol A, glycerin, trimethylolpropane and the like.

In order to obtain the urethane resin used in the present invention, the isocyanate group-containing compound and the active hydrogen group-containing compound are combined with the isocyanate group equivalent compound / active hydrogen group equivalent ratio in a range of 0.50 to 2.00, preferably 0.50 to 2.00. Can be obtained by reacting in the range of 0.80 to 1.70. At this time, it is preferable to use a urethanation catalyst.

The urethanization catalyst may be used alone or in combination of two or more as needed. These catalysts are not particularly limited, and include tertiary amines such as dimethylethanolamine, triethylenediamine, tetramethylpropanediamine, tetramethylhexamethylenediamine, dimethylcyclohexylamine, pentamethyldiethylenetriamine, stannas octoate, and dibutyltin dilaurate. Organotin compounds are mentioned. In addition, imidazoles, for example, trimethylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole and the like can be mentioned. These can be used alone or as a mixture of two or more. The amount of the urethanization catalyst used depends on the activity of the catalyst and the pot life to be set, but is preferably 5.0 parts by weight or less, more preferably 1.0 part by weight or less based on 100 parts by weight of the total of polyol and isocyanate. is there.

The primer composition of the present invention can be used by dissolving it in an organic solvent. For example, pentane, hexane, heptane, octane, cyclopentane, cyclohexane, cyclopentene, cyclohexene, cyclopentadiene, benzene, toluene, xylene, ethylbenzene Hydrocarbons such as styrene, petroleum ether and petroleum benzine; ethers and ketones such as tetrahydrofuran, acetone, ethyl ether, methyl ethyl ketone, isopropyl ether and dioxane; alcohols such as methanol, ethanol, isopropanol and butanol; methyl acetate and acetic acid Esters such as ethyl, isopropyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, methylene chloride, chloroform, trichloroethane, and Chloroethylene, freon -113, halogenated hydrocarbons such as Freon -112, etc. include those used in combination of two or more.
These may be refined with activated alumina or activated carbon if necessary.

The metathesis polymerization catalyst used in the present invention is not particularly limited as long as it is a catalyst system known as a catalyst for ring-opening polymerization of cycloolefin.

The metathesis polymerization catalyst of the present invention includes
Examples of the two-component system include complex metal halides composed of transition metals such as titanium, vanadium, molybdenum, tungsten, rhenium, iridium, ruthenium and osmium, metal carbene or Ziegler-Natta type coordination catalysts. Specific examples include tungsten compounds such as tungsten hexachloride, tungsten oxytetrachloride, tungsten oxide, and tridecyl ammonium tungstate; molybdenum compounds such as molybdenum pentachloride, molybdenum oxytrichloride, molybdenum oxide, and tridecyl ammonium molybdate; tantalum compounds such as tantalum chloride, [(cyclohexyl) ₃ P] 2RuCl2, [(phenyl) 3P] 3RuCl2, (cyclohexyl) 3-Way (p-cymene) RuCl2 [(phenyl) 3P] 3 (CO) RuH2 ruthenium compound such as And the like.

If necessary, a known cocatalyst (activator) is used in combination with the two-component metathesis polymerization catalyst system. Specific examples thereof include an alkylaluminum halide, an alkoxyalkylaluminum halide, an aryloxyalkylaluminum halide, and an organotin compound.

The one-component metathesis polymerization catalyst is obtained by combining a catalyst component and an activator as conventionally known.
Unlike the component type catalyst system, the catalyst is capable of subjecting a cycloolefin to ring-opening polymerization by a metathesis reaction without easily losing catalytic activity due to moisture in the air or water adsorbed on a solid surface. Specifically, a metal carbene-type coordination catalyst stabilized against moisture by taking a structure in which a ligand having large steric hindrance is coordinated to a central metal with a metal carbene structure of ruthenium or osmium as a central skeleton. No.

Preferred examples of the ruthenium or osmium metal carbene-type coordination catalyst include compounds represented by the following general formula (A), (B) or (C).

Embedded image M represents ruthenium or osmium; X and X1 each independently represent an anionic ligand; L and L1 each independently represent a neutral electron donating group; Q and Q1 each independently represent a hydrogen or alkyl group Alkenyl group or aromatic group, and the alkyl group, alkenyl group or aromatic group may have a substituent.

Embedded image M represents ruthenium or osmium; X and X 1 each independently represent an anionic ligand; L and L 1 each independently represent a neutral electron donating group; R 1 and R 2 each independently represent a carbon atom of 1 to 1; 18 alkyl groups, 2 to 2 carbon atoms
18 alkenyl groups, alkynyl groups having 2 to 18 carbon atoms,
Aryl group, carboxylate group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, alkenyloxy group having 2 to 18 carbon atoms, alkynyloxy group having 2 to 18 carbon atoms,
C2 to C18 allyloxy group, C2 to C18 alkoxycarbonyl group, C1 to C18 alkylthio group, C1 to C18 alkylsulfonyl group or C1 to C18 alkylsulfinyl group, R3 represents hydrogen, an aryl group or an alkyl group having 1 to 18 carbon atoms.

Further, more preferable examples from the viewpoints of high catalytic activity, high synthesis yield and economical efficiency include compounds represented by the following general formula (C).

Embedded image M represents ruthenium or osmium; X and X1 each independently represent an anionic ligand; L and L1 each independently represent a neutral electron donating group; Q and Q1 each independently represent a hydrogen or alkyl group Alkenyl group or aromatic group, and the alkyl group, alkenyl group or aromatic group may have a substituent.

X in the above formulas (A), (B) and (C)
And the anionic ligand represented by X1 is a group having a negative charge when the coordination to the central metal is removed. Such groups include, for example, hydrogen, halogen, CF ₃
CO ₂ , CH ₃ CO ₂ , CFH ₂ CO ₂ , (CH ₃ ) ₃ CO,
(CF ₃ ) ₂ (CH ₃ ) CO, (CF ₃ ) (CH ₃ ) ₂ CO,
An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group, a phenoxy group, a tosyl group, a mesyl group,
There are a trifluoromethanesulfonate group and the like, and particularly preferable ones are both halogen (particularly, chlorine). The neutral electron-donating group represented by L and L1 in the formulas (A), (B) and (C) is a group having a neutral charge when the coordination to the central metal is removed. Such groups include, for example, PR ₂ R ₃ R ₄ (where R ₂ is a secondary alkyl group or cycloalkyl group, R ₃ and R ₄ are each independently an aryl group, a C 1-10 carbon atom) A primary alkyl group or a secondary alkyl group, or a cycloalkyl group), pyridine, p-fluoropyridine, and the like. Particularly preferred are both -P (cyclohexyl). ) ₃ , -P (cyclopentyl) ₃ ,
Or -P (isopropyl) ₃ .

The metathesis polymerization catalysts include those described above. The amount of the catalyst added is 0.0001 to 100 parts by weight based on 100 parts by weight of the resin. 50 parts by weight. As the catalyst, a one-component type metal carbene type catalyst is preferable because of its good stability in air.

A cycloolefin or a coupling agent can be added to the primer composition of the present invention as needed to improve the adhesiveness. The cycloolefin is not particularly limited, but includes norbornene, dicyclopentadiene, cyclooctadiene, cyclooctene, cyclododecatriene and the like, which have metathesis polymerizability as described later. Conventionally known coupling agents can be used. Examples of silane coupling agents include γ- (methacryloxypropyl) trimethoxysilane, vinyltriethoxysilane, β- (3,4-
Epoxycyclohexyl) ethyltrimethoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-
A silane coupling agent such as mercaptopropyltrimethoxysilane can be used. In addition, known materials such as titanate-based, aluminum-based, and zirconium-based coupling agents can be used.

Fillers and reinforcing materials can be added to the primer composition of the present invention, if necessary. Examples of the filler include a powdery or granular inorganic filler and an organic filler. As the inorganic filler, for example, silica,
Silica sand, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, alumina, zinc oxide,
There are clay, talc, glass powder, barium sulfate and the like, and examples of the organic filler include wood powder, polyester and polystyrene beads. Examples of the reinforcing material include glass fibers, carbon fibers, inorganic reinforcing materials such as metal fibers and aramid fibers, polyester fibers, vinylon fibers, and olefin fibers such as polyethylene and polypropylene.
In addition, titanium or graphite whiskers,
Milled glass, cut fiber, microfiber, asbestos, rock wool, microballoon, glass flake, mica powder and the like can also be used.

Various additives such as a thixotropic agent, a colorant, a defoaming agent, a dispersant, an antioxidant and a plasticizer are added to the primer composition of the present invention for the purpose of improving physical properties, appearance, and molding workability. Can be contained.

Examples of the thixotropic agent include silica, asbestos powder,
Inorganic thixotropic agents such as fatty acid-treated calcium carbonate, organic bentonite, modified polyester polyol type organic thixotropic agents,
Examples include colloidal silica, fatty acid amide wax, and stearic acid amide.

As a coloring agent, inorganic pigments such as titanium oxide, cobalt blue, cadmium yellow, molybdenum red, chromium oxide, and alumina white, and organic pigments such as carbon black, aniline black, phthalocyanine, and quinacdrine can also be added.

As the defoaming agent, in addition to silicone oils and surfactants, those commercially available from Byk Chemie and Kusumoto Kasei Co., Ltd. can be used.

As the antioxidant, one or a combination of two or more of the above-mentioned hindered phenol-based amine-based, sulfur-based, phosphorus-based antioxidants and thermal deterioration inhibitors can be used. An ultraviolet absorber, a light stabilizer and the like can also be used in combination.

As the urethane resin used in the primer composition of the present invention, a two-component type of a polyol component (solution A) and an isocyanate component (solution B) is preferably used. In addition, the metathesis polymerization catalyst is used immediately before use for solution A or solution B,
Or it is preferable to add to both solutions. This primer composition can be easily obtained by uniformly mixing the above components at room temperature or under heating.

In order to obtain the cycloolefin polymer of the present invention, a cycloolefin and a metathesis polymerization catalyst used in known metathesis polymerization are used.

The cycloolefin used in the present invention may be any as long as it is useful in metathesis polymerization. Among them, norbornene-type cycloolefins such as substituted or unsubstituted norbornene, dicyclopentadiene, and dihydrodicyclopentadiene are preferably used. Examples of norbornene-type cycloolefins include norbornene, methylnorbornene, dimethylnorbornene,
Bicyclic norbornene such as ethyl norbornene, ethylidene norbornene, butyl norbornene, etc., tricyclic norbornene such as dicyclopentadiene (a dimer of cyclopentadiene), dihydrodicyclopentadiene, methyldicyclopentadiene, and dimethyldicyclopentadiene, and tetracyclo Tetracyclic norbornenes such as dodecene, methyltetracyclododecene, and dimethylcyclotetradodecene; pentacyclic and higher norbornenes such as tricyclopentadiene (trimer of cyclopentadiene) and tetracyclopentadiene (tetramer of cyclopentadiene) Is mentioned. Further, a compound having two or more norbornene groups, for example, norbornadiene, tetracyclododecadiene, symmetric tricyclopentadiene, or the like can be used as the polyfunctional crosslinking agent.

As other cycloolefins, cyclobutene, cyclopentene, cyclooctene, cyclooctadiene, cyclooctatriene, cyclododecatriene and the like can also be used. Further, a dicyclopentadiene-based petroleum resin obtained by thermal polymerization or cationic polymerization of dicyclopentadiene can also be used. These cycloolefins can be used alone or in combination of two or more.

Among them, dicyclopentadiene, methyltetracyclododecene, ethylidene norbornene, tricyclopentadiene, tetracyclopentadiene, cyclooctadiene,
Cyclooctene is preferred, and dicyclopentadiene is particularly preferred.

The usual commercially available dicyclopentadiene may contain vinylnorbornene, tetrahydroindene, methylvinylnorbornene, methyltetrahydroindene, methyldicyclopentadiene, dimethyldicyclopentadiene, tricyclopentadiene and the like as impurities. Yes, dicyclopentadiene of various purity is commercially available. The dicyclopentadiene used in the present invention has a purity of 80% by weight or more, preferably 90% by weight or more, although it varies depending on the intended use of the obtained polymer.

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

The cycloolefin used in the present invention includes the above-mentioned antioxidants, heat deterioration inhibitors, ultraviolet absorbers, light stabilizers, coloring agents, curing retarders, fillers, defoamers, couplings. Well-known agents such as agents, reinforcing materials, flame retardants, plasticizers, and modifiers such as elastomers may be included.

The process for producing a cycloolefin polymer according to the present invention comprises treating a substrate with a primer composition containing a metathesis polymerization catalyst and a resin, and curing a molding material containing a cycloolefin and a metathesis polymerization catalyst on the treated surface. There is no particular limitation as long as it is a production method.

The method of using the primer composition of the present invention is not particularly limited. For example, an appropriate method such as brushing, dipping, spraying, spin coating, bar coater, and roll coater may be applied to a cleaned substrate surface. When a solvent is used after coating by such a method, the solvent can be volatilized. The coating may be performed at room temperature or under heating. After the coating, the coating is dried and cured by an appropriate method such as natural drying or forced drying by heating. At this time, the primer surface is preferably in a semi-dry state. The coating amount capable of forming a coating film is such that when the thickness of the primer layer from which the solvent is removed is 0.1 to 5000 μm, preferably 10 to 500 μm, the adhesion to the base material becomes sufficiently high. It is suitable.

The composite of the cycloolefin polymer and the substrate is not particularly limited. However, the polymer must contact the treated surface to which the primer composition has been applied. For example, a solution of dicyclopentadiene containing a metathesis polymerization catalyst is applied or molded on the surface of the substrate on which the primer has been applied.
The method for coating the cycloolefin solution is not particularly limited, and brushing, dipping, spraying, spin coating, a bar coater, a roll coater, or the like can be used. The method for molding the cycloolefin solution is not particularly limited, and casting, injection molding, extrusion molding, compression molding, rotational molding and the like can be used. In this case, you may heat as needed.

[0054]

The present invention will be described below with reference to examples. In the examples, “parts” means “parts by weight” unless otherwise specified.
Dicyclopentadiene is abbreviated as DCPD. FIG. 1 shows the metathesis polymerization catalyst used.

Example 1 Nipporan 1100 (polyester polyol, trade name, manufactured by Nippon Polyurethane Industry Co., Ltd., hydroxyl value: 210 mg KOH / g), 10 parts, triphenylphosphine (manufactured by Wako Pure Chemical Industries, Ltd.) 0.02
Part A, 0.05 parts of dibutyltin dilaurate were dissolved in 10 parts of toluene, 10 parts of ethyl acetate, and 10 parts of DCPD to obtain a liquid A. Next, as liquid B, millionate 2014 was used.
(MDI prepolymer, trade name, manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate content: 6% by weight) was prepared by adding 25 parts and 0.4 part of metathesis polymerization catalyst B.

(Example 2) 50 parts of Quinton 1700 (hydroxyl-containing DCPD resin, trade name, manufactured by Zeon Corporation, hydroxyl value: 220 mgKOH / g) was dissolved in toluene 25
And A in 25 parts of ethyl acetate. Next,
As B solution, use Millionate MR-100 (Polymeric M)
DI, trade name, manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate amount 30% by weight) and 27.5 parts of metathesis polymerization catalyst A were added.

(Example 3) 50 parts of Quinton 1700 (hydroxyl-containing DCPD resin, trade name, manufactured by Zeon Corporation, hydroxyl value: 220 mgKOH / g), 25 parts of toluene,
Solution A was dissolved in 25 parts of ethyl acetate and 12.5 parts of dicyclopentadiene. Next, as liquid B, Millionate MR-100 (Polymeric MDI, trade name, manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate content 30% by weight)
27.5 parts and 0.4 parts of metathesis polymerization catalyst A were added.

(Example 4) 50 parts of Quinton 1700 (hydroxyl-containing DCPD resin, trade name, manufactured by Zeon Corporation, hydroxyl value: 220 mgKOH / g), Quinton 1325
(DCPD petroleum resin, trade name, manufactured by Zeon Corporation)
12.5 parts was dissolved in 30 parts of toluene and 30 parts of ethyl acetate to obtain a solution A. Next, as solution B, use millionate MR.
-100 (Polymeric MDI, trade name of Nippon Polyurethane Industry Co., Ltd., isocyanate content 30%) 27.5
And 0.4 parts of the metathesis polymerization catalyst A were added.

(Example 5) 10 parts of Quinton 1700 (hydroxyl-containing DCPD resin, trade name, manufactured by Nippon Zeon Co., Ltd., hydroxyl value: 220 mgKOH / g), 10 parts of toluene,
Solution A was dissolved in 10 parts of ethyl acetate. Next, a liquid B was prepared by adding 25 parts of Millionate 2014 (MDI prepolymer, trade name, manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate amount: 6% by weight) and 0.4 part of a metathesis polymerization catalyst B.

Example 7 10 parts of Quinton 1700 (hydroxyl-containing DCPD resin, trade name of Nippon Zeon Co., Ltd., hydroxyl value: 220 mgKOH / g), triphenylphosphine (manufactured by Wako Pure Chemical Industries, Ltd.) 02 parts was dissolved in 10 parts of toluene, 10 parts of ethyl acetate, and 10 parts of DCPD to obtain a solution A. Next, as liquid B, millionate 2
014 (MDI prepolymer, trade name, manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate amount 6% by weight) 25 parts,
A product to which 0.4 part of the metathesis polymerization catalyst B was added was prepared.

(Comparative Example 1) No primer is used.

(Comparative Example 2) (Metathesis polymerization catalyst B was removed from solution B of Example 1.) Nipporan 1100 (polyester polyol, trade name, manufactured by Nippon Polyurethane Industry Co., Ltd., hydroxyl value: 210 mg)
KOH / g) 10 parts, triphenylphosphine (manufactured by Wako Pure Chemical Industries, Ltd.) 0.02 parts, dibutyltin dilaurate 0.05 parts, toluene 10 parts, ethyl acetate 10 parts
And A solution were dissolved in 10 parts of DCPD. Next, B
Millionate 2014 (MDI prepolymer,
50 parts of a product manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate amount: 6% by weight) were prepared.

Comparative Example 3 (Metathesis polymerization catalyst A was omitted from Example 4.) Quinton 1700 (hydroxyl-containing DCPD resin, trade name, manufactured by Nippon Zeon Co., Ltd., hydroxyl value: 220 mgKOH / g)
50 parts, Quinton 1325 (DCPD resin DCPD
12.5 parts of a petroleum resin (trade name, manufactured by Zeon Corporation) was dissolved in 30 parts of toluene and 30 parts of ethyl acetate to obtain a liquid A. Next, Liquid B was prepared with 27.5 parts of Millionate MR-100 (Polymeric MDI, trade name of Nippon Polyurethane Industry Co., Ltd., isocyanate amount: 30% by weight).

(Comparative Example 4) (Metathesis polymerization catalyst B was omitted from Example 5.) Quinton 1700 (hydroxyl-containing DCPD resin, trade name, manufactured by Zeon Corporation, hydroxyl value: 220 mgKOH / g)
10 parts was dissolved in 10 parts of toluene and 10 parts of ethyl acetate to obtain a solution A. Next, as liquid B, millionate 201 was used.
4 (MDI prepolymer, trade name of Nippon Polyurethane Industry Co., Ltd., isocyanate content 6% by weight) was prepared in an amount of 25 parts.

A test piece was prepared from the obtained primer by the following method and evaluated. (1) Test piece preparation method Using PBT (polybutylene terephthalate, Duranex 3300 manufactured by Polyplastics Co., Ltd.) as a base material, mixing a primer A solution and a B solution, and then using a bar coater on one surface of the base material to a thickness of 100 μm (wet, wet) ) Was applied and dried at room temperature for about 15 minutes. Thereafter, the substrate was immersed in a DCPD solution to a depth of 20 mm and cured to obtain a test piece. (See FIG. 2) (2) DCPD solution blending 100 parts of DCPD having a purity of about 98% by weight, triphenylphosphine (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.)
One part and 0.11 part of the metathesis polymerization catalyst B were added to prepare a solution. Thereafter, it was cured by heating at 40 ° C./4 hours + 125 ° C./3 hours. (3) Adhesive strength test method It was carried out according to the tensile shear adhesive strength test method of the adhesive of JIS K6850. n = 5 (number of tests) Adhesive strength = Break load / Area of DCPD adhesive portion (primer portion) The obtained adhesive strength is shown in Table 1.

[0066]

[Table 1] 接着 Adhesive strength (MPa) ────────────── ──────────── Example 1 2.7 Example 2 3.3 Example 3 3.1 Example 4 3.4 Example 5 3.9 Comparative Example 1 0.3 Comparative Example 2 0.9 Comparative Example 3 0.6 Comparative Example 4 1.0──────────────────────────

As can be seen from the table, the adhesive strength between the base material and the cycloolefin is remarkably improved by using a composition obtained by adding a metathesis polymerization catalyst to a urethane resin as a primer. Similar results were obtained with epoxy resin.

[0068]

According to the present invention, a polymer obtained from a cycloolefin, for example, dicyclopentadiene as a raw material can be improved in adhesiveness to a substrate, and can be easily compounded. The range can be expanded. The cycloolefin polymer composite according to the present invention makes use of the excellent water resistance, boiling resistance, and mechanical properties of the cycloolefin polymer, for example, a septic tank, a bathtub, a kitchen top plate, a tank, a unit bath, a wall panel, and a pleasure boat. It can be used for molded articles such as wiring boards, corrugated boards, etc., and also for electric parts and electronic parts utilizing water resistance and electric characteristics.

[Brief description of the drawings]

FIG. 1 is a metathesis polymerization catalyst used in Examples.

FIG. 2 is a cross-sectional view of a test piece used in an example.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 163/00 C09D 163/00 175/04 175/04 (72) Inventor Hiromasa Kawai Wadadai, Tsukuba City, Ibaraki Prefecture 48 F-term in Hitachi Chemical Co., Ltd. Research Laboratory (reference) 4J032 CA32 CA34 CA38 CB01 CB03 CC03 CD02 CE05 CE06 4J034 CA04 CA05 CB03 CB04 CB07 CC03 CC08 CC12 CC23 CC26 CC45 CC52 CC61 CC62 CC67 CD04 DA01 DB03 DB07 DF11 DF20 DF16 DF28 DF29 DG02 DG03 DG04 DG05 DG14 DG16 DG22 DH02 DH06 DH09 DH10 DP02 DP19 DQ16 DQ18 EA12 KA01 KB02 KD12 KE02 LA14 LA33 QC05 RA07 4J036 AA01 AD08 AD21 AF06 AF08 DB21 DC03 DC07 DC01 DC01 DC01 DC01 DC01 DC01 DC01 DC01 DC01 DC01 DC01 DC01 DC01 DC01 DC01 DC01 DC01 DC01 DC01 DC01 DC01 DC07 DC01 DC01 DC01 DC01 DN011 EA011 KA03 PA19 4J040 DK021 EC061 EC071 EF111 EF131 EF181 EF191 EF201 HD41 JB02 KA14 KA16 MA02 MA10 MA11 PA10

Claims (10)

[Claims] 1. A primer composition comprising a metathesis polymerization catalyst and a resin. 2. The primer composition according to claim 1, wherein the resin is a thermosetting resin. 3. The primer composition according to claim 2, wherein the thermosetting resin is an epoxy resin or a urethane resin. 4. The primer composition according to claim 3, wherein a hydroxyl group-containing norbornene resin is used as one of the polyol components of the urethane resin. 5. The primer composition according to claim 1, wherein the metathesis polymerization catalyst is a ruthenium compound. 6. The primer composition according to claim 1, wherein the metathesis polymerization catalyst is a catalyst represented by the general formula (A). Embedded image (M represents ruthenium or osmium, X and X1 each independently represent an anionic ligand, L and L1 each independently represent a neutral electron donating group, Q and Q1 each independently represent hydrogen, alkyl Group, alkenyl group or aromatic group, and the alkyl group, alkenyl group or aromatic group may have a substituent.) 7. The primer composition according to claim 1, wherein the metathesis polymerization catalyst is a catalyst represented by the general formula (B). Embedded image (M represents ruthenium or osmium, X and X1 each independently represent an anionic ligand, L and L1 each independently represent a neutral electron donating group, R1 and R2
Are each independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group, a carboxylate group having 1 to 18 carbon atoms, An alkoxy group, an alkenyloxy group having 2 to 18 carbon atoms, an alkynyloxy group having 2 to 18 carbon atoms, an allyloxy group having 2 to 18 carbon atoms, and having 2 to 1 carbon atoms
An alkoxycarbonyl group having 8 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, an alkylsulfonyl group having 1 to 18 carbon atoms or an alkylsulfinyl group having 1 to 18 carbon atoms;
Represents hydrogen, an aryl group or an alkyl group having 1 to 18 carbon atoms. ) 8. The primer composition according to claim 1, wherein the metathesis polymerization catalyst is a catalyst represented by the general formula (C). Embedded image (M represents ruthenium or osmium, X and X1 each independently represent an anionic ligand, L and L1 each independently represent a neutral electron donating group, Q and Q1 each independently represent hydrogen, alkyl Group, alkenyl group or aromatic group, and the alkyl group, alkenyl group or aromatic group may have a substituent.) 9. A cycloolefin obtained by treating a substrate surface with the primer composition according to claim 1 and curing a molding material containing a cycloolefin and a metathesis polymerization catalyst on the treated surface. Polymer composite. 10. A cycloolefin polymer composite comprising treating a substrate surface with the primer composition according to claim 1 and curing a molding material containing a cycloolefin and a metathesis polymerization catalyst on the treated surface. Method of manufacturing a product.