JP2007224123A - Method for producing norbornene-based resin molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a norbornene-based resin molding that controls occurrence of filler content unevenness (filler deviation) in an obtained molding even in the case of addition of a filler so as to improve rigidity and strength properties, has slight reduction and dispersion of molding density and effectively prevents defects in terms of appearance and property deterioration caused by content unevenness. <P>SOLUTION: The method for producing a norbornene-based resin molding comprises a process for separately sending two or more reaction stock solutions to a mixing head, mixing the two or more reaction stock solutions in the mixing head to obtain a reaction liquid containing a norbornene-based monomer, a metathesis catalyst and a filler and a process for injecting the reaction liquid to a mold and subjecting the reaction liquid to a bulk polymerization in the mold. When the total of feed pressure of the whole reaction stock solutions constituting the reaction liquid to the mixing head is 100%, the feed pressure of the reaction stock solutions (liquid F) containing the filler to the mixing head is in the range of 20-40%. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a norbornene resin molded product obtained by bulk polymerization of a norbornene monomer in a mold.

  Conventionally, it is practical to produce molded products made of norbornene resin by injecting a reaction solution containing norbornene monomer and metathesis catalyst into the mold by reaction injection molding method (RIM) and performing bulk ring-opening polymerization. Has been. The reaction solution is usually obtained by instantaneously mixing two or more reaction stock solutions with a collision mixing device or the like. Such a reaction stock solution is not bulk polymerized with only one liquid, but when all the liquids are mixed, it becomes a reaction liquid containing each component in a predetermined ratio, and as a result, the norbornene monomer is bulk polymerized.

  It is known to mold by adding various fillers to the reaction liquid for the purpose of imparting rigidity and dimensional stability to the molded body obtained by the RIM method (less expansion and contraction due to heat of the molded body). Yes. However, in the conventional method, there are cases where the rigidity cannot be sufficiently increased or the strength characteristics are remarkably deteriorated while the rigidity is increased. In addition, the filler is used by adding to the reaction stock solution. However, when the reaction stock solution contains the filler as described above, the storage stability of the reaction stock solution may be lowered.

  For example, in Patent Document 1, a filler having an average particle diameter of 1 to 50 μm is added to a norbornene-based resin molded body obtained by the RIM method in order to improve the rigidity of the obtained molded body while maintaining dimensional stability. It has been proposed to use (for example, calcium carbonate). However, in this document, mixing failure occurs when the reaction stock solution is mixed, the inclusion of the filler (unevenness of the filler) occurs in the resulting molded body, and defects (surface color) appear on the appearance. Unevenness). In addition, the average density of the actually obtained molded product may be lower than the density calculated from the amount of filler charged (calculated density), or the density may vary depending on the part of the molded product (the variation in density is large). there were. Further, due to uneven inclusion of the filler, the effect of adding the filler becomes insufficient, and the rigidity and strength characteristics may be inferior.

JP 2003-321597 A

  The present invention was made in view of such a situation, and in the method for producing a norbornene-based resin molded body, even when a filler is contained for improving rigidity and dimensional stability, Generation of uneven inclusion of filler (unevenness of filler) is suppressed, and defects in appearance, reduction and variation in molded product density, and characteristic deterioration due to uneven inclusion are effectively prevented It is providing the manufacturing method of a resin molding.

  As a result of intensive investigations to achieve the above object, the present inventors specify the liquid feed pressure of the reaction stock solution (F solution) containing a filler when sending two or more reaction stock solutions to the mixing head. The inventors have found that the above-described object can be achieved by controlling the amount within the above range, and have completed the present invention based on this finding.

That is, the method for producing a norbornene-based resin molded body according to the present invention includes:
Two or more reaction stock solutions are separately fed into a mixing head, and two or more reaction stock solutions are mixed in the mixing head to obtain a reaction solution containing a norbornene-based monomer, a metathesis catalyst, and a filler;
A step of injecting the reaction liquid into a mold and performing bulk polymerization in the mold, and a method for producing a norbornene-based resin molded body,
The reaction stock solution consists of a reaction stock solution (F solution) containing at least a filler, and one or more other reaction stock solutions,
Regarding the liquid supply pressure for sending each reaction stock solution into the mixing head,
The feeding pressure of the reaction stock solution (F solution) containing the filler is P _F [MPa],
When the total of the liquid feeding pressures of all the reaction stock solutions constituting the reaction solution is P _S [MPa],
Wherein the total liquid feed pressure _P S 100% of the all reaction stock solution, characterized in that the feeding pressure _{P F} and 20-40% of the range of the reaction stock solution (F liquid).

Preferably, the filler contains a fibrous filler having an aspect ratio of 5 to 100 and a particulate filler having an aspect ratio of 1 to 2.
Preferably, the filler is a hybrid filler obtained by stirring the fibrous filler and the particulate filler at a high speed in a dry manner.

  According to the present invention, in a method for producing a norbornene-based resin molded body, even when a filler is included for the purpose of improving rigidity and dimensional stability, the inclusion unevenness of the filler in the obtained molded body (filler) ), Norbornene-based resins with no significant defects in appearance, low density and variation in molded product, and sufficiently improved filler addition effects (for example, rigidity and dimensional stability) A molded body can be provided.

  First, the reaction liquid used in the production method of the present invention will be described before describing the production method of the norbornene-based resin molded body of the present invention (hereinafter sometimes simply referred to as “molded body”).

Reaction solution The reaction solution used in the production method of the present invention is obtained by mixing a reaction stock solution prepared by dividing a norbornene-based monomer, a metathesis catalyst, a filler and an optional component into two or more solutions. And this reaction undiluted solution does not bulk polymerize with only one liquid, but when all the liquids are mixed, it becomes a reaction liquid containing each component at a predetermined ratio, and the norbornene monomer is bulk polymerized.
In addition, as an arbitrary component, an activator, an activity regulator, an elastomer, antioxidant, etc. are mentioned.
Hereinafter, each component contained in the reaction solution will be described.

Norbornene-based monomer The norbornene-based monomer is a compound having a norbornene ring structure, and any compound may be used as long as it is such a compound. Especially, since the molded object excellent in heat resistance is obtained, it is preferable to use the polycyclic norbornene-type monomer more than tricyclic.

  Specific examples of norbornene-based monomers include bicyclic compounds such as norbornene and norbornadiene; tricyclic compounds such as dicyclopentadiene (cyclopentadiene dimer) and dihydrodicyclopentadiene; tetracyclic compounds such as tetracyclododecene; Pentacycles such as pentadiene trimer; heptacycles such as cyclopentadiene tetramer; alkyl such as methyl, ethyl, propyl and butyl, alkenyl such as vinyl, alkylidene such as ethylidene, phenyl, tolyl, naphthyl, etc. And substituted groups having polar groups such as ester groups, ether groups, cyano groups, and halogen atoms. These monomers may be used in combination of two or more. Among these, a tricyclic, tetracyclic or pentacyclic monomer is preferable, and dicyclopentadiene is particularly preferable because it is easily available, has excellent reactivity, and has excellent heat resistance of the obtained molded body. preferable.

  In addition, it is preferable that the ring-opening polymer to be produced is a thermosetting type. For this purpose, among the norbornene-based monomers, two or more reactive double bonds such as a symmetric cyclopentadiene trimer are used. It is preferable to use at least a crosslinkable monomer. The ratio of such a crosslinkable monomer (excluding dicyclopentadiene) in all norbornene monomers is preferably 2 to 30% by weight.

  In addition, monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, and cyclododecene, which can be ring-opening copolymerized with a norbornene-based monomer, may be used as a comonomer within a range that does not impair the object of the present invention.

The filler filler is not particularly limited as long as it is a solid material insoluble in the norbornene-based monomer, but it is preferable to use a fibrous filler and a particulate filler. By using such two types of fillers, fibrous and particulate, the rigidity and dimensional stability of the obtained molded body can be improved.

  The fibrous filler preferably has an aspect ratio of 5 to 100, more preferably 10 to 50, and particularly preferably 15 to 35. If the aspect ratio is too small, the resulting molded article may have insufficient rigidity and dimensional stability. On the other hand, if it is too large, the injection nozzle may be clogged when the reaction solution is injected into the mold.

  In the present invention, the aspect ratio of the filler is a ratio between the average major axis diameter of the filler and the 50% volume cumulative diameter. Here, the average major axis diameter is a number average major axis diameter calculated as an arithmetic average value obtained by measuring the major axis diameters of 100 fillers randomly selected from an optical micrograph. The 50% volume cumulative diameter is a value obtained by measuring the particle size distribution by the X-ray transmission method.

  The 50% volume cumulative diameter of the fibrous filler is preferably 0.1 to 50 μm, more preferably 1 to 30 μm. If the 50% volume cumulative diameter is too small, the molded article may have insufficient rigidity and dimensional stability. On the other hand, if it is too large, it may settle in the tank or piping when the reaction solution is injected into the mold or the injection nozzle may be clogged.

  Specific examples of the fibrous filler include glass fiber, wollastonite, potassium titanate, zonolite, basic magnesium sulfate, aluminum borate, tetrapot type zinc oxide, gypsum fiber, phosphate fiber, alumina fiber, acicular carbonate Calcium, acicular boehmite and the like can be mentioned. Especially, since the intensity | strength of the molded object obtained with a small usage-amount can be raised and a block polymerization reaction is not inhibited, wollastonite is preferable.

  The particulate filler preferably has an aspect ratio of 1 to 2, particularly preferably 1 to 1.5. Further, the 50% volume cumulative diameter of the particulate filler is preferably 0.1 to 50 μm, more preferably 1 to 30 μm. If the 50% volume cumulative diameter is too small, the resulting molded article may have insufficient rigidity and dimensional stability. On the other hand, if it is too large, when the reaction solution is injected into the mold, it may settle in the tank or piping, or the injection nozzle may be clogged.

  Specific examples of the particulate filler include calcium carbonate, calcium silicate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, titanium oxide, zinc oxide, barium titanate, silica, alumina, carbon black, graphite, antimony oxide, Examples thereof include red phosphorus, various metal powders, clay, various ferrites, and hydrotalcite. These particulate fillers may be hollow bodies. Of these, calcium carbonate is preferable because it does not inhibit the bulk polymerization reaction.

  In the case of using a fibrous filler and a particulate filler, these ratios are preferably in a weight ratio of fibrous filler: particulate filler = 95: 5 to 5:95, 95: 5 The range of ˜50: 50 is more preferable, and the range of 80:20 to 60:40 is particularly preferable. By setting the ratio of the fibrous filler to the particulate filler within the above range, the rigidity and dimensional stability of the obtained molded body can be made uniform, and the anisotropy of the molded body is reduced. Can do.

The fibrous filler and the particulate filler to be contained as the filler are preferably used as a hybrid filler by high-speed stirring in a dry process.
The hybrid filler only needs to be obtained by high-speed stirring of the fibrous filler and the particulate filler at high speed, and the stirring conditions for high-speed stirring are not particularly limited. Can be obtained by stirring so that the peripheral speed (blade tip speed) of the rotary blade is usually 10 to 60 m / s, preferably 15 to 55 m / s. By dispersing these fibrous fillers and particulate fillers at high speed to form a hybrid filler, the dispersibility in the norbornene-based monomer can be enhanced.

  In particular, the fibrous filler and the particulate filler can be crushed by using a dry filler at high speed and using it as a hybrid filler. And since these fillers can be disperse | distributed uniformly, the dispersibility in the case of making it contain in reaction stock solution can be improved. Therefore, it can disperse | distribute favorably also in the molded object obtained, and the addition effect of these fillers can further be improved.

  In addition, it is preferable to hydrophobize the surface when the fibrous filler and the particulate filler are dry-mixed at high speed to form a hybrid filler. By carrying out the hydrophobization treatment, it is possible to further improve the dispersibility in the reaction stock solution, and as a result, it is possible to further improve the rigidity and dimensional stability of the obtained molded body. Examples of the treating agent used for the hydrophobizing treatment include silane coupling agents, titanate coupling agents, aluminum coupling agents, fatty acids, fats and oils, surfactants, waxes, and other polymers. A ring agent and a titanate coupling agent are preferable. These may be used in combination.

  The method of hydrophobizing is not particularly limited. For example, (1) a method in which each filler and treatment agent constituting the hybrid filler are combined and charged at a high speed in a dry process, and (2) each filler is combined. The method of adding the treatment agent after high-speed stirring in the dry method, and further stirring at high speed in the dry method, (3) adding the treatment agent separately to each filler, mixing after high-speed stirring in the dry method, Furthermore, the method of stirring at high speed by a dry method, etc. are mentioned. Among these, the method (2) is preferable, and in this case, in particular, it is preferable to gradually add the treatment agent by spraying or the like.

  The amount of filler in the reaction solution is preferably 5 to 60% by weight, more preferably 10 to 50% by weight. If the amount of the filler is too large, it may settle in the tank or piping when the reaction solution is injected into the mold or the injection nozzle may be clogged. On the other hand, if the amount is too small, the resulting molded article may have insufficient rigidity and dimensional stability.

Metathesis Catalyst The metathesis catalyst is not particularly limited as long as it can ring-open polymerization a norbornene monomer in the reaction injection molding method (RIM method), and may be a known one.
Examples of such a metathesis catalyst include compounds of transition metals belonging to Group 5 or Group 6 of the periodic table, metal carbene complexes having a metal atom of Group 8 of the periodic table as a central metal, and the like.

Examples of transition metal compounds of Group 5 or Group 6 of the periodic table include halides, oxyhalides, oxides, organic ammonium salts, oxyacid salts, and heteropolyacid salts of these transition metals. Among these, halides, oxyhalides and organic ammonium salts are preferable, and organic ammonium salts are more preferable. Moreover, as a transition metal, molybdenum, tungsten, and tantalum are preferable, and molybdenum and tungsten are more preferable.
Particularly preferred embodiments of the metathesis catalyst include tridodecyl ammonium molybdate and tungstate, methyl tricapryl ammonium molybdate and tungstate, tri (tridecyl) ammonium molybdate and tungstate, and Examples include trioctylammonium molybdate and tungstate.

  When the compound of transition metal belonging to Group 5 or Group 6 of the periodic table is used as a metathesis catalyst, the amount used is usually 0.01 to 50 mmol, preferably 0, per 1 mol of norbornene monomer in the reaction solution. .1-20 mmol.

In the metal carbene complex having a metal atom of Group 8 of the periodic table as a central metal, a carbene compound is bonded to the central metal atom consisting of a metal atom of Group 8 of the periodic table, and the metal atom (M) and carbene carbon (> C: ) Have a structure (M = C) directly bonded in the complex. The carbene compound is a general term for compounds having a carbene carbon, that is, a methylene free radical.
As the metal atom of Group 8 of the periodic table, ruthenium and osmium are preferable, and ruthenium is particularly preferable.
Preferable specific examples of the metal carbene complex include benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityloimidazolidine-2-ylidene) (Tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-4,5-dibromoimidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, bis (tricyclohexylphosphine) benzylidene ruthenium dichloride, and the like.

  The amount used when these metal carbene complexes are used as a metathesis catalyst is usually 0.001 to 1 mmol, preferably 0.002 to 0.1 mmol, with respect to 1 mol of the monomer in the reaction solution.

  When the amount of the metathesis catalyst used is too small, the polymerization activity is too low and the reaction takes time, and the production efficiency tends to be lowered. On the other hand, if the amount used is too large, the reaction becomes too violent, and bulk polymerization proceeds before the reaction solution is sufficiently filled in the mold, and the catalyst tends to precipitate, making it difficult to store homogeneously. Tend to be.

  The metathesis catalyst may be used by dissolving or dispersing in a small amount of an inert solvent. Examples of such inert solvents include chain aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; alicyclic carbonization such as cyclopentane, cyclohexane, methylcyclohexane, decahydronaphthalene, tricyclodecane, and cyclooctane. Hydrogen solvents; aromatic hydrocarbon solvents such as benzene, toluene and xylene; ether solvents such as diethyl ether and tetrahydrofuran. Further, a liquid anti-aging agent, a plasticizer or an elastomer may be used as a solvent as long as the activity as a catalyst is not lowered. Among these solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and alicyclic hydrocarbon solvents that are widely used industrially are preferable.

The optional component activator is used for causing the metathesis catalyst to exhibit the polymerization reaction activity when the metathesis catalyst which does not have the polymerization reaction activity alone is used.
Examples of the activator include alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride; alkoxyalkylaluminum halides obtained by substituting a part of the alkyl groups of these alkylaluminum halides with alkoxy groups; organotin compounds; The amount of the activator to be used is not particularly limited, but is usually 0.1 to 100 mol, preferably 1 to 10 mol, relative to 1 mol of the metathesis catalyst used in the whole reaction solution.

The activity regulator has an effect of changing the reaction rate, the time from mixing of the reaction solution to the start of the reaction, the reaction activity, and the like.
In the case of using a transition metal group 5 or 6 transition metal compound as the metathesis catalyst, examples of the activity regulator include compounds having an action of reducing the metathesis catalyst, alcohols, haloalcohols, Esters, ethers, nitriles and the like can be used. Of these, alcohols and haloalcohols are preferable, and haloalcohols are particularly preferable. Specific examples of alcohols include n-propanol, n-butanol, n-hexanol, 2-butanol, isobutyl alcohol, isopropyl alcohol, t-butyl alcohol and the like. Specific examples of haloalcohols include 1,3-dichloro-2-propanol, 2-chloroethanol, 1-chlorobutanol and the like.
In the case where a metal carbene complex is used as the metathesis catalyst, examples of the activity regulator include a Lewis base compound. Lewis base compounds include Lewis base compounds containing phosphorus atoms such as tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, triphenylphosphite, n-butylphosphine; n-butylamine, pyridine, 4-vinylpyridine, acetonitrile, Lewis base compounds containing nitrogen atoms such as ethylenediamine, N-benzylidenemethylamine, pyrazine, piperidine, imidazole, and the like. Further, norbornene substituted with an alkenyl group such as vinyl norbornene, propenyl norbornene and isopropenyl norbornene is the norbornene-based monomer and also serves as an activity regulator.
The amount of these activity regulators used varies depending on the compound used and is not uniform.

  Examples of the elastomer include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), and ethylene. -Propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), hydrides thereof and the like. The viscosity of the reaction solution can be adjusted by dissolving the elastomer in the reaction solution. Moreover, the impact resistance of the obtained molded object can be improved by adding an elastomer. When the elastomer is used, the amount used is usually 0.5 to 20 parts by weight, preferably 2 to 10 parts by weight, with respect to 100 parts by weight of the norbornene monomer in the reaction solution.

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

Method for Producing Norbornene Resin Molded Product Next, a method for producing the norbornene resin molded product of the present invention using the reaction solution described above will be described.
First, a reaction stock solution is prepared. The reaction stock solution is prepared by dividing each component contained in the reaction solution into two or more solutions.

The combination of two or more reaction stock solutions is not particularly limited, and various combinations can be selected. In this embodiment, it is preferable to prepare the following three types of reaction stock solutions.
That is, a reaction stock solution (solution A) containing a norbornene monomer and a catalytically active component (activator, activity regulator), a reaction stock solution (solution B) containing a norbornene monomer and a metathesis catalyst, a norbornene monomer and packing It is preferable to prepare three types of reaction stock solutions including a reaction stock solution (F solution) containing a material.
Hereinafter, the production method of the norbornene-based resin molded article of the present invention will be described in detail by exemplifying the case where the three types of reaction stock solutions A, B, and F are used as the reaction stock solution.

  The content of each component in each reaction stock solution (A solution, B solution, F solution) is not particularly limited, and the composition of the reaction solution obtained when each reaction stock solution is mixed is within the above-described range. Can be prepared. In this embodiment, the amount of filler in the reaction stock solution (F solution) is preferably 20 to 80% by weight, more preferably 35 to 65% by weight. If the amount of the filler in the reaction stock solution (F solution) is too large, the filler may settle in the tank or piping during storage. Moreover, when there are too few, the quantity of the filler in the molded object obtained will decrease, and the improvement effect of rigidity or dimensional stability may become inadequate.

Then, using each reaction stock solution prepared above, a norbornene-based resin molded body is manufactured by a reaction injection molding method using a reaction injection molding apparatus as shown in FIG.
FIG. 1 is a schematic view of a main part of a reaction injection molding apparatus according to an embodiment of the present invention.

First, as a preparation for reaction injection molding, each of the reaction stock solutions (A solution, B solution, F solution) prepared above is stored in tanks 10, 20, and 30 shown in FIG. By storing each reaction stock solution in each tank, the reaction stock solution can be sent into the mixing head 40.
Specifically, the reaction stock solution (liquid A) stored in the tank 10 is configured to be sent into the mixing head 40 through the pipe 14 by the metering pump 12. Similarly, the tank 20 30, each reaction stock solution (B solution, F solution) can also be sent to the mixing head 40 through the pipes 24, 34 by the metering pumps 22, 32, respectively.

  In addition, each liquid metering pump 12, 22, 32 for sending each reaction stock solution (A liquid, B liquid, F liquid) to the mixing head 40 can control the liquid feeding pressure independently. That is, when each reaction stock solution (A solution, B solution, F solution) is sent into the mixing head 40, it can be sent at different pressures. In addition, each liquid feeding pressure can be measured by the pressure gauges 16, 26, and 36 installed at the outlets of the metering pumps 12, 22, and 32.

  Next, each metering pump 12, 22, 32 is operated, and each reaction stock solution (A solution, B solution, F solution) stored in the tank 10, 20, 30 is continuously sent into the mixing head 40, In the mixing head 40, each reaction stock solution is collided with each other to obtain a reaction solution. Then, each reaction stock solution is continuously supplied into the mixing head 40, so that when the pressure in the mixing head 40 reaches a predetermined pressure, the pin 50 is opened, and the reaction solution obtained by collision mixing is used. Then, the mixture is injected from the mixing head 40 into the mold (not shown) connected to the pipe 52 through the pipe 52, and the norbornene monomer is polymerized in the mold. It should be noted that the time from when each metering pump 12, 22, 32 is activated to start feeding each reaction stock solution into the mixing head 40 until the pin 50 is opened is usually 0.5 to 3.5 seconds.

In the present embodiment, when the reaction stock solutions (A solution, B solution, and F solution) stored in the tanks 10, 20, and 30 are sent into the mixing head 40, the feed pressure of the reaction stock solution is as follows. It is related.
That is, the feeding pressure of each reaction stock solution (A liquid, B liquid, F liquid) is set as A liquid: P _A [MPa], B liquid: P _B [MPa], F liquid: P _F [MPa] When the total liquid supply pressure of the reaction stock solution is P _S (= P _A + P _B + P _F ) [MPa], the liquid supply pressure P _F of the F liquid is 20 with respect to the total liquid supply pressure P _S 100%. The range is ˜40%, preferably 25˜33%.

The liquid feed pressure P _F of F solution in the above range, it is possible to prevent the occurrence of containing unevenness of filler in the molded body to be obtained (bias filler), or a defect in appearance, molding It is possible to effectively prevent deterioration in characteristics due to a decrease in body density and variations, as well as deterioration in the inclusion of fillers (for example, a decrease in rigidity and dimensional stability). In addition, even if the density (calculation density) calculated from the content of the filler in the reaction liquid is the same (decrease in the average density of the molded body), the filler does not have the final density. In particular, it is caused by uneven distribution in burrs and runners removed from the product (molded product).
The liquid feed pressure _{P A, P B, P F} of the reaction stock solution can be measured by the pressure gauge 16, 26 and 36. Liquid feed pressure _{P A, P B, P F} is preferably in the range of 3～7MPa.

Even feeding pressure P _F is too high or too low of a reaction stock solution containing filler (F solution), there is a possibility that the content unevenness of filling the molded body obtained material occurs.

  The mold used for reaction injection molding (not shown) is not necessarily a rigid and expensive mold, and is not limited to a metal mold but can be a resin mold or a simple mold. . This is because reaction injection molding can be performed at a relatively low temperature and low pressure. Further, it is preferable to replace the inside of the mold with an inert gas such as nitrogen gas before injecting the reaction solution.

  The mold temperature is preferably 10 to 150 ° C, more preferably 30 to 120 ° C, still more preferably 40 to 100 ° C. The mold clamping pressure is usually in the range of 0.01 to 10 MPa. The time for bulk polymerization may be appropriately selected, but usually after 20 seconds to 20 after the completion of injection of each reaction stock solution (A solution, B solution, F solution) (that is, after the metering pumps 12, 22, 32 are stopped). Minutes, preferably 20 seconds to 5 minutes.

  In the present embodiment, a composite member formed by integrally forming a composite member and a norbornene-based resin molded body obtained by the production method of the present invention by installing the composite member in a mold may be used. Here, “being integrally formed” means that the norbornene-based resin and the composite member are in close contact with each other so that they are not easily peeled off, and may be in close contact by resin fusion. Alternatively, they may be in close contact via an adhesive layer.

  The composite member is a material that can be installed in a mold and does not have fluidity at the mold temperature during bulk polymerization. Examples of the material of the composite member include inorganic materials such as metal, glass, ceramics, and wood; organic materials such as resin and rubber. As the inorganic material, metal or glass is preferable. As the organic material, a resin is preferable. Examples of the resin include polyolefin resin, acrylic resin, ABS resin, vinyl chloride resin, unsaturated polyester resin, melamine resin, epoxy resin, phenol resin, polyurethane resin, polyamide resin, and norbornene resin. Especially, since the outstanding designability can be provided, an acrylic resin is especially preferable.

  The shape of the composite member is not particularly limited, and may be any of a sheet, a plate, a bar, a woven or non-woven fabric, various three-dimensional shapes, and the like.

  When the composite member and the norbornene-based resin are brought into close contact with each other through the adhesive layer, the adhesive layer may be formed on at least a part of the surface of the composite member that comes into contact with the reaction solution. The material used for forming the adhesive layer is not particularly limited as long as it does not inhibit the bulk polymerization reaction, and varies depending on the composite member to be used, but contains a block copolymer of styrene and conjugated diene or a hydride thereof. It is preferable. Specific examples of such block copolymers include styrene-butadiene block copolymer (SB), styrene-isoprene block copolymer (SI), styrene-butadiene-styrene block copolymer (SBS), styrene- Examples include isoprene-styrene block copolymer (SIS) and styrene-butadiene-isoprene-styrene block copolymer (SBIS). It is preferable that the composite member and the norbornene-based resin are in close contact with each other through the adhesive layer because the adhesiveness between the two is high.

Norbornene-based resin molded body As described above, a norbornene-based resin molded body can be obtained. The norbornene-based resin molded body thus obtained contains a filler in an amount of preferably 5 to 60% by weight, more preferably 10 to 50% by weight, and the unevenness of the filler in the molded body. There is no (unevenness of the filler), there are few defects in appearance, a decrease in the density of the molded body and variations, and the effect of adding the filler (rigidity and dimensional stability, etc.) is sufficiently improved.

  Further, as the filler, preferably a fibrous filler and a particulate filler are used, and the ratio thereof is preferably fibrous filler: particulate filler = 95: 5 to 55:45, more preferably 80. : By setting it to 20-60: 40, the rigidity and dimensional stability of a molded object are uniform, and anisotropy can be made small. Furthermore, the addition effect of these fibrous and particulate fillers can be further enhanced by using a fibrous filler as a filler and a particulate filler as a hybrid filler.

  When the norbornene-based resin molded body is a composite molded body, the content of the filler represents the ratio of the filler in the norbornene-based resin portion excluding the composite member.

  As mentioned above, although embodiment of this invention has been described, this invention is not limited to the embodiment mentioned above at all, and can be variously modified within the range which does not deviate from the summary of this invention.

  For example, in the above-described embodiment, the case where the A solution, the B solution, and the F solution containing each of the above-described predetermined components are used as the reaction stock solution. However, as the reaction stock solution, the above-described A solution and B solution are used. A reaction stock solution having a configuration different from that of the F solution may be used. Specifically, in the above-described example, the case where the catalytic active component (activator, activity regulator) is included in the liquid A is illustrated, but the catalytic active component is included in the liquid F together with the filler. Also good. Further, in this case, it is possible to use only the two liquids B and F as the reaction stock solution without using the liquid A.

  In the above example, the case where the catalytically active component is used is exemplified. However, when a metathesis catalyst having a polymerization reaction activity is used alone without the catalytically active component, for example, a reaction stock solution containing a norbornene-based monomer is used. And a reaction stock solution containing a metathesis catalyst and a reaction stock solution containing a norbornene-based monomer and a filler may be employed.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “part” and “%” are based on weight unless otherwise specified.

Example 1
Manufacture of hybrid filler (filler): Wollastonite as a fibrous filler in a 500 L Henschel mixer (SH-400 50% volume cumulative diameter: 20 μm, aspect ratio: 18): 75 parts as particles Calcium carbonate (Escalon # 2000 50% volume cumulative diameter: 1.8 μm, aspect ratio: 1): 25 parts as a cylindrical filler, temperature in the tank 30 ° C., rotation speed 360 rpm (circumference) Stirring at a speed of 20 m / s). Next, 0.5 parts of a silane coupling agent (Shin-Etsu Chemical Co., Ltd. KBM-1003) is added to the mixer by spraying, and after spraying is completed, the rotational speed is 720 rpm (circumferential speed 40 m / s) for 7 minutes. Stir. Thereafter, the temperature in the tank was raised to 110 ° C., and the filler was dried by stirring at a rotational speed of 360 rpm (circumferential speed 20 m / s) for 10 minutes. Subsequently, 0.75 part of titanate coupling agent (Ajinomoto Fine Techno Co., Ltd. Preneact KR-TTS) was added to the mixer by spraying. After completion of spraying, the hybrid filler was obtained by stirring for 5 minutes at a rotational speed of 360 rpm (circumferential speed 20 m / s).

Preparation of reaction stock solution (F solution) To the mixed monomer consisting of 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene: 130 parts of the hybrid filler produced above was added, and using a homogenizer, the rotational speed was 13500 rpm, By carrying out shear dispersion for 10 minutes, a reaction stock solution (solution F) containing a norbornene monomer and a hybrid filler was prepared.

Preparation of reaction stock solutions (A solution and B solution) Separately from the above, reaction stock solutions (A solution and B solution) (both RENTTEC PENTAM # 4000) were prepared. The reaction stock solution (solution A) is a reaction stock solution containing an activator, an activity regulator and an elastomer in addition to the mixed monomer. The reaction stock solution (solution B) is a metathesis catalyst, elastomer in addition to the mixed monomer. And a reaction stock solution containing an antioxidant.

A pair of reaction injection moldings having a box-shaped space (cavity) of length 1650 mm x width 750 mm x height 200 mm x thickness 6 mm inside the norbornene-based resin molded body, and having a rib shape on the bottom and sides of the box A working mold was prepared, and one mold was heated to 85 degrees and the other mold was heated to 50 degrees. This reaction injection mold has a reaction liquid injection hole at the center of the side surface.

  Then, a reaction injection molding apparatus having the configuration shown in FIG. 1 is prepared, and the reaction stock solutions (A solution, B solution, F solution) prepared above are respectively stored in the tanks 10, 20, and 30, respectively. The reaction injection molding was prepared by connecting the reaction liquid injection hole of the mold prepared above and the piping 52 of the reaction injection molding apparatus shown in FIG. As the metering pumps 12 and 22 shown in FIG. 1, an axial plunger pump (manufactured by Tsubako) was used, and as the metering pump 32, a lance cylinder pump (manufactured by Tubako) was used.

Next, with the pin 50 closed, the metering pumps 12, 22, and 32 are operated, the reaction stock solution (A solution, B solution) is 900 g / s at the rate, and the reaction stock solution (F solution) is at the rate of 1200 g / s. Each of the reaction stock solutions (A solution, B solution, F solution) was collided and mixed in the mixing head 40 to obtain a reaction solution. Then, 3 seconds after the start of liquid feeding, the pin 50 was opened, and the obtained reaction liquid was poured into the mold. In addition, the liquid feeding pressure (that is, the pressure measured by the pressure gauges 16, 26, and 36 shown in FIG. 1) immediately before opening the pin 50 is P _A (liquid feeding pressure of liquid A): 5 0.0 MPa, P _B (liquid feeding pressure of liquid B): 5.0 MPa, P _F (liquid feeding pressure of liquid F): 5.0 MPa.

  Moreover, each reaction stock solution (A liquid, B liquid, F liquid) was sent so that it might become A liquid: B liquid: F liquid = 1.0: 1.0: 1.33 (weight ratio).

  Then, after finishing the feeding of each reaction stock solution (A solution, B solution, F solution), a curing reaction was performed under the condition of a curing time of 90 seconds, then the mold was opened, and the obtained norbornene-based resin molded body was obtained. I took it out. The resulting molded product was evaluated for unevenness of the filler content according to the following criteria.

Evaluation of unevenness of filling material and uneven coloration The resulting molded product was divided, and the cross section of the molded product was visually observed to confirm the presence or absence of unevenness in the content of the filler. The content unevenness of was evaluated. The results are shown in Table 1.
○: No inclusion unevenness of the filler was observed.
(Triangle | delta): The inclusion irregularity of the filler was observed in a part of the molded body.
×: Filler unevenness was observed over almost the entire compact.
XX: The part containing the filler and the part not containing are separated. Further, the color unevenness was judged by visually observing the surface of the molded body.

The average density of the molded body and the standard deviation of the density 18 samples of a size of 20 mmφ were sampled from where the molded body had uneven color and where there was no color unevenness. Then, using the obtained sample, the average density and the standard deviation of the density were determined according to JIS K7112.

Examples 2 and 3
1 except that the pressure adjusting valve of the metering pump 32 shown in FIG. 1 was adjusted so that the feed pressure of the reaction stock solution (F solution) immediately before opening the pin 50 was the pressure shown in Table 1. Then, a norbornene-based resin molded product was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Examples 1-3
The pressure adjusting valve of the metering pump 32 shown in FIG. 1 is adjusted and the timing at which the pin 50 is opened is adjusted so that the feed pressure of the reaction stock solution (F solution) immediately before opening the pin 50 becomes the pressure shown in Table 1. A norbornene-based resin molded article was produced in the same manner as in Example 1 except that the change was made 2 seconds after the start of liquid feeding, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 4
1 except that the pressure adjusting valve of the metering pump 32 shown in FIG. 1 was adjusted so that the feed pressure of the reaction stock solution (F solution) immediately before opening the pin 50 was the pressure shown in Table 1. Then, a norbornene-based resin molded product was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

表１中、反応原液（Ｆ液）の送液圧力比率（単位は、％）は、Ｐ_Ｆ／Ｐ_Ｓ×１００である（ただし、Ｐ_Ｆは、Ｆ液の送液圧力であり、Ｐ_Ｓは、Ａ液の送液圧力Ｐ_ＡとＢ液の送液圧力Ｐ_ＢとＦ液の送液圧力Ｐ_Ｆとの合計圧力）。

In Table 1, the liquid feed pressure ratio in the reaction stock solution (solution F) (unit is%) _is a _P F / P _S × 100 (however, _{P F} is the liquid feed pressure of F solution, _{P S} Is the total pressure of the liquid feeding pressure PA of liquid _A , the liquid feeding pressure P _B of liquid _B, and the liquid feeding pressure PF of liquid _F ).

From Table 1, the following can be confirmed.
That is, in Examples 1 to 3 in which the feed pressure ratio of the reaction stock solution (F solution) is within the predetermined range of the present invention, the occurrence of uneven inclusion of filler (unevenness of filler) in the molded body is prevented. In addition, since the charged filler was not unevenly distributed in the runner part and burrs, the average density of the molded body did not decrease and the density variation was small. And the molded object which did not have the defect (color unevenness) on an external appearance, and was fully improved in the addition effect (rigidity and dimensional stability) of a filler was able to be obtained. In addition, the liquid feeding pressure ratio of the reaction stock solution (F liquid) was substantially the same from the liquid feeding start to the liquid feeding end.
On the other hand, when the liquid feed pressure ratio of the reaction stock solution (F solution) was too low or too high, the inclusion of the filler in the molded product was generated, the average density was lowered, and the density variation was large. In addition, uneven color was observed on the surface of the molded body (Comparative Examples 1 to 4).

FIG. 1 is a schematic view of a main part of a reaction injection molding apparatus according to an embodiment of the present invention.

Explanation of symbols

10, 20, 30 ... Tank 12, 22, 32 ... Metering pump 14, 24, 34, 52 ... Piping 16, 26, 36 ... Pressure gauge 40 ... Mixing head 50 ... Pin

Claims (3)

Two or more reaction stock solutions are separately fed into a mixing head, and two or more reaction stock solutions are mixed in the mixing head to obtain a reaction solution containing a norbornene-based monomer, a metathesis catalyst, and a filler;
A step of injecting the reaction liquid into a mold and performing bulk polymerization in the mold, and a method for producing a norbornene-based resin molded body,
The reaction stock solution consists of a reaction stock solution (F solution) containing at least a filler, and one or more other reaction stock solutions,
Regarding the liquid supply pressure for sending each reaction stock solution into the mixing head,
The feeding pressure of the reaction stock solution (F solution) containing the filler is P _F [MPa],
When the total of the liquid feeding pressures of all the reaction stock solutions constituting the reaction solution is P _S [MPa],
Wherein the total liquid feed pressure P _S 100% of the all reaction stock, of the norbornene-based resin molded article, characterized in that a liquid feed pressure P _F and 20-40% of the range of the reaction stock solution (F solution) Production method.   The method for producing a norbornene-based resin molded article according to claim 1, wherein the filler contains a fibrous filler having an aspect ratio of 5 to 100 and a particulate filler having an aspect ratio of 1 to 2.   The method for producing a norbornene-based resin molded body according to claim 2, wherein the filler is a hybrid filler obtained by high-speed stirring the fibrous filler and the particulate filler at high speed.

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