JPH0724864A - Production of crosslinked polymer molded product - Google Patents

Abstract

PURPOSE:To suppress the generation of air bubbles in a mold without exerting adverse effect on the physical properties of a molded product, in performing the crosslinking polymerization of metathesis polymerlzable cyclic olefin by a reactive injection molding method, by injecting a half amt. or less of a monomer mixed soln. set to specific viscosity into a mold and injecting the residual monomer mixed soln. into the mold in a state reduced in viscosity. CONSTITUTION:Both monomer solns. prepared by separately adding the catalyst component and activator component of a metathesis polymerization catalyst system to metathesis polymerizable cyclic olefin are mixed to be injected into a mold. At this time, a polymeric substance is added to the monomer mixed soln. to adjust the viscosity of the monomer mixed soln. to 300-1800cps and the volume to be injected into the mold is set to 100V and 1-50V of the monomer mixed soln. is injected in the mold. Subsequently, the polymeric substance is added in a reduced amt. or not added to reduce the viscosity of the residual monomer mixed soln. by 200cps or more to adjust the same to 10-500cps and this residual monomer mixed soln. is injected in the mold. The obtained molded product has surface smoothness and the lowering of the heat resistance thereof is not almost observed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a crosslinked polymer molded article of cyclic olefin. More specifically, the present invention relates to a method for producing a crosslinked polymer molded article having excellent physical properties with less inclusion of bubbles.

[0002]

2. Description of the Related Art Conventionally, a monomer liquid comprising a metathesis polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst system (also referred to as a metathesis catalyst system) and a monomer liquid comprising a metathesis polymerizable cyclic olefin containing an activator component. There is known a method for producing a crosslinked polymer molded article by mixing and pouring into a mold and polymerizing and crosslinking in the mold (see, for example, Japanese Patent Publication No. 28451/1990).

In this reaction injection molding method, raw material monomers that are easily available can be used, the viscosity of the monomer is low, the pressure of injection molding is low, the polymerization / crosslinking reaction is fast, the molding cycle is short, and a large molded article is used. The molded product has excellent advantages such as that it can be obtained relatively easily and that the molded product has a good balance of rigidity and impact resistance.

Since the reaction injection molding method has high reactivity, the polymerization / crosslinking reaction is extremely fast, and the reaction is usually completed within a few minutes after the injection of the raw material mixed solution is completed.
Often less than 1 minute. Since the reaction is fast, the two monomer liquids are mixed, and then the raw material mixed liquid is injected into the mold through a short pipe. This raw material mixed liquid is mainly composed of a cyclic olefin monomer, and its viscosity is extremely low as compared with the case of ordinary resin injection molding.

In the reaction injection molding method, it is easy to obtain a large-sized molded product due to the low viscosity of the raw material mixture to be injected, and there is no need for an expensive heat-resistant mold. It is a great advantage.

However, since the raw material mixture solution has a low viscosity, is injected into the mold at a high speed and the polymerization reaction is extremely fast, bubbles are apt to be generated in the mold due to gas entrainment, and the bubbles are formed. May be taken in. In particular, it has been found that the bubbles generated at the beginning of the injection of the raw material mixture or at the initial stage may remain as bubbles on the surface of the molded product.

[0007]

Therefore, the present inventor has conducted various studies on a method in which bubbles are not generated in a mold by rapid injection of a raw material mixed solution. In particular, research was conducted on a method of suppressing the generation of bubbles in the mold and not adversely affecting the characteristics of the molded product by injecting the raw material mixed liquid.

As a result, by adding a soluble polymer substance to the raw material mixture to increase the viscosity of the raw material mixture,
It has been found that the generation of bubbles in the mold can be suppressed, and in particular, the viscosity of the raw material mixture liquid at 30 ° C. is preferably 300 cps or more to suppress the generation of bubbles.
In the present specification, the unit of viscosity of the raw material mixture liquid is “cps”.
Means centipoise measured at 30 ° C. unless otherwise specified.

Further, if the viscosity is too high, the energy required for preparing the raw material mixed solution becomes large, and the mixing may be insufficient, so that a large amount of energy is required for the supply. Therefore, from this point, it is desirable that it is 1800 cps or less.

In order to adjust the viscosity to 300 to 1800 cps by mixing and dissolving a high molecular substance in the raw material mixed liquid, usually a large amount of 3 to 25% by weight of the high molecular substance must be added to the raw material mixed liquid. I have to. However, it has been found that a molded product obtained from such a raw material mixture liquid to which a large amount of a high molecular substance is added has a rather bad effect such as low heat resistance. In addition, if a large amount of polymer is added, the reaction may be hindered by various additives contained in the polymer, and the polymer is often expensive, leading to an increase in product cost. This also increases the energy required to inject the raw material mixed liquid.

Therefore, the inventor has determined that the viscosity of the raw material mixture liquid to be injected into the mold is 300 to 1800 c.p.
By injecting a raw material mixed solution having a low viscosity after that, no bubbles are observed on the surface of the obtained molded product, and reduction of heat resistance of the molded product is substantially allowed. It was found to be about. Moreover, it was found that even if a normal low-viscosity raw material mixture liquid is injected from the middle, bubbles are rarely generated, and even if they are generated, their presence is not a problem because they are confined inside the molded product.

[0012]

Means for Solving the Problems The present invention has been achieved on the basis of the above findings, and comprises a monomer liquid A (solution A) composed of a metathesis-polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst system. A monomer liquid B (solution B) containing a metathesis-polymerizable cyclic olefin containing an activator component of a metathesis polymerization catalyst system is mixed, and this mixed liquid is injected into a mold to carry out polymerization and crosslinking reaction in the mold. In the method for producing a crosslinked polymer molded article at least, when the volume of the mixed solution to be injected into the mold is 100 V, (1) an arbitrary amount of 1 V to 50 V after the injection is started. Mix the mixture [I] adjusted to a viscosity of 300-1800 cps into the mold until the mixture is injected, and (2) mix until the injection is completed until the injection is complete. The viscosity of the liquid More 200c.p.s low, and 10
A method for producing a crosslinked polymer molded article, which comprises injecting a mixed solution [II] adjusted to a viscosity of ˜500 cps into a mold.

As described above, according to the method of the present invention, a polymer material is added to increase the viscosity of a certain proportion of the total liquid mixture to be injected into the mold, and the injection is started from the start of injection. After that, the raw material mixture liquid which is adjusted to have a low viscosity, which does not contain the polymer substance or has a small content thereof, is injected. Thus, in the method of the present invention, the generation of bubbles in the mold at the beginning of the injection of the raw material mixture is suppressed,
A molded product with few bubbles can be obtained.

Moreover, in the obtained molded product, the compounding ratio of the polymer substance in the molded product as a whole was small, despite the fact that a relatively large amount of the polymer substance was added to the raw material mixture at the beginning of injection. Since it is kept low, problems with physical properties such as deterioration of heat resistance are sufficiently acceptable.

Conventionally, in the case of obtaining a crosslinked polymer molded product of a cyclic olefin using a metathesis polymerization catalyst system, a method of adding a polymer substance (polymer modifier) to a raw material mixture is known (Patent Document 1). 4-9812). The method described in this publication aims at increasing the impact strength of the molded product by 5 to 10 times by adding a polymer substance, particularly an elastomer, as compared with the case where it is not added.

According to another study by the present inventor, in order to improve the impact resistance of a cyclic olefin crosslinked polymer molded article,
Addition of polymer modifiers, especially elastomers, is typically a few percent
It is sufficient that the amount is about (weight), and the impact strength does not improve as the amount added increases even if it is added more. If it exceeds about 10% (weight), the heat resistance tends to decrease rather.

In the case where the polymer improving agent is added to improve the impact strength, the raw material mixed solution may not reach the viscosity of the raw material mixed solution [I] at the beginning of injection in the method of the present invention.
On the other hand, the viscosity (300-
1800 cps) is used for molding from the start to the completion of injection, the content of the polymer substance becomes high, the heat resistance of the molded product decreases, the cost is high, Inhibition of the effects of additives, high cost, and increase of injection pressure is unavoidable.

The method of the present invention will be described in more detail below. In the method of the present invention, as the metathesis-polymerizable cyclic olefin for forming the crosslinked polymer, those containing 1-2 metathesis-polymerizable cycloalkene groups in the molecule are used. Preferred is a compound having at least one norbornene skeleton in the molecule. Specific examples thereof include dicyclopentadiene, tricyclopentadiene, cyclopentadiene-methylcyclopentadiene co-dimer, 5-ethylidene norbornene, norbornene, norbornadiene, 5-cyclohexenyl norbornene, 1,4,5,8-dimethano -1,4,4a, 5,6,
7,8,8a-octahydronaphthalene, 1,4-methano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4,5,8-dimethano- 1,
4,4a, 5,6,7,8,8a-octahydronaphthalene,
6-ethylidene-1,4,5,8-dimethano-1,4,4a,
5,6,7,8,8a-heptahydronaphthalene, 1,4,
5,8-Dimethano-1,4,4a, 5,6,7,8,8a-hexahydronaphthalene, ethylene bis (5-norbornene) and the like can be mentioned, and a mixture thereof can also be used. Particularly, dicyclopentadiene or a mixture thereof containing 50 mol% or more, preferably 70 mol% or more is suitably used. Further, if necessary, a metathesis-polymerizable cyclic olefin having a polar group containing a different element such as oxygen and nitrogen can be used as a copolymerization monomer. Such a copolymerizable monomer also preferably has a norbornene structural unit, and the polar group is preferably an ester group, an ether group, a cyano group, an N-substituted imide group, a halogen group or the like. Specific examples of the copolymerizable monomer include 5-methoxycarbonylnorbornene and 5-methoxycarbonylnorbornene.
(2-Ethylhexyloxy) carbonyl-5-methylnorbornene, 5-phenyloxymethylnorbornene, 5
-Cyanonorbornene, 6-cyano-1,4,5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, N-butyl nadecimide, 5-chloronorbornene, etc. Can be mentioned.

The monomer liquid A (solution A) in the present invention contains a catalyst component of a metathesis polymerization catalyst system. As the catalyst component, salts such as halides of metals such as tungsten, rhenium, tantalum and molybdenum are used, and tungsten compounds are particularly preferable. As such a tungsten compound, tungsten hexahalide, tungsten oxyhalide, etc. are preferable, and more specifically, tungsten hexachloride, tungsten oxychloride, etc. are preferable. Further, organic ammonium tungstate or the like can also be used. It has been found that when such a tungsten compound is directly added to the monomer, it immediately starts cationic polymerization, which is not preferable. Therefore, such a tungsten compound is preferably suspended in an inert solvent such as benzene, toluene, chlorobenzene and the like in advance and solubilized by adding a small amount of an alcohol compound and / or a phenol compound to be used. Further, as described above, it is preferable to add about 1 to 5 mol of Lewis base or chelating agent to 1 mol of the tungsten compound in order to prevent undesired polymerization. Examples of such additives include acetylacetone, acetoacetic acid alkyl esters, tetrahydrofuran, and benzonitrile. When a polar monomer is used, it may be a Lewis base itself as described above, and it may have its action even if the above compound is not added. As described above, the monomer liquid A (solution A) containing the catalyst component has substantially sufficient stability.

On the other hand, the monomer solution B (solution B) in the present invention contains an activator component of the metathesis polymerization catalyst system. The activator component is preferably an organometallic compound centered on an alkylated compound of a metal of Group I to Group III of the periodic table, particularly tetraalkyltin, an alkylaluminum compound, and an alkylaluminum halide compound, and specifically, a chlorinated compound. Examples thereof include diethyl aluminum, diethyl aluminum chloride, trioctyl aluminum, dioctyl aluminum iodide, and tetrabutyl tin. A monomer liquid B (solution B) is formed by dissolving the organometallic compound as the activating component in the monomer.

Basically, a crosslinked polymer molded article can be obtained by mixing the solution A and the solution B and injecting them into a mold. However, with the above composition, the polymerization reaction is very fast. Since it is started, curing may occur while it does not sufficiently flow into the molding die, which often causes a problem. Therefore, it is preferable to use an activity regulator.
As such a regulator, Lewis bases are generally used, and above all, ethers, esters, nitriles and the like are used. Specific examples include ethyl benzoate, butyl ether, diglyme and the like.
Such a regulator is generally used by adding it to the solution (solution B) side of the component of the activator of the organometallic compound. When a monomer having a Lewis base is used as described above, it can also serve as a regulator.

The amount of the metathesis polymerization catalyst system used is, for example, when a tungsten compound is used as the catalyst component, the ratio of the tungsten compound to the raw material monomer is
It is about 1,000 to 1 to 1,5,000 to 1, preferably about 2,000 to 1 on a molar basis, and when an alkylaluminum is used as the activating component, an aluminum compound based on the above raw material monomer is used. The ratio used is about 100: 1 to 5,000: 1, preferably about 200: 1 to 500: 1 on a molar basis. Further, as described above, the masking agent and the adjusting agent can be appropriately adjusted and used depending on the amount of the catalyst system used by experiments.

In the method of the present invention, basically, a raw material mixed solution obtained by mixing the solution A and the solution B is poured into a mold to obtain a crosslinked polymer molded article. At that time, in the method of the present invention, when the total amount of the raw material mixture to be injected into the mold is 100 V by volume, the raw material mixed solution in an amount of 1 V to 50 V, preferably 5 V to 40 V is added with a polymer substance at 300 to 300 V. 1800 cp
s, preferably a solution adjusted to 500 to 1500 cps is used, and injection is performed from the start of injection. The raw material mixed liquid [I] having the increased viscosity is introduced into the mold from the start of injection. Then, after the injection of the raw material mixed liquid [I] is completed, the raw material mixed liquid [II] is subsequently injected. The raw material mixed liquid [II] has a viscosity lower than that of the mixed liquid [I] by 200 cps and has a viscosity of 10 to 500 cps, preferably 20 to 300 cps. The injection amount of the raw material mixed liquid [II] is 99V to 50V, preferably 95V to 60V, when the total injection amount is 100V in volume.

The raw material mixture immediately after mixing the solution A and the solution B is usually about 1 when no polymer substance is added.
It has a viscosity of 0 cps or less. A polymer substance is added to the raw material mixture liquid [I] used at the initial stage of infusion to adjust the viscosity.

The polymeric substance used is preferably one that is soluble in cyclic olefins and that does not interfere with the polymerization reaction or is difficult to do so. Particularly preferred is one having an effect on improving the physical properties of the molded product, particularly the impact strength. As such a polymer substance, an olefin-based elastomer or a diene-based elastomer is mentioned as a preferred example, and specifically, for example, styrene-butadiene-styrene block rubber, styrene-isoprene-styrene block rubber, polybutadiene, polyisoprene, butyl rubber, ethylene propylene. A wide range of elastomers such as diene terpolymers, nitrile rubbers. Other polymer substances include polystyrene, styrene acrylonitrile copolymer, methacrylic resin, petroleum resin, vinylidene chloride, polyethylene, polypropylene, and copolymers of ethylene and propylene.

In carrying out the method of the present invention, the polymer substance may be added in advance to one or both of the solution A and the solution B, but it is preferable to add the polymer substance separately from these solutions. A cyclic olefin solution (solution C) containing a substance in a high concentration is prepared. First, Solution A,
Solution B and solution C are mixed by collision at an appropriate ratio with a mixing head to adjust raw material mixture [I] to start injection, and supply of solution C to the mixing head is reduced or stopped at an appropriate time. Then, the raw material mixed liquid [II] may be adjusted and the injection may be continued until the end.

Further, the crosslinked polymer molded product according to the present invention may contain various additives in order to improve or maintain its properties in practical use. Such additives include fillers, pigments, oxidative spinning agents, light stabilizers and the like. Such an additive can be used as a viscosity modifier like the above-mentioned polymer substance.

The simplest method is the solution A described above.
And the solution B may be added in advance to either or both of them, but in that case, the reaction with the catalyst component or the activator component having a strong reactivity in the solution may not be practically supported. And should not hinder the polymerization. If the reaction is unavoidable but coexistence does not substantially inhibit polymerization,
It is also possible to add it to the solution C and mix and use it.

The filler is effective in improving the bending modulus. As such, glass fiber, mica,
Examples thereof include carbon black and wollastonite. Those obtained by surface-treating these with a silane coupler or the like can be preferably used.

Further, it is desirable to add a phenol type or amine type antioxidant to the solution in advance. Specific examples of these antioxidants include 2,6-di-t-butyl-p-cresol, N, N'-diphenyl-p-phenylenediamine and tetrakis [methylene (3,5-di-t-
Butyl-4-hydroxycinnamate)] methane and the like.

[0031]

EFFECTS OF THE INVENTION According to the present invention, it is possible to obtain a crosslinked polymer molded article which can suppress the generation of bubbles in a mold and has a smooth surface free from bubbles. In addition, the molded product shows almost no deterioration in heat resistance, and maintains excellent properties.

[0032]

EXAMPLES The method of the present invention will be specifically described with reference to the following examples. Example 1 (1) Preparation of Catalyst Component Solution (A-1) 20 parts by weight of tungsten hexachloride were added to 70 parts by weight of dry toluene under a nitrogen stream, and then nonylphenol 2 was added.
A 0.5M tungsten-containing catalyst solution was prepared by adding a solution consisting of 1 part by weight and 16 parts by weight of toluene, and the solution was purged with nitrogen gas overnight to produce tungsten hexachloride and nonylphenol. The hydrogen chloride gas was removed, and 1 part by volume of acetylacetone was added to 10 parts by volume of the solution to prepare a polymerization catalyst. To a monomer mixture consisting of 95 parts by weight of purified dicyclopentadiene and 5 parts by weight of purified ethylidene norbornene, 3.5 parts by weight of ethylene-propylene-ethylidene norbornene polymer rubber containing 70 mol% of ethylene, and 2 parts by weight of ethanox 702 as an oxidation stabilizer. The above catalyst solution for polymerization was added to the solution containing
A solution (A-1) containing a catalyst component was prepared so that the amount became mol / liter. The viscosity of this solution (A-1) is 3
It was 200 cps at 0 ° C.

(2) Preparation of catalyst component solution (A-2) In the above (1) except that 4.5 parts by weight of ethylene-propylene-ethylidene norbornene polymer rubber containing 70 mol% of ethylene is used. A catalyst component solution (A-2) was prepared in the same manner as in. This solution (A-2)
Had a viscosity of 500 cps at 30 ° C.

(3) Preparation of activator component solution (B-1) A mixture of trioctylaluminum 85, dioctylaluminum iodide 15 and diglyme 100 was prepared and mixed to prepare a polymerization activator mixture solution, which was purified into dicyclopentadiene. 95 parts by weight, 5 parts by weight of purified ethylidene norbornene, and 3.5 parts by weight of ethylene-propylene-ethylidene norbornene polymerized rubber containing 70 mol% of ethylene were mixed in an aluminum content of 0.03 mol / l. A solution (B-1) containing an activator component was prepared. The viscosity of the solution (B-1) is 30 ° C.
Was 200 cps.

(4) Preparation of Activator Component Solution (B-2) In the above (3), except for using 4.5 parts by weight of ethylene-propylene-ethylidene norbornene polymer rubber containing 70 mol% of ethylene, the above ( An activator component solution (B-2) was prepared in the same manner as 3). This solution (B-
The viscosity of 2) was 500 cps at 30 ° C.

(5) Preparation of Solution C A solution C comprising 95 parts by weight of purified dicyclopentadiene, 5 parts by weight of purified ethylidene norbornene and 6.5 parts by weight of ethylene-propylene-ethylidene norbornene polymer rubber containing 70 mol% of ethylene was prepared. did. The viscosity of solution C was 2500 cps at 30 ° C.

(6) Manufacture of Molded Article Using the equipment shown in FIG. 1, under a nitrogen atmosphere, Solution A-1, Solution B-1 and Solution C were placed in the storage tanks 1, 2 and 3, respectively, and the results are shown in Table 1. Injection was performed under the conditions shown in. In FIG. 1, 1 is a solution A-1 storage tank, 2 is a solution B-1 storage tank, and 3 is a solution C storage tank. The respective solutions are circulated between the mixing head 7 and the storage tanks 1, 2, 3 by the pipes 4, 4 ', 5, 5'and 6, 6', respectively.
When a signal for injection into the mold 8 is transmitted, the flow path in the mixing head 7 is changed, and the solution A, the solution B, and the solution C are changed.
Are injected into the space in the mixing head 7, and the mixture of the solutions is usually achieved by collision during the injection. At this time, the injection of the solution A-1, the solution B-1, and the solution C was started at the same time, and the injection of the solution C was completed earlier than the injection of the solution A-1 and the solution B-1.

Solution A-1 was injected at a rate of 350 g / second, solution B-1 was injected at a rate of 350 g / second, and solution C was injected at a rate shown in Table 1. In the table, "elastomer concentration" means 1 after starting injection when the total injection amount is 100V (volume).
The elastomer concentration (% by weight) of the mixed liquid corresponding to V to 50 V, and the viscosity is the viscosity (cps) of the mixed liquid. The mold 8 is an iron mold having a plate-like space of 550 mm x 550 mm x 4 mm, and injection components that exceed the amount filling the space overflow into a container (liquid pool) provided at the mold outlet. I decided to go out. The mold temperature was 90 ° C. on one side and 60 ° C. on the other side in advance. One minute after the completion of injection, the mold was opened to obtain a molded product. FIG. 2 is a cross-sectional view of this mold, in which 9 is a liquid injection port, 11 is a liquid reservoir, and 1 is a liquid reservoir.
2 indicates a vent. At the start of the liquid injection, the injected liquid flows as shown by the arrow, but when it enters the mold, it falls downward, causing turbulence in the flow and generating bubbles as shown in the enlarged view of FIG. There is a case. The "state of bubbles" in Table 1 is the result of observing the state of the bubbles thus generated from the molded product.

The results obtained are summarized in Table 1.

[0040]

[Table 1]

Example 2 A solution made of an iron mold having a plate-like space having a size of 550 mm × 550 mm × 10 mm was used, and the solution A-2 was 400 times.
g / sec, Solution B-2 was injected at a rate of 400 g / sec, Solution C was injected at a rate shown in Table 2, and the injection time of each solution shown in Table 2 was used. ) A molded product was obtained in the same manner as in the production of the molded product. The results are summarized in Table 2.

[0042]

[Table 2]

[0043]

[Brief description of drawings]

1 shows a schematic view of an apparatus for carrying out the method of the invention.

FIG. 2 shows a cross-sectional view and a partially enlarged view of a mold used in an example of the present invention.

[Explanation of symbols]

 1 Reservoir 2 Reservoir 3 Reservoir 4 Piping 4'Piping 5 Piping 5'Piping 6 Piping 6'Piping 7 Mixing head 8 Mold 9 Liquid injection port 10 Bubble generator 11 Liquid pool 12 Vent

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 11, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0002

[Correction method] Change

[Correction content]

Conventionally, a monomer liquid comprising a metathesis polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst system (also referred to as a metathesis catalyst system) and a monomer liquid consisting of a metathesis polymerizable cyclic olefin containing an activator component have been used. Mixed (in this specification, this mixed model
The Nomer solution may be referred to as a raw material mixed solution or a mixed solution) ,
A method for producing a crosslinked polymer molded article by injecting it into a mold and polymerizing and crosslinking in the mold is known (for example, Japanese Patent Publication No.
-28451 gazette).

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

In the case where the polymer improving agent is added to improve the impact strength, the raw material mixed solution may not reach the viscosity of the raw material mixed solution [1] at the beginning of injection in the method of the present invention.
On the other hand, the viscosity (300-
1800c. p. when molded using the raw material mixture having a s) from the start to the completion of the injection, the higher the content of the polymer material, lowering of heat resistance of the molded article, high cost, due to the additives in the polymer material In many cases , adverse effects and obstruction such as increase in injection pressure are unavoidable .

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

Solution A-1 was injected at a rate of 350 g / second, solution B-1 was injected at a rate of 350 g / second, and solution C was injected at a rate shown in Table 1. The term "elastomer concentration" in the table when the total injection volume was 100 V (volume), soluble from the start of injection
It is the elastomer concentration (% by weight) of the mixed liquid while the injection of the liquid C is continued , and the viscosity is the viscosity (c.
p. s). Mold 8 is 550mm × 550mm × 4
An iron mold having a plate-shaped space of mm was used, and an injection component exceeding the amount filling the space overflowed into a container (liquid pool) provided at the mold outlet. The mold temperature was 90 ° C. on one side and 60 ° C. on the other side in advance.
One minute after the completion of injection, the mold was opened to obtain a molded product. Figure 2
It is a cross-sectional view of this mold, 9 is a liquid injection port, 11 is a liquid reservoir, and 12 is a vent. At the start of injecting the liquid, the injected liquid flows as shown by the arrow, but when it enters the mold, it falls downward, causing turbulence in the flow and generating bubbles in the 10 portion as shown in the enlarged view of FIG. There is a case. The "state of bubbles" in Table 1 is the result of observing the state of the bubbles thus generated from the molded product.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

[0042]

[Table 2]

Claims (5)

[Claims] 1. A monomer liquid A (solution A) containing a metathesis polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst system and a monomer containing a metathesis polymerizable cyclic olefin containing an activator component of a metathesis polymerization catalyst system. In a method of mixing a liquid B (solution B) and injecting the mixed liquid into a mold to cause polymerization and crosslinking reaction in the mold to produce a crosslinked polymer molded article, it should be injected into the mold. When the volume of the mixed solution was 100 V, (1) the viscosity was adjusted to 300 to 1800 cps from the start of injection until the injection of an arbitrary amount of the mixed solution of 1 V to 50 V. The mixed solution [I] is injected into the mold, and (2) until the injection is completed, the viscosity of the mixed solution [I] injected at the start of the injection is 200 cps or more lower and 10 to 5
A method for producing a crosslinked polymer molded article, which comprises injecting a mixed solution [II] adjusted to a viscosity of 00 cps into a mold. 2. The viscosity of the mixed solution [I] is 500 to 1500.
The manufacturing method according to claim 1, wherein the manufacturing method is adjusted to cps. 3. The mixed solution [I] is 5V after the injection is started.
The method according to claim 1, wherein an amount of -40V is injected into the mold. 4. The mixed solution [II] is 2 more than the mixed solution [I].
The viscosity is lower than 00c.p.s and is 20 to 300c.p.s.
A method according to claim 1 having a viscosity of. 5. The method according to claim 1, wherein the mixed liquid [I] contains an olefin-based elastomer and / or a diene-based elastomer.