JP2003127152A - Method for producing norbornene resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a norbornene resin laminate which can laminate norbornene resin layers different in physical properties simply and efficiently by subjecting a norbornene monomer to bulk ring-opening polymerization. SOLUTION: The method includes a process in which a reaction liquid (1) containing a norbornene monomer (1) and a metal-carbene complex (1) is injected into a molding mold (1) and subjected to the bulk ring-opening polymerization to form the fires norbornene resin layer and a process in which a reaction liquid (2) containing a norbornene monomer (2) and a metal-carbene complex (2) is injected into a molding mold (2) and subjected to bulk ring-opening polymerization to laminate the second norbornene resin layer on the first norbornene resin layer. The composition of the reaction liquid (1) is different from that of the reaction liquid (2).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to the production of a norbornene-based resin laminate in which norbornene-based resin layers having different physical properties are laminated by sequentially injecting reaction liquids having different compositions into a molding die for bulk ring-opening polymerization. Regarding the method. here,
“Physical properties” refer to physical and chemical properties imparted to the norbornene-based resin layer such as color, rigidity, elasticity, weather resistance, specific gravity, coefficient of thermal expansion, and flame retardancy.

[0002]

2. Description of the Related Art Heretofore, a resin laminate having laminated resin layers having different physical properties, such as a sandwich structure having a non-foamed layer (skin layer), a foamed layer and a skin layer, has been manufactured. And this thing is building materials, park materials,
It is used as a housing material, leisure goods, transportation equipment, transportation container, storage container material, etc.

As a method of manufacturing such a resin laminate,
By attaching a member made of a metal plate or a hard plastic as a surface layer to the molding die, injecting a reaction liquid containing a norbornene-based monomer and a metathesis polymerization catalyst such as tungsten-based or molybdenum-based, and performing bulk ring-opening polymerization, A method for producing a composite material in which a norbornene-based resin layer is laminated on the surface of a member is known (Japanese Patent Laid-Open No. 14782/1993).
No. 2).

However, in this method, in order to improve the adhesion between the member and the norbornene-based resin layer, it is necessary to previously coat the surface of the member with a polymer that does not inhibit the bulk ring-opening polymerization, and the molding die is also treated. Since it is necessary to attach the members in advance and then to form them, there is a problem that the degree of freedom in selecting the material and shape of the composite member is low and the production efficiency is poor. Moreover, a laminate having four or more layers cannot be obtained by this method.

[0005]

SUMMARY OF THE INVENTION The present invention has been made under the above circumstances, and a norbornene resin layer having different physical properties can be laminated easily and efficiently by subjecting a norbornene monomer to bulk ring-opening polymerization. An object of the present invention is to provide a method for producing a resin laminate.

[0006]

It is well known that when the composition of a reaction liquid containing a polymerizable monomer is changed, the physical properties of a resin layer obtained by polymerization are different. The present inventors
By changing the composition of the reaction solution containing the norbornene-based monomer and the metathesis catalyst, and sequentially injecting the reaction solution into the mold and performing bulk ring-opening polymerization, the norbornene-based resin layers having different physical properties are laminated. Tried to do. However, even if an attempt is made to stack the norbornene resin layers using a conventional tungsten-based or molybdenum-based metathesis polymerization catalyst, the adhesion between the norbornene-based resin layers formed is poor, and if a repeated load is applied, the interface between the layers will be reduced. However, the desired norbornene-based resin laminate could not be obtained.

On the other hand, in recent years, it has been reported that a carbene complex of ruthenium or osmium is useful as a metathesis polymerization catalyst for norbornene-based monomers (US Pat. Nos. 5,710,298 and 5,884,984).
51 publication, WO99 / 51344 specification and WO00
/ 58322, WO00 / 71554).

The inventors of the present invention have used a metal carbene complex of a metal such as ruthenium or osmium as a metathesis polymerization catalyst to sequentially perform bulk ring-opening polymerization of reaction liquids having different compositions. As a result, norbornene-based resin layers having different physical properties are formed. They have found that they can be simply and efficiently laminated, and that the obtained norbornene-based resin layer has extremely excellent interlayer adhesion, and have completed the present invention.

Thus, according to the first aspect of the present invention, the reaction liquid (1) containing the norbornene-based monomer (1) and the metal carbene complex (1) is injected into the mold (1) to perform bulk ring-opening polymerization. Norbornene-based resin layer (1)
And a reaction liquid (2) containing the norbornene-based monomer (2) and the metal carbene complex (2) is injected into the molding die (2), and bulk ring-opening polymerization is performed. Laminating a norbornene-based resin layer (2) on the resin layer (1), wherein the reaction liquid (1) and the reaction liquid (2) have different compositions. A method of manufacturing a body is provided.

In the manufacturing method of the present invention, a second norbornene resin layer having a specific gravity different from the specific gravity of the first norbornene resin layer by 0.1 g / cm ³ or more is provided on the first norbornene resin layer. Is preferably laminated. Further, as the molding die (2), it is preferable to use a molding die having a common part with the molding die (1).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The production method of the present invention comprises the steps of injecting a reaction solution (1) into a molding die (1) and performing bulk ring-opening polymerization to form a norbornene-based resin layer (1). Injecting the reaction liquid (2) into the molding die (2) and performing bulk ring-opening polymerization to laminate the norbornene-based resin layer (2) on the norbornene-based resin layer (1). . Hereinafter, the method for producing the norbornene-based resin laminate of the present invention will be described in detail.

1) Formation of Norbornene Resin Layer (1) The norbornene resin layer (1) is formed by injecting the reaction liquid (1) into the molding die (1) and subjecting it to bulk ring-opening polymerization. You can The reaction liquid (1) is a liquid containing the norbornene-based monomer (1), the metal carbene complex (1) and, if necessary, an additive.

The norbornene-based monomer (1) is a bicyclic or tricyclic or more polycyclic hydrocarbon compound having a norbornene ring structure which may have a substituent. Specific examples of the norbornene-based monomer (1) include norbornene, norbornadiene, methylnorbornene, dimethylnorbornene, ethylnorbornene, chlorinated norbornene, ethylidenenorbornene, chloromethylnorbornene, trimethylsilylnorbornene, phenylnorbornene, cyanonorbornene, dicyanonorbornene, methoxycarbonyl. Bicyclic norbornenes such as norbornene, pyridyl norbornene, nordic anhydride of norbornene, and nadic acid imide of norbornene;

Tricyclonorbornenes such as dicyclopentadiene (dimer of cyclopentadiene), dihydrodicyclopentadiene and alkyl, alkenyl, alkylidene or aryl substitution products thereof; dimethanohexahydronaphthalene, dimethanooctahydronaphthalene and its Tetracyclic norbornenes such as alkyl, alkenyl, alkylidene or aryl substituents; pentacyclic norbornenes such as tricyclopentadiene (trimer of cyclopentadiene) and hexacyclic norbornenes such as hexacycloheptadecene; dinorbornene, two Compounds in which the norbornene ring is bound by a hydrocarbon chain or an ester group, and compounds containing a norbornene ring such as an alkyl- or aryl-substituted product thereof are listed.

The above norbornene-based monomers may be used alone or in combination of two or more. In the case of using two or more kinds, various norbornene-based monomers can be obtained by appropriately combining a norbornene-based monomer having one double bond which is a thermoplastic resin and a norbornene-based monomer having a plurality of double bonds which is a thermosetting resin. The resin layer (1) can be formed. Further, when two or more kinds of norbornene-based monomers are used in combination as compared with the case of using a norbornene-based monomer alone, a monomer having a high freezing point temperature can be handled as a liquid because the freezing point is lowered.

Among these norbornene-based monomers, dicyclopentadiene is preferably used as a main component, from the viewpoint of obtaining a norbornene-based resin layer excellent in activity during bulk polymerization and excellent in heat resistance, and 80% by weight or more is preferable. More preferably it is dicyclopentadiene. Such dicyclopentadiene may be a high-purity product of 99% by weight or more, or may contain a trimer of cyclopentadiene in the range of 2 to 20%. When the latter is used, a norbornene resin layer having excellent mechanical strength can be formed.

The metal carbene complex (1) is a compound in which a carbene compound is bound to a central metal atom, and has a structure in which a carbene carbon is double-bonded to a metal atom (M) (M = C, hereinafter referred to as "reaction center carbene compound"). Also referred to as "structure").

The metal carbene complex (1) is preferably a metal carbene complex (1) containing a metal atom of groups 5, 6 and 8 of the periodic table as a central metal. Among these, a carbene complex of Group 8 ruthenium or osmium is preferable, a ruthenium carbene complex is more preferable, and a carbene compound containing a hetero atom other than the carbene structure of the reaction center is further bonded to ruthenium. Is particularly preferable. Since the ruthenium heteroatom-containing carbene complex has excellent catalytic activity during bulk polymerization, it is possible to efficiently form a norbornene-based resin layer having little odor derived from unreacted norbornene-based monomer.

Specific examples of the ruthenium heteroatom-containing carbene complex include ruthenium compounds represented by the following general formula (1) or (2).

[0020]

[Chemical 1]

(In the formulae, R ¹ and R ² may independently of each other be C ₁ which may contain a hydrogen atom, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom.
~C represents a _{2 0} hydrocarbon group. X ¹ and X ² independently of each other represent any anionic ligand. L ¹ represents a hetero atom-containing carbene compound, and L ² represents a hetero atom-containing carbene compound or any neutral electron-donating compound. ^Also, 2 of ^{R 1, R 2, X 1} , X 2, L 1 and ^{L 2}
One or more may combine with each other to form a polydentate chelating ligand. )

Here, the hetero atom means an atom of groups 15 and 16 of the long periodic table, specifically, N,
Examples thereof include O, P, S, As and Se atoms.
Of these, N, O, P, and S atoms are preferable for obtaining a stable carbene compound, and N atom is particularly preferable.

The carbene compound is a general term for compounds having a methylene free group, and is a compound having an uncharged divalent carbon atom represented by (> C :, also referred to as carbene carbon). Generally, a carbene compound exists as an unstable intermediate generated during a chemical reaction, but a carbene compound having a hetero atom can be isolated as a relatively stable carbene compound.

The preferred hetero atom-containing carbene compound for L ¹ is 1,3 represented by the following general formula (3):
-Disubstituted imidazolidine-2-ylidenes and 1,3-disubstituted-4-imidazoline represented by the general formula (4)-
2-ylidenes are mentioned.

[0025]

[Chemical 2]

(In the formula, R ^{3 to} R ⁶ are independently carbon atoms having 1 to 20 carbon atoms and may contain a hydrogen atom, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom. Represents a hydrogen group.)

A bulky group is preferred as the substituent bonded to R ^{3 to} R ⁶ and the hetero atom adjacent to the carbene carbon of the carbene compound containing a hetero atom. Specific examples of the bulky group include alkyl groups having a branched structure such as isopropyl group and tertiary butyl group; alicyclic groups such as cyclohexyl group and adamantyl group; phenyl group, methylphenyl group, methylnaphthyl group, 2,6 -Substituted or unsubstituted aromatic ring groups such as a diisopropylphenyl group and a mesityl group.

Further, as a preferable hetero atom-containing carbene compound other than the compounds represented by the general formulas (3) and (4), 1,3,4,5-tetrasubstituted imidazolidine-2 is used.
-Ylidenes, 1,3,4,5-tetrasubstituted-4-imidazoline-2-ylidenes, 1,3,4-trisubstituted-2,3
4,5-Tetrahydro-1H-1,2,4-triazole-5-ylidenes, 3-substituted-2,3,4,5-tetrahydrothiazole-2-ylidenes, 1,3-disubstituted hexahydropyrimidines -2-ylidene-N, N,
N ′, N′-tetrasubstituted formamidinylidenes, 3-substituted-2,3-dihydrothiazole-2-ylidenes and the like can be mentioned.

X ¹ and X ² are ligands having a negative charge when separated from the central metal. For example,
F, Br, Cl, I and other halogen atoms; hydrogen atoms; chain, branched or cyclic substituted or unsubstituted hydrocarbon groups such as alkyl groups, alkenyl groups, substituted allyl groups and substituted cyclopentadienyl groups; Aromatic hydrocarbon group such as aryl group; acetylacetonato group, diketonate group, alkoxy group,
Aryloxy group, a hydrocarbon group containing an oxygen atom such as an alkoxycarbonyl group or a carboxyl group; a hydrocarbon group containing a sulfur atom such as an alkylthio group, an alkenylthio group or an arylthio group; an alkylsulfonate group or an arylsulfonate group , A hydrocarbon group containing an oxygen atom and a sulfur atom, such as an alkylsulfonyl group and an alkylsulfinyl group. Among these, a halogen atom is preferable, and a chlorine atom is more preferable.

When L ² is a neutral electron-donating compound, L ² is a ligand having a neutral charge when separated from the central metal, and is a neutral electron-donating compound, That is, any Lewis base may be used. Specific examples thereof include oxygen; water; substituted or unsubstituted unsaturated hydrocarbon compounds such as aromatic compounds, cyclic diolefins and olefins; and oxygen atoms such as ethers, carbonyls and esters. Hydrocarbon compounds; Hydrocarbons containing nitrogen atoms such as amides, amines and pyridines; Hydrocarbons containing oxygen atoms and nitrogen atoms such as nitriles and isocyanides; Phosphines, phosphinites and phosphites Hydrocarbons containing an oxygen atom and a phosphorus atom such as;
Hydrocarbons containing oxygen and sulfur atoms such as sulfoxides and thioethers; compounds containing nitrogen and sulfur atoms such as thiocyanates; compounds containing antimony atoms such as stibines; Lewis bases such as Can be mentioned. Among these, phosphines are preferable, and trisubstituted phosphines such as trialkylphosphines and triarylphosphines are more preferable.

[0031] R ¹ and R ² are, independently of one another are hydrogen or halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, which may C ₁ ~ containing phosphorus atom or silicon atom
It represents a C ₂₀ hydrocarbon group. As the hydrocarbon group, C ₂
To C ₂₀ alkenyl group, alkynyl group, alkyl group,
Examples thereof include an aryl group, a carboxyl group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group and an alkylsulfinyl group.

Examples of the compound represented by the general formula (1) include benzylidene (1,3-dimesitylimidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and (1,3-dimesityl). Imidazolidine-2-ylidene) (3-methyl-2-butene-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) Ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) Ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydrobenzimidazole-2) − Isopropylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-l, 2,4
-Triazole-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidine-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl imidazolidine-2- Ruthenium complex compound in which a hetero atom-containing carbene compound such as ylidene) pyridine ruthenium dichloride and a neutral electron-donating compound are bonded;

Benzylidenebis (1,3-dicyclohexylimidazolidin-2-ylidene) ruthenium dichloride, benzylidenebis (1,3-diisopropyl-4)
-Imidazoline-2-ylidene) Ruthenium complex compounds in which two hetero atom-containing carbene compounds such as ruthenium dichloride are bonded.

Examples of the compound represented by the general formula (2) include (1,3-dimesitylimidazolidin-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t
-Butylvinylidene) (1,3-diisopropyl-4-
Examples include imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylidene ruthenium dichloride, and the like.

The amount of the metal carbene complex (1) used is usually 1: 2,000 to 1: 2,000,000, preferably 1: 5,000, in terms of the molar ratio of metal atom / norbornene type monomer in the complex. ˜1,000,000, more preferably 1: 10,000 to 1: 500,000. If this ratio is too small, the activity during bulk polymerization will be insufficient, and if it is too large, the activity for bulk polymerization will be too high, and poor curing and poor filling into the mold will be likely to occur.

The metal carbene complex (1) can be used by dissolving it in a small amount of an inert solvent, if necessary. Examples of such an inert solvent include chain aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, methylcyclohexane and cyclooctane; benzene, toluene, xylene and the like. Aromatic hydrocarbon solvent; ether type solvents such as diethyl ether and tetrahydrofuran can be used. Further, a liquid antioxidant, a plasticizer or an elastomer may be used as a solvent as long as it does not reduce the activity of the metal carbene complex as a metathesis catalyst. Among these solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents and alicyclic hydrocarbon solvents which are industrially widely used are preferable.

In addition to the norbornene-based monomer (1) and the metal carbene complex (1), the reaction liquid (1) can further contain additives. The additive is added for the purpose of imparting various physical properties to the norbornene resin layer (1).

The additive is not particularly limited as long as it does not inhibit the bulk ring-opening polymerization of the norbornene-based monomer (1), and is appropriately selected and used according to the physical properties imparted to the norbornene-based resin layer (1). be able to. Examples of the additives include colorants, wood powder, antioxidants, ultraviolet absorbers, light stabilizers, elastomers, glass fibers, fillers and foaming agents.

The colorant and the wood powder are added for the purpose of imparting a design property to the norbornene resin layer (1). As the colorant, a dye, a pigment or the like is used. Pigments are preferable because they can give a bright color to a molded product. There are various kinds of dyes, and known dyes may be appropriately selected and used. For example, nitro dye, nitroso dye, azo dye, ketoimine dye, triphenylmethane dye, xanthene dye, acridine dye, quinoline dye, methine dye, thiazole dye, indamine dye, azine dye, oxazine dye,
Examples thereof include thiazine dyes, sulfur dyes, aminoketone dyes, anthraquinone dyes, indigoid dyes and phthalocyanine dyes. Further, as the pigment, for example, carbon black, titanium black, mica, ultramarine blue, Berlin blue, cobalt oxide, titanium yellow, strontium chromate, black iron oxide, molybdenum red, molybdenum white, emerald green, cobalt blue, titanium white. , Graphite, yellow lead, iron oxide yellow, titanium dioxide, zinc oxide, trilead tetraoxide, red lead,
Examples include chromium oxide and dark blue. The wood powder is a finely pulverized tree or the like, and is added for the purpose of imparting a wood texture to the norbornene-based resin layer.

The amount of the colorant added is usually 0.005 to 10 parts by weight based on 100 parts by weight of the norbornene-based monomer. The amount of wood powder added is usually 1 to 200 parts by weight with respect to 100 parts by weight of the norbornene-based monomer.

The antioxidant is added for the purpose of improving the storage stability of the norbornene-based monomer (1) and the norbornene-based resin laminate. The antioxidant is preferably soluble in norbornene-based monomers. Examples of the antioxidant used include various hindered phenol-based, phosphorus-based, amine-based, and other antioxidants for plastics and rubbers. Among these, hindered phenolic antioxidants, which have excellent effects, are preferable.

Examples of hindered phenolic antioxidants are 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol,
Stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] Methane, 2,2'-
Methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-)
Butylphenol), 4,4'-methylenebis (2,6
-Di-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4)
-Hydroxybenzyl) benzene, 1,3,5-tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H,
5H) trione and the like. These antioxidants can be used alone, but it is preferable to use two or more kinds in combination. It is also possible to use an antioxidant capable of copolymerizing with the monomer. As a concrete example,
Examples thereof include norbornenylphenol compounds such as 5- (3,5-di-t-butyl-4-hydroxybenzyl) -2-norbornene (see JP-A-57-83522).

The ultraviolet absorber and the light stabilizer are added for the purpose of imparting good weather resistance to the norbornene resin layer (1). As the ultraviolet absorber, for example, an organic substance such as benzotriazole, benzophenone, salicylate, or an inorganic substance such as fine particle zinc oxide, cerium oxide, or titanium oxide can be used. As the light stabilizer, a hindered amine radical scavenger such as bis- (2,2,6,6-tetramethyl-4-pyrrolidinyl) sebacate or a piperidine radical radical scavenger can be used. The addition amount of the antioxidant, the ultraviolet absorber and the light stabilizer is usually 50 to 50 with respect to the norbornene-based monomer.
10,000ppm or less, but 10,000ppm
You may add more than.

The elastomer is added for the purpose of imparting elasticity or improving impact resistance to the norbornene resin layer (1). Examples of the elastomer used 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 Examples include a combination (EVA) and a hydride thereof. Among these, those having a styrene skeleton or a butadiene skeleton are preferable. Further, it is preferable to add these elastomers to the reaction liquid because not only impact resistance is given to the obtained polymer but also the viscosity of the reaction liquid can be adjusted and the reaction liquid becomes easy to handle.

The amount of the elastomer used is usually 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 2 to 100 parts by weight of the obtained norbornene resin.
10 parts by weight. If the amount of the elastomer used is too small, the impact resistance imparting effect of the obtained norbornene-based resin laminate is small, and if it is too large, the viscosity of the reaction solution becomes too high, and the operability during bulk polymerization decreases. Alternatively, the resulting norbornene-based resin molded body tends to have a low heat deformation temperature and a low flexural modulus.

The filler is added for the purpose of imparting rigidity or flame retardancy to the norbornene resin layer (1). An inorganic filler and / or an organic filler can be used as the filler. Specific examples of the inorganic filler include, for example, titanium oxide, zircon oxide, antimony oxide, zinc oxide, magnesium oxide, aluminum oxide,
Magnesium hydroxide, aluminum hydroxide, calcium carbonate, kaolin clay, nepheline sinite, silica,
Silica gel, fused silica, synthetic silicic acid, quartz powder, silica stone powder, diatomaceous earth, barium sulfate, calcium sulfate, pumice powder,
Examples include glass fiber and whiskers. In addition, for the purpose of flame retardancy, metal hydroxides such as magnesium hydroxide and aluminum hydroxide; phosphorus such as yellow phosphorus and red phosphorus; antimony compounds such as antimony oxide; boron compounds such as boric acid and ammonium borate; Can also be used. These inorganic fillers may be obtained as a mineral resource, may be industrially synthesized, and are generally powdery or granular.

Specific examples of the organic filler include beads of resin such as polyester, polystyrene, acrylic resin and urea resin; silicone resin, polyamide resin, polyester resin, polyphenylene oxide resin, polyphenylene sulfide resin and phenolic thermosetting resin. Fine particles of resin such as; fibers such as carbon fiber, aramid fiber, polyamide fiber, polyester fiber; and carbon black.

It is also preferable to use a filler which has been surface-treated in advance. In that case, a surface treatment method using a general silane coupling agent can be adopted.
The amount of the filler used is not particularly limited, but the weight ratio of the norbornene-based monomer to the filler is 80/20 to 20/80.
Is preferable, and 70/30 to 50/50 is particularly preferable.

The foaming agent is added for the purpose of reducing the apparent specific gravity (reducing the weight) of the norbornene-based resin layer (1) as a foamed structure (lightening) and imparting heat insulation. As the foaming agent used, a chemical foaming agent that gives a foamed structure in which the reaction product gas is contained in the resin layer by a chemical reaction as long as it does not inhibit the bulk ring-opening polymerization, and voids in the resin layer Any physical foaming agent (mechanical foaming agent) in which the part-containing material is contained to provide a foamed structure can be used.

Examples of the chemical foaming agent include inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, sodium borohydride and silicon oxyhydride; azo compounds such as azodicarbonamide, azobisisobutyronitrile and diazobenzene. Sulfonylhydrazide compounds such as paratoluenesulfonyl hydrazide and 4,4-dioxybisbenzenesulfonyl hydrazide; dinitrosopentamethylenetetramine, N, N-dimethyl-N,
Organic blowing agents such as nitroso compounds such as N-dinitrosoterephthalamide can be mentioned. Examples of the physical foaming agent include microballoons (or microspheres) containing a gas or an organic solvent having a low boiling point, glass balloons, and the like. Among these, the use of a physical foaming agent is preferable from the viewpoints of handleability and the possibility of inhibiting the polymerization reaction.

The amount of the foaming agent used is not particularly limited and can be appropriately determined according to the set foaming degree. For the purpose of weight reduction, it is preferable to add a foaming agent so that the specific gravity ratio of the non-foaming layer and the foaming layer is in the range of 5/1 to 30/1 in the non-foaming layer / foaming layer.

In the present invention, in addition to the above-listed additives, other additives may be added within the range not impairing the object of the present invention. Examples of other additives include a reaction retarder, a Lewis acid, a molecular weight modifier, and monocyclic cycloolefins.

The reaction retarder is a component that delays the start of the bulk polymerization, and if the bulk ring-opening polymerization is started too quickly after mixing the norbornene-based monomer and the metal carbene complex, poor mixing may occur. , Is added for the purpose of preventing it. Specific examples of the retarder include Lewis base compounds containing a nitrogen atom such as n-butylamine, pyridine, 4-vinylpyridine, acetonitrile, ethylenediamine, N-benzylidenemethylamine, pyrazine, piperidine and imidazole; tricyclopentylphosphine, tricyclohexyl. Lewis base compounds containing a phosphorus atom such as hexylphosphine, triphenylphosphine, triphenylphosphite, n-butylphosphine;
Examples thereof include olefin compounds such as vinyl norbornene, propenyl norbornene, and isopropenyl norbornene. The amount of retarder added depends on the metal carbene complex (metal atom).
The ratio is preferably 0.1 to 1000 mol with respect to 1 mol.

The Lewis acid is added to improve the polymerization reaction rate and the like. Examples of the Lewis acid include trialkoxy aluminum, triphenoxy aluminum, dialkoxyalkyl aluminum, alkoxy dialkyl aluminum, trialkyl aluminum, dialkoxy aluminum chloride, alkoxyalkyl aluminum chloride, dialkyl aluminum chloride, trialkoxy scandium, tetraalkoxy titanium. , Tetraalkoxytin, tetraalkoxyzirconium, and the like. The Lewis acid is used in a molar ratio of (metal atom in metal carbene complex: Lewis acid) of usually 1: 0.05 to 1: 100, preferably 1: 0.2.
˜1: 20, more preferably 1: 0.5 to 1:10.

As the molecular weight modifier, for example, a compound having a vinyl group can be used. In particular,
Α-olefins such as 1-butene, 1-pentene, 1-hexene, 1-octene; styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; halogen such as allyl chloride Vinyl compounds containing;
Examples thereof include vinyl ester compounds such as allyl acetate, allyl alcohol and glycidyl methacrylate, and nitrogen-containing vinyl compounds such as acrylamide.

The amount of the vinyl compound used can be appropriately selected according to the molecular weight of the desired polymer, and is usually in the range of 0.1 to 10 mol% based on the norbornene-based monomer. Further, at the end of the polymerization reaction, the vinyl compound may be added again to release the ruthenium complex compound from the growth end of the polymer, if desired, to terminate the polymerization.

Specific examples of monocyclic cycloolefins include cyclobutene, cyclopentene, cyclooctene, cyclododecene, and monocyclic cycloolefin derivatives having a substituent.

The reaction liquid (1) can be prepared by mixing the norbornene-based monomer (1), the metal carbene complex (1) and, if necessary, an additive. Reaction liquid (1)
There is no particular restriction on the preparation method of. To prepare the reaction solution (1),
A known stirrer, homogenizer, static mixer or collision mixer can be used.

The norbornene resin layer (1) can be formed by injecting the reaction solution (1) obtained above into the molding die (1) and subjecting it to bulk ring-opening polymerization. The mold (1) has, for example, a split mold structure, that is, a male mold and a female mold, and one of these molds can be replaced with a mold having another shape, a split mold structure, and a movable mold. A mold having a part, a mold having a structure with an open upper surface, or the like can be used.

When the reaction solution (1) is poured into the molding die (1) for bulk polymerization, a known molding machine such as an RTM machine or a RIM machine can be used. The RTM machine generally comprises a tank for liquid containing norbornene-based monomer, a tank for liquid containing catalyst, a metering pump, a mixer and the like. With a metering pump, the liquid containing the monomer and the liquid containing the catalyst were sent into the mixer at a volume ratio of 1,000: 1 to 10: 1 and mixed to form a reaction liquid, and then the temperature was controlled to a predetermined temperature if necessary. It is possible to inject it into a molding die and immediately perform bulk polymerization there to form the norbornene-based resin layer (1).

In the case of using the RIM machine, the liquid containing the norbornene-based monomer and the liquid containing the catalyst are sent to the mixing head, mixed by the collision energy to form a reaction liquid, and then injected into the molding die, whereupon it is immediately injected. Bulk polymerization is performed to obtain a molded product. A preferable molding method using a RIM machine is to divide a norbornene-based monomer into two parts, and prepare a liquid in which a catalyst is dissolved in a small amount of a solvent as a third liquid,
In this method, these three liquids are collision-mixed and reaction injection molding is performed.

Temperature of the reaction solution before being poured into the mold
Is preferably 20 to 80 ° C. The viscosity of the reaction solution is
For example, at 30 ° C, usually 2 to 1000 cP, preferably
5 to 500 cP. Reaction liquid in the cavity
The filling pressure (injection pressure) at the time of filling is usually 0.1 to 10
0 kgf / cm^Two, Preferably 0.2 to 50 kgf / c
m^TwoIs. If the filling pressure is too low, the inner circumference of the cavity will
The transfer surface formed on the surface tends not to be transferred well.
Yes, if the filling pressure is too high, the rigidity of the mold must be increased.
It's not economical. Mold clamping pressure is usually 0.1 to 1
00 kgf / cm ^TwoWithin the range of. Polymerization time is selected appropriately
It may be selected, but is usually 10 seconds to 20 minutes, preferably 5 seconds.
Within minutes.

When the reaction solution mixed by the above-mentioned RTM machine or RIM machine is injected into the cavity of the molding die, the bulk polymerization reaction is immediately started and the composition is cured. Polymerization is an exothermic reaction. According to this polymerization method, the temperature of the mold is 40 to 10
Even if the temperature is set to 0 ° C, the temperature of the reaction solution rises sharply, and 140 to 2 in a short time (for example, 10 seconds to 5 minutes).
The norbornene-based resin layer (1) can be formed by reaching the peak temperature of 30 ° C.

When a mold having a structure with an open upper surface is used, the reaction solution (1) is poured to a predetermined height in the mold (1) with a structure having an open upper surface, and if necessary, the upper surface is formed. The norbornene-based resin layer (1) can be formed by capping the above and applying a certain load to the ring-opening polymerization. Examples of the method of applying a load from the top surface during the bulk ring-opening polymerization include a method of placing a weight of several kg to several hundred kg on the lid, a method of applying a predetermined pressure from the top of the lid with a pressing machine or the like.

2) Formation of norbornene-based resin layer (2) After forming the norbornene-based resin layer (1), the mold (1) is changed to the mold (2), and the reaction solution (1) is replaced with the reaction solution (2). In the same manner as above (reaction conditions may be changed if necessary), the norbornene resin layer (2) can be formed to obtain a norbornene resin laminate.

The time from the formation of the norbornene-based resin layer (1) to the formation of the norbornene-based resin layer (2) is not particularly limited, but if it is too long, the productivity of the norbornene-based resin laminate decreases, which is preferable. If it is too short, it is difficult to change the molding die (1) to the molding die (2), which is not preferable. The time from the injection of the reaction liquid (1) into the molding die (1) to the injection of the reaction liquid (2) into the molding die (2) is preferably 10 seconds to 120 minutes, more preferably Is 20 seconds to 30 minutes, particularly preferably 30 seconds to 10 minutes.

The reaction liquid (2) is a liquid containing the norbornene-based monomer (2), the metal carbene complex (2) and, if necessary, an additive. As the norbornene-based monomer (2) and the metal carbene complex (2) used here, the same norbornene-based monomer (1) and metal carbene complex (1) as described above can be used. The amounts and preferred modes of use of these are also the same as in the case of the norbornene-based monomer (1) and the metal carbene complex (1). Further, as the additive, the same ones as listed above as those which can be added to the reaction solution (1) can be used according to the same purpose of use. The amount of additive used is also the same as in the case of the reaction solution (1).

In the present invention, as the reaction solution (2),
The one having a composition different from that of the reaction solution (1) is used. Examples of the method for making the composition of the reaction solution (2) different from that of the reaction solution (1) include (i) norbornene-based monomer (2)
As a method of using a norbornene-based monomer different from the norbornene-based monomer (1), (ii) a method of adding another polymerizable monomer to the reaction solution (1), (iii) a different type from the metal carbene complex (1) Examples thereof include a method of using the metal carbene complex (2), (iv) a method of changing the type and / or addition amount of the additive, and (v) a method of combining two or more of these. Among these, the method (i), (ii), (iv) or (v) is preferable, and the method (ii), (iv) or (v) is more preferable from the viewpoint of productivity and handleability. The reaction solution (2) can be prepared in the same manner as the reaction solution (1).

As the molding die (2), a molding die having an internal shape (also referred to as "cavity") different from that of the molding die (1) is used. The molding die (2) may be completely separate from the molding die (1), but it is preferable that it has a common part with the molding die (1). By using such a mold, norbornene-based resin layers having different physical properties can be efficiently and continuously laminated.

The molding die (2) having a common part with the molding die (1) has, for example, a split mold structure, that is, a male mold and a female mold, and one of these molds is replaced with a mold having another shape. Possible molds, molds with split structures, molds with moving parts, molds with split structures, spacers between them to have a new shape, and molds with open tops Examples include molds.

When a molding die of the type (1) is used,
First, the reaction solution (1) is injected into the molding die (1), and bulk ring-opening polymerization is performed to form the norbornene-based resin layer (1), and then either the male mold or the female mold of the molding die (1). One of the molds is replaced with a mold having another shape to form a mold (2), the reaction solution (2) is injected into the mold (2), and bulk ring-opening polymerization is performed to form a norbornene resin. The norbornene-based resin layer (2) can be laminated on the layer (1).

When using a molding die of the type
Norbornene-based resin layer (1) in the same manner as above
After forming the mold (1), the movable part in either or both of the male mold and the female mold of the molding die (1) is moved to move the molding die (2).
Then, the reaction liquid (2) is injected into the molding die (2), and the norbornene-based resin layer (2) can be laminated in the same manner as in the above case.

When the mold of (1) is used, the norbornene resin layer (1) is formed using the mold (1) having a split mold structure, and then the male mold of the mold (1) or A norbornene-based resin layer (2) can be formed by attaching a spacer of a predetermined size between the female molds and using this as a mold (2).

The layered product obtained by bulk polymerization using the forming die having the split mold structure described above can usually be released by opening the forming die while being attached to the male die.
The adhesion of the laminate to the female mold is performed by controlling the molding conditions. The higher the mold temperature or the longer the cooling time (curing time) after the bulk polymerization, the more the polymer adheres to the male mold. It is also possible to shorten the curing time and attach the laminate to the female mold when the mold is opened. However, even if it is attached to the male mold, if the curing time is too long, shrinkage due to cooling of the laminated body will proceed to a considerable extent, so if the laminated body is not cooled excessively, demolding with a demolding device such as an air ejector Good.

When a molding die of the type (1) is used,
The reaction liquid (1) is poured to a predetermined height in a molding die (1) having an open upper surface, and if necessary, the upper surface is covered with a lid and a certain load is applied to perform bulk ring-opening polymerization to perform norbornene-based resin. After forming the layer (1), the lid is removed, the reaction solution (2) is poured, the lid is placed on the upper surface if necessary, and a certain load is applied to perform bulk ring-opening polymerization to perform the norbornene-based resin layer (2). Can be formed. In this case, the mold after forming the norbornene-based resin layer (1) becomes the mold (2) as it is. Examples of the method of applying a load from the top surface during the bulk ring-opening polymerization include a method of placing a weight of several kg to several hundred kg on the lid, a method of applying a predetermined pressure from the top of the lid with a pressing machine or the like. This molding method is called a hand lay-up (hand-stack molding) method.

When any of the above-mentioned molds is used, a new mold is formed after the norbornene-based resin layer (2) is formed, and a reaction solution having a different composition is injected into the mold. By performing bulk ring-opening polymerization, a number of norbornene-based resin layers having different physical properties can be laminated on the norbornene-based resin layer (2).

According to the manufacturing method of the present invention, since the norbornene-based resin layer (1) and the norbornene-based resin layer (2) are formed by polymerizing reaction liquids having different compositions, various norbornene-based resin layers are formed. A combination can be produced. In a preferred embodiment of the present invention, the difference in specific gravity between the norbornene-based resin layer (1) and the norbornene-based resin layer (2) is 0.1 g / cm ³ or more, and in a particularly preferred embodiment, 0.15 g / cm ³ or more. A norbornene-based resin laminate having a difference in specific gravity can be manufactured.

A specific example of the norbornene-based resin laminate thus obtained is shown in FIG. The wall material 1a shown in FIG. 1 (a) includes a norbornene-based resin layer (1) (thickness of about 3 mm) 2a provided with rigidity obtained from a reaction liquid to which glass fiber and calcium carbonate are added as additives. The norbornene-based resin layer (2) (thickness of about 7 mm) 3a having a design property, which is obtained from a reaction liquid to which a gray pigment and an antioxidant are added as an agent.

In the slope plate 1b shown in FIG. 1 (b), a norbornene resin layer (1) (thickness of about 3 mm) 2b obtained from a reaction liquid containing a pigment and an antioxidant, and a glass balloon as an additive were added. A norbornene-based resin layer (2) (thickness: 40 mm) obtained from the reaction solution and having foamability
3b, a norbornene-based resin layer (3) (thickness of about 3 mm) 4b provided with rigidity obtained from a reaction liquid to which glass fiber is added as an additive, dicyclopentadiene and octadiene as norbornene-based monomers, and an additive A norbornene-based resin layer (4) (elastomer layer; thickness of about 5 mm) 4b provided with elasticity, which is obtained from a reaction liquid to which a pigment, an antioxidant and an ultraviolet absorber are added.
Consists of. The norbornene-based resin layer (4) 5b also has a non-slip function.

Flooring flooring agent 1c shown in FIG. 1 (c)
Is a norbornene-based resin layer (1) (elastomer layer; thickness 10) to which elasticity is imparted, which is obtained from a reaction solution containing a mixture of dicyclopentadiene and octadiene as a norbornene-based monomer and an antioxidant as an additive.
2c, a norbornene-based resin layer (2) (thickness: about 15 mm) 3 provided with rigidity obtained from a reaction liquid to which glass fiber and calcium carbonate are added as additives.
c, a norbornene-based resin layer (3) (thickness of about 3 mm) 4c having a design property obtained from a reaction liquid to which wood powder, an antioxidant and an ultraviolet absorber are added as additives.

Although not shown, the manufacturing method of the present invention can be applied to manufacture of a propeller for a wind power generator. For example, a norbornene-based resin layer (1) having foamability (weight reduction) obtained from a reaction liquid obtained by adding H-steel as a core material and glass balloons as an additive thereon, and the norbornene-based resin layer On the norbornene-based resin layer (2) to which rigidity is imparted (stiffness imparted), which is obtained from a reaction liquid obtained by adding glass fiber and calcium carbonate as an additive thereto, and on the norbornene-based resin layer (2), It can be produced by sequentially laminating a norbornene-based resin layer (3) having weather resistance, which is obtained from a reaction solution containing an antioxidant and an ultraviolet absorber.

.. The norbornene-based resin laminate obtained by the production method of the present invention is not limited to that shown in FIG. 1, but the kind of physical properties imparted to the norbornene-based resin layer, the number of laminated norbornene-based resin layers, and The layer thickness and the like can be freely changed without departing from the gist of the present invention.

The production method of the present invention can be applied to the production of norbornene-based resin laminates of any application, shape and size. The norbornene-based resin laminate obtained by the present invention is, for example, a material for use as a substitute for wood such as building materials, construction materials and park materials; septic tanks, bathtubs, unit baths, washstands, wall panels and kitchen top plates. It is useful as a housing material; leisure products such as leisure boats; materials for transportation equipment, transportation containers or storage containers; propellers for wind power generators.

[0084]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. Example 1 Production of Sandwich Structure 3 kg of dicyclopentadiene (containing about 10% by weight of cyclopentadiene trimer) as a norbornene-based monomer was placed in a 20 L reactor equipped with a rotary stirrer having a plurality of stirring blades. The mixture was cooled in an ice bath until the liquid temperature reached 10 ° C. Benzylidene (1,3-dimesityl imidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride (Org.
Lett. 1.86 g (dissolved based on the description in Vol. 1, page 953 in 1999) dissolved in 40 ml of toluene (ruthenium complex / norbornene-based monomer =
Solution 1 was obtained by adding 1/10000 (mol / mol)) to the above reactor to make a reactive mixture (time 0 seconds), and stirring with a stirrer until it became uniform visually.

Glass fiber (chop strand, strand diameter 30 μ, length 5 mm) 1 was added to the solution A as a filler.
kg and 1 kg of calcium carbonate were added (weight ratio of norbornene-based monomer / filler 60/40), and the mixture was stirred with a stirrer until visually uniform, and then the stirrer was removed. The time when the mixing of the filler was completed was 90 seconds.
As a molding die, a square SUS container having a bottom surface of 300 mm × 300 mm was prepared, and a part of the contents of the reactor was quickly poured into the SUS container, and 300 mm × 3 from the top.
A 00 mm plate-shaped lid was placed (the lid does not have a closed structure and an appropriate vent gap is provided), and a weight of 10 kg was used for pressing. At a time of about 200 seconds, the temperature started to rise, the polymerization reaction started and then ended. When the plate-shaped lid was taken from the reactor and the inside was confirmed, it was 300 mm × 300 mm × thickness 15
A norbornene-based resin molded body (norbornene-based resin layer 2d) having a size of mm was formed.

Next, a solution containing a norbornene-based monomer and a ruthenium carbene complex was prepared in the same manner as the solution A except that the scale was doubled (solution B). In this solution B, a glass balloon (3M and Zeelan
Industries, Inc. Made by 3M Scot
chlite Glass Bubbles Gene
ral Purpose Series K25, heat resistance 750 psi, true specific gravity 0.25) 1 kg and antioxidant 30 g were added, and the mixture was stirred by a stirrer until visually uniform, and then the stirrer was removed. The time when the mixing of the filler was completed was 90 seconds.

A plate-like lid is taken from the reactor in which the polymerization reaction has been carried out, and a part of the contents of the reactor is poured into a molding die,
A plate-like lid of 300 mm × 300 mm was placed thereon (the lid does not have a closed structure and an appropriate vent gap is provided), and a weight of 100 kg was used for pressing. At a time of about 200 seconds, the temperature started to rise, the polymerization reaction started and then ended. After removing the plate-shaped lid from the reactor and checking the inside,
A foamable norbornene-based resin molded body (norbornene-based resin layer 3d) having a size of 300 mm × 300 mm × thickness of 45 mm was formed. Norbornene-based resin layer 3d
Was laminated on the norbornene-based resin layer 2d, and both were in close contact.

Then, as a filler, glass fiber (chop strand, strand diameter 30 μ, length 5 mm) 1 k
g and calcium carbonate 1 kg, glass fiber 0.
5 kg, 0.5 kg of calcium carbonate, and 1 kg of wood flour were used (weight ratio of norbornene-based monomer / filler 6
(0/40) except that the norbornene-based resin layer 4d was formed on the norbornene-based resin layer 3d in the same manner as the norbornene-based resin layer 2d. The reaction started and then ended. When the plate-shaped lid was removed from the reactor and the inside was confirmed, the norbornene-based resin layer 4d was 300 mm × 3
The norbornene-based resin molded body had a size of 00 mm × thickness of 15 mm. The norbornene-based resin layer 4d was laminated on the norbornene-based resin layer 3d, and both were in close contact with each other.

As described above, the norbornene resin layer 2d having rigidity, the norbornene resin layer 3d having foamability, and the norbornene resin layer 4d having rigidity and design are formed. A norbornene-based resin laminate 1d having a sandwich structure was obtained. The specific gravity of the norbornene-based resin layer 2d is 1.6, and the norbornene-based resin layer 3
The specific gravity of d was 0.8, and the specific gravity of the norbornene-based resin layer 4d was 1.2. A structural cross-sectional view of the obtained norbornene-based resin laminate is shown in FIG.

When the cross section of the norbornene resin laminate 1d obtained in the example was cut and visually observed, three layers of the norbornene resin layers 2d, 3d and 4d were firmly adhered to each other, and the surface irregularities and It was a good one with no curing defects on the surface and inside, and no defective filling in the mold. In addition, a person having a weight of 60 kg steps on and off this norbornene-based resin laminate by repeating 1000 times,
It was tested whether delamination due to repeated loading occurred, but no delamination was observed and the result was good.

Comparative Example 1 Dicyclopentadiene (containing about 10% by weight of cyclopentadiene trimer) as a norbornene-based monomer,
Liquid A containing 41 mmol of diethylaluminum chloride, 41 mmol of isopropyl alcohol and 21 mmol of silicon tetrachloride with respect to dicyclopentadiene, dicyclopentadiene (containing about 10 wt% of tricyclopentadiene), dicyclopentadiene Tri (tridecyl) ammonium molybdate 10 against cyclopentadiene
Millimeter concentration and 1 kg of glass fiber (chop strand, strand diameter 30μ, length 5 mm) as filler
And a solution B containing 1 kg of calcium carbonate were prepared.

As a molding die, the bottom surface is 300 mm × 300
A SUS container in which the inside of a square of mm was replaced with nitrogen was prepared, and a part of the liquid prepared by mixing the liquid A and the liquid B at a mixing ratio of 1: 1 under a nitrogen atmosphere was quickly placed in the SUS container. It was poured, and a plate-like lid of 300 mm × 300 mm was placed thereon (the lid does not have a closed structure and an appropriate vent gap is provided), and a weight of 100 kg was used for pressing. Time about 600
The temperature started rising in seconds, the polymerization reaction started, and then ended. When the plate-shaped lid was removed from the reactor and the inside was confirmed, a norbornene-based resin molded body (norbornene-based resin layer 2 having a size of 300 mm × 300 mm × thickness 15 mm)
e) had been formed.

Next, the scale was doubled, and instead of glass fiber and calcium carbonate as a filler, a glass balloon (3M and Zeelan Industry) was used.
s, Inc. 3M Scotchlite Gla
ss Bubbles General Purpos
e Series K25, heat resistance 750 psi, true specific gravity 0.25) 1 kg, and the polymerization reaction was performed in the same manner as in the case of forming the norbornene-based resin layer 2e except that 60 g of the antioxidant was added. Remove the plate-shaped lid from the reactor,
Pour the contents of the reactor into the mould, 30 from above
A 0 mm × 300 mm plate-shaped lid was placed (the lid does not have a closed structure and an appropriate vent gap is provided), and a weight of 100 kg was used for pressing. The temperature starts to rise at about 200 seconds,
The polymerization reaction started and then ended. After removing the plate-shaped lid from the reactor and checking the inside, the size was 300 mm ×
A foamable norbornene-based resin molded body having a size of 300 mm and a thickness of 45 mm was formed. Norbornene-based resin layer 3
e was laminated on the norbornene-based resin layer 2e,
The adhesion between the two was poor, and the norbornene-based resin layer 3e was easily separated from the norbornene-based resin layer 2e. for that reason,
The following work was stopped.

[0094]

According to the method for producing a norbornene-based resin laminate of the present invention, a norbornene-based resin laminate having different physical properties can be produced simply and efficiently by subjecting a norbornene-based monomer to bulk ring-opening polymerization. You can Further, the norbornene-based resin laminate manufactured by the manufacturing method of the present invention has excellent adhesion between norbornene-based resin layers. Further, it is excellent in impact resistance, heat resistance, dimensional stability, water absorption resistance, and the like, and has an excellent feature that it is lightweight because it can be molded thin.

[Brief description of drawings]

FIG. 1 is a structural cross-sectional view of an example of a norbornene-based resin laminate obtained by the production method of the present invention. Figure 1
Inside, (a) is a wall material, (b) is an example of a slope board, (c) is an example of a flooring floor material.

FIG. 2 is a structural cross-sectional view of a sandwich-structured norbornene-based resin laminate obtained in an example.

[Explanation of symbols]

1a ... Norbornene-based resin laminate (wall material) produced by the present invention 1b ... Norbornene-based resin laminate (slope plate) produced by the present invention 1c ... Norbornene-based resin laminate produced by the present invention (flooring floor) Material) 1d ... Norbornene-based resin laminates 2a, 2b, 2c ... Norbornene-based resin layer (1) 3a, 3b, 3c ... Norbornene-based resin layer (2) 4b, 4c. Resin layer (3) 5b ... Norbornene resin layer (4) 2d, 3d, 4d ... Norbornene resin layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI theme code (reference) B29L 9:00 B29L 9:00 F term (reference) 4F100 AK02A AK02B BA02 BA07 BA16 BA26 JA13A JA13B JL02 4F202 AA12D AA12L AG03 CA01 CA11 CB01 CB22 4F204 AA12 AG03 EA03 EB01 EB22 EF01 EF02 EF27 EK24 4J032 CA34 CA36 CA43 CB01 CB03 CC03 CC07 CD02 CE03 CE06 CE22

Claims (3)

[Claims] 1. A first norbornene-based monomer is obtained by injecting a reaction liquid (1) containing a norbornene-based monomer (1) and a metal carbene complex (1) into a molding die (1) and performing bulk ring-opening polymerization. The step of forming a resin layer and the reaction liquid (2) containing the norbornene-based monomer (2) and the metal carbene complex (2) are injected into the molding die (2) to perform bulk ring-opening polymerization, Laminating the norbornene resin layer (2) on the norbornene resin layer (1), wherein the reaction liquid (1) and the reaction liquid (2) have different compositions. Method for manufacturing resin laminate. 2. A norbornene-based resin layer (2) having a specific gravity different from that of the norbornene-based resin layer (1) by 0.1 g / cm ³ or more is laminated on the norbornene-based resin layer (1). A method for producing the norbornene-based resin laminate described. 3. The method for producing a norbornene-based resin laminate according to claim 1, wherein a mold having a common part with the mold (1) is used as the mold (2).