JP2007009055A - Norbornene resin molded item and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin molded item exhibiting excellent dimensional stability, a manufacturing method of the resin molded item that causes no nozzle clogging in a molding apparatus on molding, and a reaction stock solution that exhibits excellent preservation stability and is suitably employable for the manufacturing method. <P>SOLUTION: The norbornene resin molded item is obtained by bulk polymerization of norbornene monomers in a mold and contains aluminum hydroxide having an aspect ratio of 5-100. Preferably, the average major axis diameter of aluminum hydroxide is 5-500 μm. Especially preferably, the molded item comprises 100 pts.wt. of norbornene monomers and, incorporated therewith, 5-400 pts.wt. of aluminum hydroxide. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a norbornene-based resin molded article containing a specific shape of aluminum hydroxide and a method for producing the same. Moreover, this invention relates to the reaction undiluted solution used suitably for this manufacturing method.

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

  In order to improve the impact resistance of the resin molded body obtained by the RIM method, it is known to mold by adding various fillers to the reaction solution. For example, Patent Document 1 discloses that a resin molded article having excellent impact resistance can be obtained using aluminum hydroxide as a filler.

  However, these conventional methods have the disadvantage that the dimensional stability at the time of molding by the RIM method is poor and it is difficult to obtain a resin molded body having a desired size. In addition, there is a case where molding becomes difficult due to clogging of the nozzle opening of the molding apparatus during molding.

2002-327106

  The object of the present invention is (a) a resin molded article excellent in dimensional stability, (b) a method for producing the resin molded article in which nozzle clogging of a molding apparatus does not occur during molding, and (c) storage stability. An object of the present invention is to provide a reaction stock solution that is excellently used in the above production method.

As a result of intensive studies to solve the above problems, the present inventors have
(I) The cause of the deterioration of the dimensional stability is the aspect ratio of aluminum hydroxide used as a filler,
(II) By controlling the aspect ratio of aluminum hydroxide, not only the dimensional stability is improved, but also the storage stability of the reaction stock solution is improved, and (III) the nozzle port of the molding device is clogged during molding. The inventors have found that the phenomenon that molding becomes difficult can be prevented, and have completed the present invention.

That is, the present invention
(1) A norbornene-based resin molded product obtained by bulk polymerization of norbornene-based monomers in a mold, which contains aluminum hydroxide having an aspect ratio of 5 to 100. body,
(2) The norbornene-based resin molded article as described above, wherein the average major axis diameter of aluminum hydroxide is 5 to 500 μm,
(3) The norbornene-based resin molded article as described above, which contains 5 to 400 parts by weight of aluminum hydroxide with respect to 100 parts by weight of the norbornene-based monomer,
(4) The norbornene-based resin molded article as described above, wherein the aluminum hydroxide is boehmite,
(5) The above, wherein a reaction liquid containing a norbornene-based monomer, a metathesis catalyst, and aluminum hydroxide having an aspect ratio of 5 to 100 is poured into a mold, and bulk polymerization is performed in the mold. A reaction stock solution (α) used in the production method described above, comprising the norbornene-based resin molded product according to the description, and (6) the norbornene-based monomer and aluminum hydroxide having an aspect ratio of 5 to 100,
Is to provide.

  Since the norbornene-based resin molded product of the present invention is excellent in dimensional stability (since the linear expansion coefficient of the resin molded product is small, it means that a resin molded product having a desired size can be obtained). It can be suitably used for a wide variety of applications such as equipment, general building parts, electrical parts, and automobile parts. Further, the reaction stock solution of the present invention does not cause a phenomenon that molding becomes difficult due to clogging of the nozzle opening of the molding apparatus when used for reaction injection molding. Furthermore, the reaction stock solution can produce a molded article having excellent storage stability, uniform and excellent dimensional stability.

The norbornene-based resin molded body of the present invention (hereinafter sometimes simply referred to as “molded body”) is a norbornene-based resin molded body obtained by bulk polymerization of a norbornene-based monomer in a mold, and has an aspect ratio of 5 to 5. 100 aluminum hydroxide (hereinafter abbreviated as “acicular aluminum hydroxide”) is contained.
The molded article of the present invention can be produced by the production method of the present invention. The production method of the present invention is characterized in that a reaction liquid containing a norbornene-based monomer, a metathesis catalyst, and acicular aluminum hydroxide is injected into a mold and bulk polymerization is performed in the mold.

  The reaction solution is usually obtained by mixing a reaction stock solution prepared by dividing a norbornene monomer, a metathesis catalyst, acicular aluminum hydroxide, and an optional component into two or more solutions. The reaction stock solution is not bulk polymerized by only one liquid, but when all the liquids are mixed, it becomes a reaction liquid containing each component in a predetermined ratio, and the norbornene monomer is bulk polymerized. Examples of the optional component include an activator, an activity regulator, an elastomer, and an antioxidant.

  The norbornene-based monomer used in the present invention is a compound having a norbornene ring structure, and any compound may be used as long as it is such a compound. Among them, it is preferable to use a tricyclic or higher polycyclic norbornene-based monomer because a molded product having excellent heat resistance can be obtained. The norbornene-based monomer may have a polar group.

  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; Examples thereof include pentacycles such as pentadiene trimer; heptacycles such as cyclopentadiene tetramer; and substituted products thereof. Examples of the substituent of the above-mentioned substituent include alkyl groups such as methyl, ethyl, propyl and butyl; alkenyl groups such as vinyl; alkylidene groups such as ethylidene; aryl groups such as phenyl, tolyl and naphthyl; ester groups; ether groups; Group; and a halogen atom; and the like. These monomers may be used in combination of two or more. Tricyclic, tetracyclic and pentacyclic monomers are preferred because they are readily available, have excellent reactivity, and are excellent in heat resistance of the resulting molded article.

  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. Those containing at least a crosslinkable monomer are preferably used. The proportion of the crosslinkable monomer in all norbornene monomers is preferably 2 to 30% by weight.

  In addition, monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, and cyclododecene that can undergo ring-opening copolymerization 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 acicular aluminum hydroxide used in the present invention has an aspect ratio of 5 to 100, more preferably 10 to 70, still more preferably 20 to 60, and particularly preferably 30 to 50. When the aspect ratio is smaller than the above range, the dimensional stability is deteriorated. If the aspect ratio is larger than the above range, the injection nozzle of the molding apparatus may be clogged (hereinafter abbreviated as “nozzle clogging”) when injecting into the mold, and the liquid norbornene monomer and acicular aluminum hydroxide May be separated (meaning that “storage stability” is poor). Molding may become difficult or a uniform molded product may not be obtained.
The aspect ratio of aluminum hydroxide is a value obtained by dividing the average major axis diameter of aluminum hydroxide by the 50% volume cumulative diameter. Here, the average major axis diameter is a number average length calculated as an arithmetic average value obtained by measuring the diameters of circumscribed circles of 100 aluminum hydroxides selected at random in 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 average major axis diameter of acicular aluminum hydroxide is preferably 5 to 500 μm, more preferably 100 to 400 μm, and particularly preferably 100 to 300 μm. By making it in the above range, the effect of the present invention becomes more remarkable.

  As the acicular aluminum hydroxide, boehmite is preferable. Boehmite is a kind of orthorhombic pyrite mineral and is represented by the composition formula γ-AlOOH. By using boehmite as acicular aluminum hydroxide, the effect of the present invention becomes even more remarkable.

  The norbornene-based resin molded article of the present invention is manufactured using preferably 5 to 400 parts by weight, more preferably 10 to 100 parts by weight of acicular aluminum hydroxide with respect to 100 parts by weight of the norbornene-based monomer. It is preferable.

  The surface of acicular aluminum hydroxide is preferably subjected to a hydrophobic treatment. By using needle-shaped aluminum hydroxide that has been hydrophobized, it is possible to uniformly disperse needle-shaped aluminum hydroxide in the resulting molded body, and molding with uniform strength and dimensional stability and low anisotropy. You can do it with your body. Examples of the treating agent used in the hydrophobizing treatment include silane coupling agents, titanate coupling agents, aluminum coupling agents, fatty acids, fats and oils, surfactants, waxes, and other polymers.

  The method of hydrophobizing treatment is not particularly limited, and untreated acicular aluminum hydroxide and the hydrophobizing agent are contained in separate reaction stock solutions, and when two or more reaction stock solutions are mixed, the reaction solution preparation and needle-like properties are performed. Although the hydrophobization treatment of aluminum hydroxide can be performed simultaneously, it is preferable to prepare the reaction stock solution using the hydrophobized acicular aluminum hydroxide. By using needle-shaped aluminum hydroxide that has been hydrophobized, aggregation of the needle-shaped aluminum hydroxide can be prevented, so that dispersibility in the reaction stock solution can be improved and sedimentation of the needle-shaped aluminum hydroxide can be suppressed.

  The amount of acicular aluminum hydroxide in the reaction solution is preferably 5 to 60% by weight, more preferably 11 to 50% by weight. If the amount of acicular aluminum hydroxide is too large, it may settle in the tank or piping or clog the injection nozzle when the reaction solution is injected into the mold. On the other hand, if the amount is too small, the dimensional stability of the resulting molded product may deteriorate.

The metathesis catalyst used in the production method of the present invention is not particularly limited as long as it can ring-open polymerization a norbornene monomer by a reaction injection molding method (RIM method), and may be a known one. Examples thereof include halides, oxyhalides, oxides, organic ammonium salts, oxyacid salts, and heteropolyacid salts of Group 5 or Group 6 transition metals. As the compounds of Group 5 or Group 6 transition metals, halides, oxyhalides and organic ammonium salts are preferable, and organic ammonium salts are more preferable. Further, as the transition metal, molybdenum, tungsten and tantalum are preferable, and molybdenum and tungsten are more preferable. Preferred specific examples of metathesis catalysts include tridodecyl ammonium molybdate and tungstate, methyl tricapryl ammonium molybdate and tungstate, tri (tridecyl) ammonium molybdate and tungstate, and trioctyl ammonium molybdenum. And acid salts and tungstates.
The amount of these metathesis catalysts used is usually 0.01 to 50 mmol, preferably 0.1 to 20 mmol, with respect to 1 mol of norbornene monomer in the reaction solution.

As the metathesis catalyst, it is particularly preferable to use a metal carbene complex having a metal atom of Group 8 of the periodic table as a central metal because the effects of the present invention are more remarkably exhibited. A metal carbene complex has a structure (M = C <) in which a carbene compound is bonded to a central metal atom and a metal atom (M) and a carbene carbon are directly bonded. 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 bis (tricyclohexylphosphine) -3-methyl-2-butenylidene ruthenium (IV) dichloride, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tri Cyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-4,5-dibromoimidazoline-2-ylidene) ( Tricyclohexylphosphine) ruthenium dichloride, bis (tricyclohexylphosphine) benzylideneruthenium dichloride, and the like.
When these metal carbene complexes are used as a metathesis catalyst, the amount used is usually 0.001 to 1 mmol, preferably 0.002 to 0.3 mmol, with respect to 1 mol of the monomer in the reaction solution. If the amount of metathesis catalyst used is too small, the polymerization activity is too low and the reaction takes a long time, resulting in poor production efficiency. If the amount used is too large, the reaction is too intense and bulk polymerization is performed before filling the mold sufficiently. Or the catalyst is likely to precipitate and it is difficult to store it homogeneously.

The metathesis catalyst may be used by dissolving or dispersing in a small amount of an inert solvent. Examples of the inert solvent in this case include liquid paraffin; chain aliphatic hydrocarbon solvents such as pentane, hexane and heptane; fats such as cyclopentane, cyclohexane, methylcyclohexane, decahydronaphthalene, tricyclodecane and cyclooctane. Cyclic hydrocarbon solvents; aromatic hydrocarbon solvents such as benzene, toluene and xylene; ether solvents such as diethyl ether and tetrahydrofuran can be used. 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, liquid paraffin, aromatic hydrocarbon solvent, aliphatic hydrocarbon solvent and alicyclic hydrocarbon solvent are preferable.

  Examples of the activator include alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride; alkoxyalkylaluminum halides in which part of the alkyl groups of these alkylaluminum halides are substituted with alkoxy groups; organotin compounds; Although the usage-amount of an activator is not specifically limited, Usually, it is 0.1-100 mol with respect to 1 mol of metathesis catalysts used with the whole reaction liquid, Preferably it is 1-10 mol.

  The activity regulator can change the reaction rate, the time from the 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 compound of Group 5 or Group 6 of the periodic table as the metathesis catalyst, examples of the activity regulator include compounds having an action of reducing the metathesis catalyst. Alcohols, haloalcohols, esters , Ethers, and nitriles 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, and t-butyl alcohol. Specific examples of haloalcohols include 1 , 3-dichloro-2-propanol, 2-chloroethanol, 1-chlorobutanol and the like.

  A Lewis base compound is mentioned as an activity regulator in the case of using a metal carbene complex as a metathesis catalyst. Examples of Lewis base compounds include Lewis base compounds containing phosphorus atoms such as tricyclopentylphosphine, tricyclohexylhexylphosphine, triphenylphosphine, triphenylphosphite, and n-butylphosphine; n-butylamine, pyridine, 4-vinylpyridine, Lewis base compounds containing nitrogen atoms such as acetonitrile, ethylenediamine, N-benzylidenemethylamine, pyrazine, piperidine, and imidazole. 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.

The reaction solution may contain optional components such as an elastomer and an antioxidant.
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), and hydrides thereof. The viscosity of the reaction solution can be adjusted by dissolving the elastomer in the reaction solution. Moreover, the impact resistance of the norbornene-based resin molded body and composite molded body obtained can be improved by adding an elastomer. The usage-amount of an elastomer is 0.5-20 weight part normally with respect to 100 weight part of norbornene-type monomers in a reaction liquid, Preferably it is 2-10 weight part.

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

  Each of the above components is divided into two or more solutions to prepare a reaction stock solution. Examples of the combination of two or more reaction stock solutions include the following two types (a) and (b) depending on the type of metathesis catalyst used.

(A): As the metathesis catalyst, one that does not have polymerization reaction activity by itself, but that exhibits polymerization reaction activity by using an activator in combination can be used. In this case, a reaction stock solution containing the norbornene monomer and the activator (A1 solution) and a reaction stock solution containing the norbornene monomer and the metathesis catalyst (B1 solution) are mixed to obtain the above reaction solution. be able to. Further, a reaction stock solution (C1 solution) containing a norbornene-based monomer and containing neither a metathesis catalyst nor an activator may be used in combination.

(B): When using a metathesis catalyst having a polymerization reaction activity alone, a reaction stock solution containing a norbornene monomer (A2 solution) and a reaction stock solution containing a metathesis catalyst (B2 solution) are mixed. Thus, the reaction solution can be obtained. At this time, as the reaction stock solution (B2 solution), a solution obtained by dissolving or dispersing a metathesis catalyst in a small amount of an inert solvent is usually used.

  In any case, acicular aluminum hydroxide and the above-mentioned optional components may be contained in any reaction stock solution. Especially, it is preferable that acicular aluminum hydroxide is contained in the reaction stock solution containing a norbornene-type monomer. Specifically, in the case of the above (a), there is an embodiment in which acicular aluminum hydroxide is contained in one reaction stock solution selected from A1 solution, B1 solution, and C1 solution. Moreover, in the case of said (b), the aspect in which acicular aluminum hydroxide is contained in A2 liquid or B2 liquid is mentioned.

  The reaction stock solution (α) of the present invention contains a norbornene-based monomer and acicular aluminum hydroxide and is used in the production method of the present invention.

  The reaction stock solution (α) of the present invention is excellent in storage stability without causing precipitation by using acicular aluminum hydroxide. The amount of acicular aluminum hydroxide in the reaction stock solution (α) is preferably 9 to 80% by weight, more preferably 15 to 65% by weight. If the amount of acicular aluminum hydroxide is too large, it may settle in the tank or piping during storage. Moreover, when there is too little, the quantity of acicular aluminum hydroxide in the molded object obtained will decrease, and the improvement effect of dimensional stability may deteriorate.

In the production method of the present invention, a collision mixing apparatus conventionally known as a reaction injection (RIM) molding apparatus can be used for mixing the reaction stock solution. Two or more reaction stock solutions are instantaneously mixed with a mixing head of a RIM machine, the obtained reaction solution is poured into a mold, and bulk polymerization is performed in the mold to obtain the norbornene resin molded body of the present invention.
In addition to the collision mixing device, a low-pressure injector such as a dynamic mixer or a static mixer can also be used.

  The mold used for the reaction injection molding does not necessarily need to be a high-rigid and expensive mold, and is not limited to a metal mold, and a resin mold or a simple mold can be used. This is because reaction injection molding can be performed at a relatively low temperature and low pressure using a low-viscosity reaction stock solution. 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, and still more preferably 50 to 100 ° C. The mold clamping pressure is usually in the range of 0.01 to 10 MPa. The bulk polymerization time may be appropriately selected, but is usually 20 seconds to 40 minutes, preferably 20 seconds to 7 minutes after the injection of the reaction stock solution.

  In the production method of the present invention, when the composite member is installed in the mold, a norbornene resin composite molded body in which the composite member and the norbornene resin are integrally formed can be obtained. Here, “integrally formed” means that the norbornene-based resin and the composite member are in close contact so that they are not easily peeled off, and may be in close contact by fusion of the resin. It may be in close contact via an adhesive layer.

The composite member is a material that can be placed 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. Among these, acrylic resin is particularly 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.

  As described above, the molded article of the present invention is obtained. The amount of acicular aluminum hydroxide in the molded article of the present invention is preferably 5 to 70% by weight, more preferably 9 to 60% by weight, and particularly preferably 12 to 50% by weight. However, when the molded body of the present invention is a composite molded body, the above represents the amount of acicular aluminum hydroxide in the norbornene-based resin portion excluding the composite member. When there is too much quantity of acicular aluminum hydroxide, the intensity | strength and impact resistance of a molded object may fall. On the other hand, if the amount is too small, the dimensional stability of the molded body may deteriorate.

  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. Moreover, each characteristic was measured by the method shown below.

(1) 50% volume cumulative diameter of aluminum hydroxide The 50% volume cumulative diameter of aluminum hydroxide was determined by measuring the particle size distribution by X-ray transmission method using a cedy graph (manufactured by Micromeritics).
(2) Aspect ratio of aluminum hydroxide The aspect ratio of aluminum hydroxide is the number calculated as the arithmetic average value of the diameters of 100 circumscribed circles of 100 aluminum hydroxides selected at random in an optical micrograph. The average length (average major axis diameter) was divided by the 50% volume cumulative diameter.
(3) Flexural modulus The flexural modulus of the norbornene-based resin molded product was measured according to JIS K 7171.
(4) Bending strength The bending strength of the norbornene-based resin molding was measured according to JIS K 7171.
(5) Tensile strength The tensile strength of the norbornene-based resin molding was measured in accordance with JIS K 7161.
(6) Linear expansion coefficient (It is an index of the dimensional stability of the molded body. The smaller the linear expansion coefficient, the better the dimensional stability.)
The linear expansion coefficient of the norbornene resin molded product was measured according to JIS K 7197. However, a test piece having a length of 10 mm, a width of 5 mm, and a thickness of 4 mm was used.

Example 1
As aluminum hydroxide, boehmite (product number: Cerasur BMI, manufactured by Kawai Lime Industry Co., Ltd.) having an average major axis diameter of 200 μm and an aspect ratio of 40 was prepared (referred to as “aluminum hydroxide a”).
11 parts of aluminum hydroxide a is added to a mixed monomer composed of 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene, and further a dispersant (titanate coupling agent, manufactured by Ajinomoto Fine Techno Co., product number: Preneact KR TTS). After adding 0.1 part of the mixture, the mixture was stirred and mixed to obtain a reaction stock solution (α) (corresponding to the A2 solution).
On the other hand, bis (tricyclohexylphosphine) -3-methyl-2-butenylidene ruthenium (IV) dichloride is dispersed in liquid paraffin at a concentration of 7% by weight as a reaction stock solution containing a metathesis catalyst (corresponding to the B2 solution). A catalyst dispersion was prepared (referred to as “catalyst dispersion b”).
Next, two stainless plates with a length of 200 mm and a width of 300 mm were prepared, and one of them was heated by attaching a heater wire to the entire surface. A silicon packing having a thickness of 4 mm and a width of 20 mm was installed on the periphery of two stainless steel plates, an injection port was provided, and the stainless steel plate was overlaid so that the heater portion was on the outside to form a mold.
The inner surface of the stainless steel was heated to 90 ° C., and 1 part of the catalyst dispersion b was mixed with 111.1 parts of the above reaction stock solution (α) to obtain a reaction liquid, which was poured from the inlet. After the injection, it was cured for 30 minutes and taken out from the mold. Subsequently, it was post-cured at 110 ° C. for 120 minutes to obtain a molded product.
In addition, nozzle clogging did not occur during the experiment, and the storage stability was good.
The results are shown in Table 1.

(Example 2)
The amount of aluminum hydroxide added was changed to 25 parts, the amount of dispersant added was changed to 0.2 parts, and 1 part of catalyst dispersion b was mixed with 125.2 parts of reaction stock solution (α) for reaction. A molded product was obtained in the same manner as in Example 1 except that the liquid was used.
In addition, nozzle clogging did not occur during the experiment, and the storage stability was good.
The results are shown in Table 1.

(Example 3)
The amount of aluminum hydroxide added was changed to 67 parts, the amount of dispersant added was changed to 0.6 parts, and 1 part of catalyst dispersion b was mixed with 167.6 parts of reaction stock solution (α) to react. A molded product was obtained in the same manner as in Example 1 except that the liquid was used.
In addition, nozzle clogging did not occur during the experiment, and the storage stability was good.
The results are shown in Table 1.

Example 4
To a mixed monomer consisting of 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene, 3 parts of a styrene-isoprene-styrene block copolymer (manufactured by Nippon Zeon Co., Ltd., product number: QUINTAC 3421) and 1.1 of diethylaluminum chloride. 4 parts, 1.5 parts of 1,3-dichloro-2-propanol and 0.1 part of silicon tetrachloride were added and mixed and dispersed uniformly to obtain a reaction stock solution containing an activator (corresponding to the above A1 solution) ).
On the other hand, 3 parts of styrene-isoprene-styrene block copolymer (manufactured by Nippon Zeon Co., Ltd., product number: QUINTAC 3421) in a mixed monomer consisting of 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene, phenolic antioxidant 3 parts of an agent (manufactured by Ciba Specialty Chemicals Co., Ltd., product number: Irganox 1010) and 4.5 parts of tri (tridecyl) ammonium molybdate were added and mixed and dispersed uniformly. Next, 30 parts of aluminum hydroxide a was added to 100 parts of the dispersion and mixed and dispersed uniformly to obtain a reaction stock solution (α) (corresponding to the B1 liquid).
Next, two stainless plates with a length of 200 mm and a width of 300 mm were prepared, and one of them was heated by attaching a heater wire to the entire surface. A silicon packing having a thickness of 4 mm and a width of 20 mm was installed on the periphery of two stainless steel plates, an injection port was provided, and the stainless steel plate was overlaid so that the heater portion was on the outside to form a mold.
The inner surface of the stainless steel was heated to 90 ° C., and 100 parts of the reaction stock solution containing the activator was mixed with 100 parts of the reaction stock solution (α) described above to prepare a reaction solution, which was poured from the inlet. After the injection, it was cured for 5 minutes and taken out from the mold to obtain a molded product.
In addition, nozzle clogging did not occur during the experiment, and the storage stability was good.
The results are shown in Table 1.

(Comparative Example 1)
As aluminum hydroxide, a granular material, that is, an average major axis diameter of 3 μm and an aspect ratio of 2 (manufactured by Kawai Lime Industry Co., Ltd., product number: Cerasur BMB) was prepared (“aluminum hydroxide b”) To express.).
A molded product was obtained in the same manner as in Example 1 except that aluminum hydroxide b was used instead of aluminum hydroxide a. In addition, nozzle clogging did not occur during the experiment, and the storage stability was good. The results are shown in Table 1.

(Comparative Example 2)
A molded product was obtained in the same manner as in Example 1 except that aluminum hydroxide was not used and 1 part of the catalyst dispersion b was mixed with 100 parts of the reaction stock solution (α) to obtain a reaction solution. The results are shown in Table 1. In addition, nozzle clogging did not occur during the experiment, and the storage stability was good.
The results are shown in Table 1.

  From Table 1, in Examples 1 to 4 using acicular aluminum hydroxide (aluminum hydroxide a), Comparative Example 1 using granular aluminum hydroxide (aluminum hydroxide b) and aluminum hydroxide were not used. Compared with Comparative Example 2, the dimensional stability was greatly improved because the linear expansion coefficient was small.

Claims (6)

  A norbornene-based resin molded article obtained by bulk polymerization of a norbornene-based monomer in a mold, comprising an aluminum hydroxide having an aspect ratio of 5 to 100.   The norbornene-based resin molded article according to claim 1, wherein an average major axis diameter of the aluminum hydroxide is 5 to 500 µm.   3. The norbornene-based resin molded product according to claim 1, wherein 5 to 400 parts by weight of the aluminum hydroxide is contained with respect to 100 parts by weight of the norbornene-based monomer.   The norbornene-based resin molded product according to any one of claims 1 to 3, wherein the aluminum hydroxide is boehmite.   5. A reaction liquid containing a norbornene-based monomer, a metathesis catalyst, and aluminum hydroxide having an aspect ratio of 5 to 100 is injected into a mold, and bulk polymerization is performed in the mold. The manufacturing method of the norbornene-type resin molding in any one of these.   A reaction stock solution (α) used in the production method according to claim 5, comprising a norbornene-based monomer and aluminum hydroxide having an aspect ratio of 5 to 100.