JP3145571B2 - Crosslinked polymer molded article and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cyclic cycloolefin crosslinked polymer molded article and a method for producing the same. More specifically, the present invention relates to a crosslinked polymer molded article having effectively improved chemical or physical properties or functions, and a production method for obtaining the same by reaction injection molding.

[0002]

2. Description of the Related Art Conventionally, a monomer solution 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 solution comprising a metathesis polymerizable cyclic olefin containing an activator component Are mixed, injected into a mold, polymerized and cross-linked in the mold to produce a crosslinked polymer molded product (see, for example, Japanese Patent Publication No. 3-28451). This reaction injection molding method can use easily available raw material monomers, the viscosity of the monomers is low, the injection molding pressure is low,
The polymerization / crosslinking reaction is rapid, the molding cycle is short, a large molded product can be obtained relatively easily, and the molded product has excellent advantages such as good balance between rigidity and impact resistance.

On the other hand, in order to impart or improve various properties and functions of a molded article obtained by this reaction injection molding method, a reinforcing agent, a filler, a pigment, an antioxidant, a light stabilizer, a polymer modifier, It is also known that additives such as agents and flame retardants are used.

Further, in order to impart or improve various properties and functions of a molded article obtained by the reaction injection molding method, copolymerization with a plurality of metathesis polymerizable cyclic olefins (JP-A-63-227623 and JP-A-63-227623). JP-A-61-1
79214), an activity regulator comprising a Lewis base for regulating the reaction rate, or a reaction rate regulator comprising an allene compound (JP-A-4-264124).
Catalyst activator comprising a halogenated hydrocarbon and a metal halide compound for reducing monomers remaining in a molded article (JP-A-60-79035), a catalyst component of a metathesis polymerization catalyst system and a metathesis polymerization catalyst It is also known that changing the ratio of the activator component of the system affects reactivity and physical properties of molded articles. In order to mix these additive components in a molded article, the molding method has been carried out by dissolving or dispersing these additive components in a monomer mixture, supplying the resulting solution to a mold, and molding.

[0005] In some cases, it is desirable that these additives are uniformly blended throughout the molded article, but the additives are locally blended such as a skin layer or an inner layer according to the purpose. If that is the case, the goal is often achieved. For example, an antioxidant or a pigment achieves its purpose if it is mainly blended in the skin layer, and hardly exerts its effect if it is blended in the inner layer. Conversely, for example, if the reinforcing agent or the foaming agent is contained in the inner layer rather than the skin layer, the purpose can be more effectively achieved.

In addition, for example, for the purpose of obtaining a large molded product, the purpose of the reaction retardant is achieved if it is mainly incorporated in the skin layer, and its effect is small if it is incorporated in the inner layer. Contrary to this, for example, the catalyst component and the activator component have a small effect that the heat generated by the reaction is removed by the mold in the inner layer, so that the reaction can proceed sufficiently even with a smaller amount than the skin layer. is there.

[0007] On the other hand, when the additive component is incorporated into a resin molded article, if the mixing ratio is increased to achieve the object, disadvantages such as a decrease in other physical properties and an increase in cost are generally caused. Brought. Therefore, it is self-evident that it is desirable from the viewpoint of both the purpose and the cost if the necessary amount of the additive can be intensively added to the desired portion according to the purpose.

[0008]

Therefore, the present inventor has proposed:
A molded article obtained by polymerizing and cross-linking a cyclic olefin using the above-mentioned metathesis polymerization catalyst system and a method for producing the same, wherein a molded article in which an additive component is selectively and selectively blended into a skin layer or an inner layer, and We researched the manufacturing method. As a result, by changing the compounding condition of the additive component in the raw material cyclic olefin liquid containing the catalyst system to be injected into the mold, depending on the injection time, the compounding state of the additive component in the obtained molded article is changed. It was found to change. That is, according to the study of the present inventor, as is apparent from a model experiment described later, when a raw material liquid containing an additive component is used at the beginning or early stage of the period of injecting the raw material liquid, the additive component is mainly When the raw material liquid containing the additive component is added to the skin layer of the molded article during the later to completion time of the injection, the additive component is mainly compounded into the inner layer portion of the molded article, so that the predetermined efficiency can be efficiently achieved. It was found to be effective.

[0009]

Thus, according to the present inventors, a monomer liquid A (solution A) comprising a metathesis polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst system and activation of the metathesis polymerization catalyst system are provided. And a monomer liquid B (solution B) composed of a metathesis polymerizable cyclic olefin containing an agent component, and the raw material mixture is injected into a mold, and a polymerization and cross-linking reaction is performed in the mold. A crosslinked polymer article, wherein the article is (1) formed from at least two different crosslinked polymer phases, and (2) one crosslinked polymer phase comprises 40 A crosslinked polymer molded article characterized in that a skin layer is formed at 100%.

Further, according to the present inventor, in a method of mixing a solution A and a solution B to obtain a molded article of the raw material mixture by a reaction injection molding method, a certain period of time from the start of injection to the completion of injection is provided. The method for producing a crosslinked polymer molded article according to the present invention is characterized in that a raw material mixture in which an additive component is further mixed is used for the period of part.

Hereinafter, the molded article and the production method of the present invention will be described in more detail. First, model experiments performed by the inventor and the results thereof will be described. A monomer solution containing a catalyst component of a metathesis polymerization catalyst system (solution A) and a monomer solution containing an activator component (solution B) are mixed with a metathesis polymerizable cyclic olefin, and polymerized in a mold.
In the reaction injection molding method for cross-linking, the structure is such that the third component is mixed, and a slurry in which carbon black is dispersed in the cyclic olefin is used as the third component (solution C). And solution B
A molded article was prototyped by mixing and pouring only during the initial period of the pouring time. In this case, the active component that causes polymerization and crosslinking is a mixed component of solution A and solution B. This method will be described in more detail using the example of FIG.

In FIG. 1, 1 is a solution A and 2 is a solution B
, And 3 are reservoirs for solution C. The respective solutions are circulated between the mixing head 7 and the storage tanks 1, 2, 3 by 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 injected into the space inside the mixing head 7, and usually, during the injection, The mixing of the solutions is achieved by the collision of. At this time, the injection of the solution A, the solution B and the solution C are simultaneously started, and the injection of the solution C is completed at the same time.
Was performed earlier than the end of the injection.

When the cross section of the crosslinked polymer molded article thus obtained was examined, it was observed that the crosslinked polymer molded article was formed of two polymer phases, a skin layer and an inner layer, as shown in the enlarged view of FIG. The skin layer is a black colored portion in which carbon black is dispersed, and the inner layer is a polymer substantially containing no carbon black. The boundary between the skin layer and the inner layer was relatively clearly observed from the difference in color in the cross section. According to some such model observations, such an epidermis layer is affected by the progress of the reaction between the solution A and the solution B, and the area formed and the thickness of the epidermis are affected. By doing so, it is also possible to cover the entire molded article. A monomer solution A (solution A) containing a catalyst component of a metathesis polymerization catalyst system and a monomer solution B (solution B) containing an activator component are mixed with the metathesis polymerizable cyclic olefin, and polymerized and crosslinked in a mold. In the reaction injection molding method, the viscosities of the solution A, the solution B, and the solution C at 30 ° C. are set to 300 cps, and the time at which these solutions substantially lose fluidity when mixed at 30 ° C. is set to 20 seconds. Adjusting them and injecting them into the mold at 30 ° C., set the injection time of the solution A and the solution B to 1.5 seconds, and set the solution C to the first 0.5 second, until the mold reaches the mold. Assuming that the temperature of the flow path is 30 ° C. and the temperature of the mold is 80 ° C., observation of the molded product shows that the portion before reaching the mold is not black at all, and the portion inside the mold is a skin. Layer turns black Rukoto was observed.

As described above, such a molded article does not need to be black over all parts of the molded article for the purpose of coloring, for example, and obtains a molded article that appears black in appearance. For this purpose, carbon black can be dispersed in the skin layer to reduce its usage.

The present invention provides a wide variety of other uses. For example, only in the skin layer (or conversely, the inner layer)
To achieve the intended purpose with a very small amount of addition by adding various additives such as expensive UV absorbers, weather resistance improvers, coloring agents, curing agents, softening agents, etc. Becomes possible. In addition, if the same amount is added, it can be mainly compounded in a necessary portion.

In the above example, the solution C is injected at the beginning of the injection of the solution A and the solution B. However, different effects can be obtained by injecting the solution C into the middle or at the end of the injection. It is also possible to get. For example, when the solution C contains a foaming agent, if the solution C is injected in the middle or at the end of the injection, the molded article has a foamed inner layer, and the overall weight can be greatly reduced. Further, when the solution C is injected into the middle or at the end of the injection of the solution A and the solution B, the injection of the solution A and the solution B may be stopped during the injection. In addition, an additive is added to the solution A and / or the solution B, and the additive C and the catalyst C or the activator are not contained (the solution C may contain either one).
It is also conceivable to adjust the additive concentration of the epidermis layer or the inner layer by adding the compound during injection.

In the above example, the solution of the cyclic olefin was used as the solution C. However, if circumstances permit, other completely different components may be used, and in some cases, the solution may not be solidified. As an example of such a case, there is a case where heavy fuel oil C is used as the solution C to reduce the product cost.

Further, it is conceivable that a plurality of solutions are used instead of the solution C. In this case, these solutions
It may be a resin for reaction injection molding, a resin of a type that is solidified by heating, a resin for injection molding in some cases, or a resin that does not solidify.

According to another embodiment of the present invention, for example, when solution C contains a cyclopentadiene trimer, when this solution C is injected in the middle or at the end of the injection,
In the molded article, a polymer phase in which cyclopentadiene trimer is copolymerized is formed only in the inner layer, heat resistance is improved, and since the surface layer does not contain this component, cyclopentadiene trimer is entirely copolymerized. It is possible to prevent a decrease in impact resistance, which is a drawback when polymerized. Expensive cyclopentadiene 3
It goes without saying that the amount of the monomer used can be reduced.

Further, when the solution C is injected into the middle or at the end of the injection of the solution A and the solution B, the injection of the solution A and the solution B may be stopped during the injection. However, in this case, it is necessary that the solution C contains a catalyst that causes metathesis polymerization. This is achieved by using another solution containing a catalyst and a solution containing an activator as solution C. When such a method is employed, it is possible to change the type and concentration of the catalyst and activator in the skin layer and the inner layer. That is, when a catalyst system in which a metathesis polymerization reaction occurs slowly is used for the solution A and the solution B to be initially injected, and a catalyst that causes the metathesis polymerization to occur faster than that in the solution C, A metathesis polymerization reaction occurs simultaneously inside the mold, and a shift in the reaction due to a difference in the injection time can be eliminated, and a uniform molded article without distortion can be obtained. Further, a specific additive component is added to the solution A and / or the solution B, and the solution C containing no such additive component (in the case of a catalyst or an activator, it is possible to include either one) can be added during the injection. The addition can dilute the additive component and adjust the concentration of the additive component in the skin layer or the inner layer.

Further, a case in which a plurality of solutions are used instead of the solution C may be considered. In this case, these solutions
What is necessary is just to disperse and inject a plurality of additive components into a plurality of solutions.

Next, the metathesis polymerizable cyclic olefin, the catalyst component of the metathesis polymerization catalyst system (metathesis catalyst system) and the activating component used for obtaining the crosslinked polymer molded article of the present invention will be described.

As the metathesis-polymerizable cyclic olefin for forming the crosslinked polymer of the present invention, those containing one or two metathesis-polymerizable cycloalkene groups in the molecule are used. Preferred are compounds having at least one norbornene skeleton in the molecule. Specific examples of these include dicyclopentadiene, tricyclopentadiene, cyclopentadiene-methylcyclopentadiene codimer, 5-ethylidene norbornene, norbornene,
Norbornadiene, 5-cyclohexenylnorbornene, 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-dimetano-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, ethylenebis (5-norbornene), and the like, and a mixture thereof can also be used. In particular, dicyclopentadiene or a mixture containing 50 mol% or more, preferably 70 mol% or more thereof is suitably used. Further, if necessary, a metathesis polymerizable cyclic olefin having a polar group containing a different element such as oxygen or nitrogen can be used as a copolymer monomer. Such a copolymer monomer also preferably has a norbornene structural unit, and as a polar group, an ester group,
Preferred are an ether group, a cyano group, an N-substituted imide group, a halogen group and the like. Specific examples of such a copolymerized monomer include 5-methoxycarbonylnorbornene, 5- (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-butylnadecimide, 5-chloronorbornene, and the like.

The monomer solution A (solution A) in the present invention contains a catalyst component of a metathesis polymerization catalyst system. As such a catalyst component, salts such as halides of metals such as tungsten, rhenium, tantalum and molybdenum are used, and a tungsten compound is particularly preferable. As such a tungsten compound, tungsten hexahalide, tungsten oxyhalide and the like are preferable, and more specifically, tungsten hexachloride, tungsten oxychloride and the like are preferable. WOCl ₂ (2,6-dichloro-4-t-octylphenoxy) ₂ is also preferred. Further, an organic ammonium tungstate can be used. It has been found that such a tungsten compound immediately starts cationic polymerization when added directly to a monomer, which is not preferable.
Therefore, it is preferable that the tungsten compound is used by suspending it in an inert solvent such as benzene, toluene, chlorobenzene or the like in advance and solubilizing by adding a small amount of an alcohol compound and / or a phenol compound. Further, as described above, in order to prevent undesired polymerization, 1 mole of the tungsten compound
It is preferred to add about 1 to 5 moles of a Lewis base or chelating agent. Examples of such additives include acetylacetone, alkyl acetoacetates, tetrahydrofuran, and benzonitrile. When a polar monomer is used, as described above, the polar monomer itself may be a Lewis base, and in some cases, the compound may have its action without adding any of the above compounds. As described above, the monomer liquid A containing the catalyst component (solution A) has substantially sufficient stability.

On the other hand, the monomer solution B (solution B) of the present invention contains an activator component of a metathesis polymerization catalyst system. The activator-forming component is preferably an organometallic compound mainly composed of an alkylated metal of Group I to Group III of the periodic table, particularly a tetraalkyltin, alkylaluminum compound or alkylaluminum halide compound. Examples thereof include diethyl aluminum, ethyl aluminum dichloride, trioctyl aluminum, dioctyl aluminum iodide, and tetrabutyl tin. By dissolving the organometallic compound as an activator component in a monomer, a monomer liquid B (solution B) is formed.

Basically, a crosslinked polymer molded article can be obtained by mixing the solution A and the solution B and injecting the mixture into a mold. Since it is started, curing may occur while not sufficiently flowing into the molding die, and 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 being added to the solution (solution B) 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 a catalyst component, the ratio of the tungsten compound to the raw material monomer is as follows:
When the activator component is an alkylaluminum, an aluminum compound based on the above-mentioned raw material monomer is about 1,000: 1 to 1,500: 1, preferably about 2,000: 1 on a molar basis. Is used in a molar ratio of about 100: 1 to 5,000: 1, preferably around 200: 1 to 500: 1. Further, as described above, the masking agent and the adjusting agent can be appropriately adjusted and used according to the amount of the catalyst system to be used by experiments.

The molded article of the present invention can be basically obtained by mixing the above-mentioned solution A and solution B and injecting them into a mold. In this case, the catalytic activity of the metathesis catalyst system formed by mixing the solution A and the solution B can be represented by the time from when the two solutions are mixed to when the mixture loses fluidity. That is, if the time until the fluidity is lost is defined as the time from when both solutions are placed in a glass container equipped with a stirrer until the solution gels and entangles on the stirring shaft of the stirrer, the present invention is defined as follows. The solution A and the solution B may lose the fluidity at 30 ° C. for 1 to 1 time.
It is desirably 20 seconds, preferably between 2 and 100 seconds.

The molded article of the present invention is formed from the above-mentioned crosslinked polymer of a metathesis polymerizable cyclic olefin as a resin component. As described above, the molded article comprises (1) at least two different crosslinked polymers. And (2) one cross-linked polymer phase is formed on the entire surface of the molded article.
It is characterized in that a skin layer is formed at 0 to 100%. In a preferred embodiment, the molded article of the present invention is substantially formed of a crosslinked polymer phase forming a skin layer and another crosslinked polymer phase forming an inner layer.

The molded article of the present invention is formed by two or more different crosslinked polymer phases, and one of the factors that distinguishes the polymer phases is that the added components do not substantially directly participate in the reaction. Cases (referred to as "molded article I") and cases where components are substantially directly involved in the reaction (referred to as "molded article II"). This classification is merely for ease of explanation, and the case where both are satisfied simultaneously to form two or more different crosslinked polymer phases is also included in the scope of the molded article of the present invention.

Next, each of the molded article I and the molded article II of the present invention will be specifically described.

Molded Article I The molded article I of the present invention is formed from the above-mentioned crosslinked polymer of metathesis polymerizable cyclic olefin as a resin component, and each polymer phase is formed depending on the state of addition of an additive component which does not directly participate in the reaction. It is characterized by being distinguished. That is, the molded article is characterized in that it satisfies the following conditions (1) to (3). (1) formed from at least two different crosslinked polymer phases, (2) each crosslinked polymer phase is substantially distinguished by the presence, absence, type or content of additive components; and (3) 1 The two crosslinked polymer phases form a skin layer on 40 to 100% of the entire surface of the molded article.

The molded article I of the present invention is formed of at least two different crosslinked polymer phases when its cross section is examined in the thickness direction. Each of the crosslinked polymer phases may have (a) the presence or absence of a certain additive component, (b) the difference in the content ratio of the certain additive component, or (c) the additive component. They are substantially distinguished by type and combination, and each crosslinked polymer phase is distinguished by a relatively distinct interface. Further, one crosslinked polymer phase forms a skin layer in 40 to 100%, preferably 50 to 100% of the whole surface of the molded article. A typical molded article is one in which nearly 100% of the surface is formed by one crosslinked polymer phase.

The number of the crosslinked polymer phases forming the formed article I of the present invention is 2 to 4, preferably 2 to 3, and particularly preferably 2. A typical form of the molded article formed by the two crosslinked polymer phases is a skin core type, that is, a form entirely covered by the skin layer.

The case of a molded product formed from the two phases of the skin-core type is roughly described as the following types (a) and (b). (A) A certain additive component is mainly blended in the crosslinked polymer phase forming the skin layer (skin), and the additive component is substantially contained in the crosslinked polymer phase forming the inner layer (core). If not included or the content ratio is substantially lower than the skin layer,
(B) In the crosslinked polymer phase forming the skin layer (skin), there is substantially no certain additive component or the content thereof is substantially lower than that of the inner layer (core). A) when a certain additive component is mainly contained in the crosslinked polymer phase forming the above.

In the above (A) and (B), a molded article composed of two crosslinked polymer phases in which the presence or absence or the mixing ratio of a specific additive component is different has been described. May be formed from crosslinked polymer phases in which the types or combinations of additive components are different from each other. For example, the skin layer may be formed from a crosslinked polymer phase containing a pigment, and the inner layer may be formed from a crosslinked polymer phase containing a reinforcing agent.

The crosslinked polymer phase forming the skin layer of the molded article I of the present invention advantageously accounts for 0.1 to 50% by weight, preferably 1 to 40% by weight, based on the molded article.
The molded article of the present invention preferably has a skin layer thickness of 0.05 mm or more and 1/5 or less of the average thickness of the molded article,
It is particularly preferred that the thickness be 0.1 mm or more and 1/7 or less of the average thickness of the molded article.

The additive component blended in the crosslinked polymer phase in the molded article I of the present invention is non-reactive with the monomeric metathesis polymerizable cyclic olefin, and is soluble in the monomer. And may be insoluble. The additive component may be any component that can improve or impart a certain function by blending it with the molded article, and those generally used as resin additives are used.

The additives include fillers, reinforcing agents, antioxidants, heat stabilizers, pigments, light stabilizers, ultraviolet absorbers,
Lubricants, antistatic agents, flame retardants, foaming agents, softeners, tackifiers, plasticizers, mold release agents, deodorants, fragrances, extenders, or polymers can be mentioned. The above can be used in combination. The mixing ratio of these additive components depends on the type thereof, but is suitably in the range of 0.01 to 50% by weight, preferably 0.1 to 30% by weight, based on the crosslinked polymer phase to be mixed. . Hereinafter, specific examples of the additive component will be described.

Fillers and reinforcing agents such as calcium carbonate, clay, aluminum oxide, glass fiber, polyethylene powder, polypropylene powder, synthetic fiber powder (fibrous and particulate), wollastonite, talc, barium sulfate, carbon fiber, metal Fibers, carbon black, graphite, whisker antioxidants, heat stabilizers , hindered phenolic antioxidants such as 2,6-di-tert-butyl-4-methylphenol, sulfur such as dilaurylthiodipropionate, etc. Antioxidants,
Phosphorous antioxidant pigments such as trisnonylphenyl phosphite, for example, titanium oxide, carbon black, red iron oxide, phthalocyanine blue, cadmium yellow

Light stabilizers and ultraviolet absorbers such as benzophenone, benzotriazole, benzoate, salicylic acid derivatives, acrylonitrile derivatives, light stabilizers having a hindered piperidine skeleton (HA)
LS) Lubricant such as hydrocarbons such as liquid paraffin, esters such as butyl stearate, fatty acid amides such as stearic acid amide, higher fatty acid metal salts such as barium stearate Antistatic agent such as anionic surfactant such as alkyl sulfonate Agent,
Cationic surfactants such as alkyltrimethylammonium, nonionic surfactants such as glyceric acid ester and alkyldiethanolamine, esters of polyhydric alcohols such as pentaerythritol, phosphates such as phosphoric acid triesters, quaternary ammonium salts, Polyethylene glycol

Flame retardants such as antimony oxide, various organic bromine compounds, various organic chlorine compounds, various phosphate esters, various nitrogen compound blowing agents such as C4 to C7 aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, and fluorinated compounds Aliphatic hydrocarbons, particulate powder of organic compounds wrapped with low-boiling components, and gas such as nitrogen, argon, etc. previously dissolved in an injection solution Softeners such as paraffin oil, naphthenic oil, aromatic oils Tackifiers such as cumarone resin , Phenolic resin, rosin derivative,
Terpene resins, petroleum hydrocarbon resin plasticizers such as polyesters such as phthalates, epoxy systems such as epoxidized triglycerides, phosphate release agents such as tricresyl phosphate such as silicone oils, metal soaps, stearic esters, and waxes Deodorants, perfumes such as hexahydro-4,7-methanoindene-5 (or 6) -yl-acetate, 2-buten-1-one-1
-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl), 2,6,6-trimethyl-1-crotonyl-cyclohexene-1,1,4-dionel, methyl salicylate, citronellyl ether 1,3,5-undecatriene extender, eg recovered polyethylene powder, waste oil, C heavy oil polymer, eg polystyrene, olefin elastomer

Molded Article II The molded article II of the present invention is characterized in that each polymer phase is distinguished depending on the state of addition of an additive component substantially directly involved in the reaction. That is, the molded product is characterized in that the following conditions (1) to (3) are satisfied. (1) It is formed from at least two different crosslinked polymer phases. (2) Each crosslinked polymer phase is substantially the same as the following (i) to (vi) in the presence or absence, type or content of the specific additive component. And (3) one crosslinked polymer phase has 4
The skin layer is formed at 0 to 100%. (i) metathesis polymerizable cyclic olefin copolymerizable (ii) catalyst component (iii) activator component (iv) activity regulator (v) reaction rate regulator (vi) catalyst activator

When the cross section of the molded article II of the present invention is examined in the thickness direction, the molded article II is formed of at least two different crosslinked polymer phases. And each crosslinked polymer phase mutually (a) the presence or absence of the additive component,
(B) a difference in the content ratio of the additive component, or (c)
Substantially distinguished by the type and combination of additive components,
Also, each crosslinked polymer phase is distinguished by a relatively clear interface. One further crosslinked polymer phase is:
40 to 100% of the entire surface of the molded article, preferably 50 to 1
At 00%, a skin layer is formed. A typical molded article is one in which nearly 100% of the surface is formed by one crosslinked polymer phase.

The number of the crosslinked polymer phases forming the molded article II of the present invention is two or three or more. A typical form of the molded article formed by the two crosslinked polymer phases is a skin core type, that is, a form entirely covered by the skin layer.

The case of a molded article formed from the two phases of the skin-core type will be roughly classified into the following types (a) and (b). (A) A certain additive component is mainly blended in the crosslinked polymer phase forming the skin layer (skin), and the additive component is substantially contained in the crosslinked polymer phase forming the inner layer (core). If not included or the content ratio is substantially lower than the skin layer,
(B) In the crosslinked polymer phase forming the skin layer (skin), there is substantially no certain additive component or the content thereof is substantially lower than that of the inner layer (core). A) when a certain additive component is mainly contained in the crosslinked polymer phase forming the above.

In the above (a) and (b), a molded article composed of two crosslinked polymer phases which differ in the presence or absence or the mixing ratio of a specific additive component has been described. May be formed from crosslinked polymer phases in which the types or combinations of additive components are different from each other. For example, the skin layer is formed of a crosslinked polymer phase containing a small amount of unreacted metathesis-polymerizable cyclic olefin in which a catalyst activator is blended, and the inner layer is a crosslinked polymer in which a compound copolymerizable with the metathesis-polymerizable cyclic olefin is blended. It may be formed from a phase.

The crosslinked polymer phase forming the skin layer of the molded article II of the present invention advantageously accounts for 5 to 50% by weight, preferably 10 to 40% by weight, based on the molded article.
The molded article of the present invention preferably has a skin layer thickness of 0.05 mm or more and 1/5 or less of the average thickness of the molded article,
It is particularly preferred that the thickness be 0.1 mm or more and 1/7 or less of the average thickness of the molded article.

The specific agent incorporated in the crosslinked polymer phase in the molded article II of the present invention may be soluble or insoluble in the monomer. The specific agent may be any agent that can improve or impart a certain function by blending it with the molded article. The mixing ratio of these additive components depends on the type thereof, but is suitably in the range of 0.01 to 50% by weight, preferably 0.1 to 30% by weight, based on the crosslinked polymer phase to be mixed. .

Hereinafter, specific examples of the additive components (i) to (vi) in the present invention will be described. These can be used alone or in combination of two or more.

(I) A copolymerizable metathesis polymerizable cyclic ester
Lefin: for example, 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- One,
4,4a, 5,6,7,8,8a-octahydronaphthalene,
6-ethylidene-1,4,5,8-dimetano-1,4,4a,
5,6,7,8,8a-Heptahydronaphthalene, 1,4,
5,8-Dimethano-1,4,4a, 5,6,7,8,8a-hexahydronaphthalene, ethylenebis (5-norbornene), 5-methoxycarbonylnorbornene, 5- (2
-Ethylhexyloxy) carbonyl-5-methylnorbornene, 5-phenyloxymethylnorbornene, 5-cyanonorbornene, 6-cyano-1,4,5,8-dimetano-1,4,4a, 5,6,7, 8,8a-octahydronaphthalene, N-butylnadecimide, 5-chloronorbornene

(Ii) Catalyst component of the metathesis polymerization catalyst system:
For example, tungsten hexachloride, tungsten oxychloride and the like are preferable. Further, an organic ammonium tungstate is previously suspended in benzene, toluene, chlorobenzene, or the like, and is solubilized by adding a small amount of an alcohol compound and / or a phenol compound. 5 mol of base or chelating agent selected from acetylacetone, alkyl acetoacetates, tetrahydrofuran, benzonitrile, etc.

(Iii) Activating agent for metathesis polymerization catalyst system
Minutes: For example, a complex compound obtained by adding an activity modifier to diethyl aluminum chloride, ethyl aluminum chloride, trioctyl aluminum, dioctyl aluminum iodide, tetrabutyl tin

(Iv) Activity regulator: Lewis base such as ethyl benzoate, butyl ether, diglyme, etc.

(V) Reaction rate regulator: substituted acetylene compounds such as phenylacetylene, hexyne-1, hexyne-2, etc.

(Vi) Catalyst activators: halogenated hydrocarbon compounds such as dichlorodiphenylmethane, hexachloroxylene, α, α, α-trichloroethane, carbon tetrachloride, 1,1,1-trichloroethane, allyl chloride, benzyl chloride and the like. Also, silicon, boron, sulfur,
Halogen compounds containing phosphorus element. In addition, it is possible to dissolve or dilute with a solvent or a metathesis polymerizable cyclic olefin before adding. As the catalyst activator, it is sufficient that the catalyst activator has the function of activating the catalyst activity.
For example, those having the effect of reducing the amount of residual monomers in the molded article are also included.

The molded article of the present invention is obtained by mixing the solution A and the solution B described above, injecting the raw material mixture into a mold, and polymerizing and crosslinking in the mold. It is obtained by using a raw material mixture in which an additive component is blended during a certain part of the injection period from the start of injection to the completion of injection as the raw material mixture to be injected into the mist. To give a typical example for explanation, a raw material mixture containing a desired concentration of an additive component is mixed with (i) an initial period of the start of injection, (ii) an intermediate period of the injection period, or (iii). It is sufficient to supply the mixture to the mold during any of the latter periods of the injection period, and to supply the raw material mixture containing no additive during the other period. Further, an additive is added to the solution A and / or the solution B, and the additive and the catalyst or the activator are not included (it is possible to include either one).
It is also possible to adjust the additive concentration of the skin layer or the inner layer by adding the solution C during the injection, but the following is an example of the former method.

In order to obtain a formed article formed from two kinds of crosslinked polymer phases, the following two methods are mentioned as typical examples. (1) The injection of the raw material mixture in which the additive component is mixed is started from the start of the injection of the raw material mixture into the mold, and is terminated halfway before the completion of the injection. A method for producing a molded article having a polymer phase formed thereon. (2) The injection of the raw material mixture in which the additive component is mixed is started from the middle of the injection of the raw material mixture into the mold, and is performed until the injection is completed. A method for producing a molded article having a phase formed.

In the molded article of the present invention, since the raw material mixture for the reaction is highly reactive and easily polymerized, several solutions are prepared in advance, and the solutions are colliding and mixed with a mixing head as appropriate. What is necessary is just to inject the obtained raw material mixed liquid into a metal mold immediately, and to manufacture by a reaction injection molding method.

Next, the types of solutions supplied to the mixing head for carrying out the molding method of the present invention, combinations of the solutions, and the timing of supplying each solution will be described. This description states that certain additive components were blended into the raw material mixture during the initial period of the start of the injection to form a crosslinked polymer phase containing the additive component in the skin layer. This is an example of obtaining a molded product.

The solutions prepared in advance and their basic compositions are as follows. Solution A; Monomer solution containing metathesis polymerization type catalyst component Solution A '; Solution A containing additive component Solution B; Monomer solution solution containing metathesis polymerization type activator component Solution B'; Additive component Containing solution B solution C; additive component or monomer solution containing additive component

The solutions are roughly classified into means I to IV according to the type and supply timing of the solution supplied to the mixing head.
The results are shown in Table 1 below. Solid line in Table 1 (← →)
Represents the supply period of the solution to the mixing head.
Therefore, in each means, the mixed solution of the solution shown by the solid line is supplied to the mold. In addition, it is needless to say that "in the middle of injection" in Table 1 can be appropriately changed before and after depending on the type, purpose and use of the additive.

[0063]

[Table 1]

Each of the means shown in Table 1 is a method for blending an additive component at an early stage of the injection of a raw material mixture, and a method of blending an additive component at a later stage of the injection. May be reversed in the compounding time. In other words, the respective solutions may be supplied by reversing “injection start” and “injection completion” in the above table.

As an alternative to the above means I and II,
A method of mixing the additive component-containing liquid from the start (or initial stage) of the injection of the raw material mixture and injecting the raw material mixture while gradually decreasing the content ratio, or conversely, starting the injection of the raw material mixture (or It is also possible to implement a method of injecting the raw material mixture while gradually increasing the mixing ratio of the additive component from the initial stage).

[0066]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the examples, “%” means “% by weight” unless otherwise specified.

[Example 1] (Preparation of solution A) 20 parts by weight of tungsten hexachloride was added to 70 parts by weight of dry toluene in a nitrogen stream, and then a solution consisting of 2 parts by weight of nonylphenol and 16 parts by weight of toluene was added. To prepare a 0.5M tungsten-containing catalyst solution, and purging the solution with nitrogen gas overnight to remove hydrogen chloride gas generated by the reaction between tungsten hexachloride and nonylphenol, and further prepare the solution. 1 part by volume of acetylacetone was added to 10 parts by volume to prepare a polymerization catalyst.

Next, 95 parts by weight of purified dicyclopentadiene (purity 99.7% by weight, the same applies hereinafter) and 50 parts of purified ethylidene norbornene (purity 99.5% by weight, the same applies hereinafter)
7 parts by weight of ethylene based on the monomer mixture
The above-mentioned catalyst solution for polymerization was added to a solution obtained by adding 3 parts by weight of a 0 mol% ethylene-propylene-ethylidene norbornene polymerized rubber and 2 parts by weight of Ethanox 702 as an oxidation stabilizer so that the tungsten content became 0.01 mol / L. Thus, a monomer solution A (solution A) containing a catalyst component was prepared.

(Preparation of Solution B) A polymerization activator mixed solution prepared by mixing and adjusting the molar ratio of trioctyl aluminum 85, dioctyl aluminum iodide 15, and diglyme 100 was 95 parts by weight of purified dicyclopentadiene and 5 parts by weight of purified ethylidene norbornene. Part, ethylene content 70
A monomer liquid B (solution B) containing an activator component was mixed with a monomer mixture consisting of 3 parts by weight of an ethylene-propylene-ethylidene norbornene polymerized rubber in an amount of 0.03 mol / l. Was prepared. Solution B had a viscosity of 300 cps at 30 ° C.

(Preparation of Solution C1) A monomer mixture consisting of 95 parts by weight of purified dicyclopentadiene and 5 parts by weight of purified ethylidene norbornene was mixed with 3 parts by weight of an ethylene-propylene-ethylidene norbornene polymer rubber containing 70 mol% of ethylene and oxidized. 702 as an agent
(Hereinafter referred to as DCDP solution) 9
0 parts by weight and 10 parts by weight of carbon black (Denka Chemical / HS-100) were mixed to obtain a solution C1.

(Time to lose flowability) Solution A10 at 30 ° C.
ml, 10 ml of solution B and a predetermined amount of solution C1 were previously purged with nitrogen, poured into a 50 ml container placed under the same temperature as the solution, rapidly stirred by a stirrer, and when the resin was entangled with the shaft of the stirrer, The time from the start of stirring and the start of stirring to this point was defined as "time to lose flowability". here,
The amount of the C1 solution relative to the total of 20 ml of the solution A and the solution B is the same as the ratio of C1 to the total amount of the solution A and the solution B to be injected into the mold (the sum of the products calculated by multiplying the injection speed and the injection time). It was made to become. 80 ℃
Was measured in the same manner. Similar values were measured in Examples 2 to 12, and are shown in Table 2.

(Molding) The storage tank 1 of the injection device shown in FIG.
Solution A1, solution B, and solution C1 as a third component were put in a nitrogen atmosphere in the second and third components, respectively, and the speeds of the solutions A, B, and the third component were 450 g / sec, 450 g / sec, and 100 g, respectively.
g / sec, and the injection time of each liquid was set as shown in Table 2, and molding was performed. In Table 2, the total injection time represents the time from the start to the end of injection regardless of the solution A, B or C1 in seconds, and the injection start time is always 0. The injection time of the solution A, the injection time of the solution B, and the injection time of the solution C1 represent the time from the start to the end of injection of each solution in seconds.

A mold made of iron having a plate-shaped space of 550 mm × 550 mm × 4 mm is used, and an injection component exceeding an amount filling the space overflows into a container provided at an outlet of the mold. did. The mold temperature must be 90
° C and the other side was 60 ° C. One minute after the end of the injection, the mold was opened to obtain a molded product. The obtained molded product was a good molded product having a uniform black surface. The molded product was cut and its cross section was examined.
A 0.4 mm black layer and a whitish inner layer were observed inside.

Example 2 Instead of the solution C1, a solution C2 prepared in the following manner was used, and the solutions A, B, C2
The molding was carried out in the same manner as in Example 1 except that the injection time was set as shown in Table 2. (Preparation of solution C2) 90 parts by weight of DCPD solution, 9 parts by weight of 2,6-di-tert-butyl-4-methylphenol and 1 part by weight of carbon black (Denka Chemical / HS
-100) to obtain a solution C2. The added carbon black was added to confirm that a plurality of phases of the skin layer and the inner layer were formed by the color. The obtained molded product was a good molded product having a uniform surface. The molded product was cut, and its cross section was examined. As a result, a black layer having a thickness of 0.2 to 0.4 mm as a skin layer and an inner layer having a brown color were observed inside the black layer.

Example 3 Instead of the solution C1, a solution C3 prepared in the following manner was used, and solutions A, B, and C3 were used.
The molding was carried out in the same manner as in Example 1 except that the injection time was set as shown in Table 2. (Preparation of Solution C3) 90 parts by weight of a DCPD solution, 9 parts by weight of Microsphere-F-301 (Matsumoto Yushi Co., Ltd.)
Co., Ltd.) and 1 part by weight of carbon black (DENKA CHEMICAL /
HS-100) to obtain a solution C3. The microsphere-F-301 is a heat-expandable microcapsule containing a vinylidene chloride copolymer as a shell wall and containing a low-boiling hydrocarbon. The added carbon black was added to confirm that a plurality of phases of the skin layer and the inner layer were formed by the color. The obtained molded product was a good molded product having a uniform surface. In the cross section, an amber layer mainly composed of dicyclopentadiene having a skin phase of 0.2 to 0.4 mm and a black layer containing microspheres were observed inside.

Example 4 The same as Example 1 except that the solution C4 prepared in the following manner was used instead of the solution C1 and the injection times of the solutions A, B and C were set to the conditions shown in Table 2. Was formed. (Preparation of Solution C4) 90 parts by weight of a DCPD solution, 9 parts by weight of polyvinylidene chloride and 1 part by weight of carbon black (Denka Chemical / HS-100) were mixed, and the solution C4 was mixed.
And The added carbon black was added to confirm that a plurality of phases of the skin layer and the inner layer were formed by the color. The obtained molded product was a good molded product having a uniform surface. In the cross section, a black layer containing 0.2 to 0.4 mm of polyvinylidene chloride as a skin phase and a light-colored inner layer were observed inside the black layer.

Example 5 The same as Example 1 except that the solution C5 prepared in the following manner was used instead of the solution C1, and the injection times of the solutions A, B and C were set to the conditions shown in Table 2. Was formed. (Preparation of Solution C5) 98 parts by weight of a DCPD solution, 1 part by weight of a nonylphenol ethylene oxide adduct (nonionic surfactant) and 1 part by weight of carbon black (Denka Chemicals / HS-100) were mixed. did. The added carbon black was added to confirm that a plurality of phases of the skin layer and the inner layer were formed by the color. The obtained molded product was a good molded product having a uniform surface. Its cross section is a black layer containing a surfactant of 0.2 to 0.4 mm as a skin phase,
A whitish inner layer was observed inside.

Example 6 Instead of the solution C1, the solution C6 prepared in the following manner was used, and the injection rates of the solutions A, B, and C6 were 250 g / sec, 250 g / sec, and 250 g / sec, respectively.
The molding was carried out in the same manner as in Example 1 except that the conditions were as shown in Table 2 and the injection times of the solutions A, B and C6 were set to g / sec. (Preparation of Solution C6) 84 parts by weight of a DCPD solution, 15 parts by weight of polystyrene and 1 part by weight of carbon black (Denka Chemical / HS-100) were mixed to obtain a solution C6. The added carbon black was added to confirm that a plurality of phases of the skin layer and the inner layer were formed by the color. The obtained molded product was a good molded product having a uniform surface. In the cross section, a black layer containing 0.2 to 0.4 mm of polystyrene as a skin phase and an inner layer of a brown color were observed inside the black layer.

[Example 7] Instead of the solution C6, a solution C7 prepared in the following manner was used, and solutions A, B and C7 were used.
The molding was carried out in the same manner as in Example 6, except that the injection time of was set as shown in Table 2. (Preparation of solution C7) 70 parts by weight of a DCPD solution, 29 parts by weight of a petroleum resin (Eastotac II-142 manufactured by Eastman Co.)
R) and 1 part by weight of carbon black (Denka Chemical /
HS-100) to obtain a solution C7. The added carbon black was added to confirm that a plurality of phases of the skin layer and the inner layer were formed by the color. The obtained molded product was a good molded product having a uniform surface. Its cross section is 0.2 to 0.4 as a skin phase.
A black layer containing 1 mm of petroleum resin and a whitish inner layer were observed inside the black layer.

Example 8 Example 6 was repeated except that the solution C8 prepared in the following manner was used instead of the solution C6, and the injection times of the solutions A, B and C8 were set to the conditions shown in Table 2.
Molding was performed in the same manner as in (Preparation of Solution C8) 50 parts by weight of a DCPD solution, 49 parts by weight of antimony oxide and 1 part by weight of carbon black (Denka Chemical / HS-100) were mixed to obtain a solution C8. The added carbon black was added to confirm that a plurality of phases of the skin layer and the inner layer were formed by the color. The obtained molded product was a good molded product having a uniform surface. In the cross section, a black layer containing 0.2 to 0.4 mm of antimony oxide as a skin phase and an inner layer of a brown color were observed inside the black layer.

Example 9 Instead of the solution C6, a solution C9 prepared in the following manner was used, and the solutions A, B, and C9 were used.
The molding was carried out in the same manner as in Example 6, except that the injection time of was set as shown in Table 2. (Preparation of Solution C9) 90 parts by weight of a DCPD solution, 9 parts by weight of Fuel Oil C and 1 part by weight of carbon black (Denka Chemical / HS-100) were mixed to obtain a solution C9. The added carbon black was added to confirm that a plurality of phases of the skin layer and the inner layer were formed by the color. The obtained molded product was a good molded product having a uniform surface. Its cross section is 0,0 as the epidermis.
A layer mainly composed of dicyclopentadiene having a thickness of 2 to 0.4 mm and a black layer containing heavy oil C were observed inside the layer.

Example 10 Instead of the solution C6, a solution C10 prepared in the following manner was used.
Molding was performed in the same manner as in Example 6, except that the injection time of C10 was set to the conditions shown in Table 2. (Preparation of Solution C10) A solution C10 was prepared by mixing 50 parts by weight of a DCPD solution, 9 parts by weight of polyethylene and 1 part by weight of carbon black (Denka Chemical / HS-100). The added carbon black was added to confirm that a plurality of phases of the skin layer and the inner layer were formed by the color. The obtained molded product was a good molded product having a uniform surface. The cross section is a layer containing polyethylene of 0.2 to 0.4 mm as a skin phase,
A whitish inner layer was observed inside.

[Example 11] Instead of the solution C6, a solution C11 prepared in the following manner was used.
The molding was performed in the same manner as in Example 6, except that the injection time of C11 was set to the condition shown in Table 2. (Preparation of solution C11) DCPD solution of 20 parts by weight, 79
Parts by weight of liquid paraffin and 1 part by weight of carbon black (Denka Chemical / HS-100)
It was set to 1. The added carbon black was added to confirm that a plurality of phases of the skin layer and the inner layer were formed by the color. The obtained molded product was a good molded product having a uniform surface. In the cross section, a black layer composed of liquid paraffin having a skin phase of 0.2 to 0.4 mm and an inner layer of a brown color were observed inside.

[Example 12] Instead of the solution C6, a solution C12 prepared in the following manner was used.
The molding was performed in the same manner as in Example 6, except that the injection time of C12 was set to the condition shown in Table 2. (Preparation of solution C12) 50 parts by weight of DCPD solution and 50 parts by weight
A part by weight of titanium oxide was mixed to obtain a solution C12. The obtained molded product was a good molded product having a uniform surface. In the cross section, a white layer containing 0.2 to 0.4 mm of titanium oxide as a skin phase and an inner layer of a tan color were observed inside the white layer.

[0085]

[Table 2]

Example 13 (Preparation of Solution A) 20 parts by weight of tungsten hexachloride was added to 70 parts by weight of dry toluene under a nitrogen stream, and then a solution consisting of 2 parts by weight of nonylphenol and 16 parts by weight of toluene was added. To prepare a 0.5M tungsten-containing catalyst solution, and purging the solution with nitrogen gas overnight to remove hydrogen chloride gas generated by the reaction between tungsten hexachloride and nonylphenol, and further prepare the solution. 1 part by volume of acetylacetone was added to 10 parts by volume to prepare a polymerization catalyst.

Next, a monomer mixture comprising 95 parts by weight of purified dicyclopentadiene (purity: 99.7% by weight, the same applies hereinafter) and 5 parts by weight of purified ethylidene norbornene (purity: 99.5% by weight, the same applies hereinafter) was mixed with ethylene containing 70
3% by weight of an ethylene-propylene-ethylidene norbornene polymerized rubber in mole%, and Ethanox 7 as an oxidation stabilizer
To the solution containing 022 parts by weight, the above-mentioned catalyst solution for polymerization was added so that the tungsten content became 0.01 mol / L, to prepare a monomer solution A containing the catalyst component (solution A). Solution A had a viscosity of 300 cps at 30 ° C.

(Preparation of Solution B) 95 parts by weight of purified dicyclopentadiene and 5 parts by weight of purified ethylidene norbornene were prepared by mixing a polymerization activator mixed solution prepared by mixing and adjusting the molar ratio of trioctyl aluminum 85, dioctyl aluminum iodide 15, and diglyme 100 in a molar ratio. Part, ethylene content 70
A monomer liquid B (solution B) containing an activator component was mixed with a monomer mixture consisting of 3 parts by weight of an ethylene-propylene-ethylidene norbornene polymerized rubber in an amount of 0.03 mol / l. Was prepared. Solution B had a viscosity of 300 cps at 30 ° C.

(Preparation of Solution C-1) A solution was prepared by adding 15% by weight of dichlorodiphenylmethane to a monomer mixture consisting of 95 parts by weight of purified dicyclopentadiene and 5 parts by weight of purified ethylidene norbornene to obtain solution C-1. . Dichlorodiphenylmethane is an agent having an effect of reducing the amount of unreacted metathesis polymerizable cyclic olefin in the reaction molded product. As a result, the odor of the molded product due to the unreacted metathesis polymerizable cyclic olefin can be reduced.

(Molding) The storage tank 1 of the injection device shown in FIG.
Solution A, solution B and solution C-1 were put into 2, 3 respectively, and the speed of solution A, B and C-1 was 500 g each.
/ Sec, 500 g / sec and 20 g / sec, and the injection time of each liquid is set as shown in the column of “injection time” in Table 2 (liquid C is injected at the initial time of the start of injection), and molding is performed. Was. In Table 3, the time from the start of the injection of the solutions A, B and C-1 to the end thereof is expressed in seconds. 0 second means the start of injection of the solutions A, B and C-1.

A mold made of iron having a plate-shaped space of 550 mm × 550 mm × 4 mm is used, and an injection component exceeding an amount filling the space overflows into a container provided at the exit of the mold. did. The mold temperature must be 90
° C and the other side was 60 ° C. One minute after the end of the injection, the mold was opened to obtain a molded product.

[0092]

[Table 3]

Comparative Example 1 Table 3 shows the injection time of the solution C-1.
Example 13 except that the injection of the liquid C-1 was stopped as described above.
Molding was carried out under the same conditions as described above.

Comparative Example 2 Table 2 shows the injection time of the solution C-1.
The molding was carried out under the same conditions as in Example 13 except that the liquid C-1 was injected from the start to completion in the same manner as the injection of the solutions A and B.

When the odor of the molded article of Example 13 was compared with the odor of the molded articles of Comparative Examples 1 and 2 by sensory inspection, all three inspectors found that the molded article of Comparative Example 1 had the strongest odor. The molded products of Example 13 and Comparative Example 2 were determined to be equivalent. Next, when the amount of unreacted dicyclopentadiene in each molded product was measured, the results shown in Table 3 were obtained. According to this table, the smell of the molded product of Comparative Example 2 was comparable to that of Comparative Example 1.
It is considered that the lower odor of the molded article was due to a decrease in the amount of unreacted dicyclopentadiene. In the molded article of Example 13, the reason why the unreacted dicyclopentadiene is not so small in spite of being not so small is considered that dichlorodiphenylmethane reduces unreacted dicyclopentadiene in the skin layer.

Example 14 Solution C in Example 13
-1 was replaced with an iron mold having a plate-shaped space of 550 mm × 550 mm × 4 mm using the solution C-2 prepared in the following manner, and 550 mm × 1000 mm × 8
Solution A, using an iron mold having a plate-shaped space of
The injection rates of B and C-2 were 200 g / sec and 200 g / sec, respectively.
g / sec and 8 g / sec and solutions A, B and C-
Molding was performed in the same manner as in Example 13, except that the injection time of No. 2 was set under the conditions shown in Table 3 (injection of the liquid C-2 at the initial stage of the start of injection).

(Preparation of Solution C-2) A solution was prepared by adding 1.5% of phenylacetylene to a monomer mixture consisting of 95 parts by weight of purified dicyclopentadiene and 5 parts by weight of purified ethylidene norbornene. And As shown in Japanese Patent Publication No. 4-264124, phenylacetylene has a function of delaying the polymerization reaction rate.

Comparative Example 3 Table 3 shows the injection time of the solution C-2.
Example 14 except that the injection of the liquid C-2 was stopped as described above.
Molding was carried out under the same conditions as described above.

Comparative Example 4 Table 2 shows the injection time of the solution C-2.
The molding was performed under the same conditions as in Example 14 except that the liquid C-2 was injected from the start to the completion in the same manner as the injection of the solutions A and B. As a result, although molding could be performed without problems in Example 14 and Comparative Example 4, in Comparative Example 3, the liquid leaked out from the vicinity of the injection port before the injection was completed, and the molded product was completely filled with the mold. Did not become.

Example 15 In the preparation of the solution A, the catalyst solution was added so that the tungsten content became 0.007 mol / l, and the monomer solution A containing the catalyst component was added.
(Solution A) was prepared, the solution C-3 prepared in the following manner was used in place of the solution C-1, and the injection times of the solutions A, B, and C-3 were as shown in Table 3 (C- Molding was performed in the same manner as in Example 13 except that the three liquids were injected at the initial stage of the injection start).

(Preparation of Solution C-3) A catalyst solution was added to a monomer mixture consisting of 95 parts by weight of purified dicyclopentadiene and 5 parts by weight of purified ethylidene norbornene so that the tungsten content was 0.5 mol / L. A solution was prepared, and used as solution C-3.

Comparative Example 5 Table 3 shows the injection time of the solution C-3.
Molding was carried out under the same conditions as in Example 1 except that the injection of the C-3 liquid was stopped as described above. As a result, a good molded product was obtained in the molding of Example 15, but in the molding of Comparative Example 5, when the mold was opened after injection, steam of an unreacted product was observed, and the surface of the molded product was poor. there were.

[Example 16] Instead of the solution C-1, the solution C-4 prepared in the following manner was used, and the injection rates of the solutions A, B and C-4 were 400 g / sec and 400 g, respectively.
/ S and 400 g / s and solutions A, B and C
Molding was carried out in the same manner as in Example 13 except that the injection time of No. -4 was set to the conditions shown in Table 2 (injection of the solution C-4 after the injection of the solutions A and B, and injection until completion).

(Preparation of Solution C-4) Purified dicyclopentadiene 65 parts by weight, purified cyclopentadiene trimer 32
A solution consisting of 3 parts by weight of an ethylene-propylene-ethylidene norbornene polymerized rubber containing 70 parts by weight of ethylene and containing 70 mol% of ethylene was prepared, and was referred to as solution C-4. Cyclopentadiene trimer, as a copolymer component, has the effect of improving the heat resistance of the resulting polymer, but also has the disadvantage of lowering the impact resistance.

Example 17 Molding was performed under the same conditions as in Example 13 except that the injection time of the solution C-4 was as shown in Table 3 (injection of the liquid C-4 at the initial stage of the start of injection). did.

Comparative Example 6 Table 3 shows the injection time of the solution C-4.
The molding was carried out under the same conditions as in Example 13 except that the liquid C-4 was injected from the start to completion in the same manner as the injection of the solutions A and B. When the heat distortion temperature of the obtained molded product was measured, the results shown in Table 3 were obtained. That is, Example 16 and Example 17 differ from Comparative Example 6,
Heat resistance can be improved without impairing impact resistance. This is because the cyclopentadiene trimer remains only in the inner layer or the outer layer, and the cyclopentadiene trimer is present in the entire layer and is not copolymerized.

Examples 18 to 36 and Comparative Examples 7 to 10 By using the injection apparatus shown in FIG.
Inch) molded plate was formed by a reaction injection molding method. Anti
Injection molding machine (hereinafter referred to as "RIM machine")
We used two small RIM machines (this RIM machine
University of the Department of Chemical Engineering and
 Commercially available from Materials Sciences). FIG.
, Each RIM machine has a pair of storage tanks 21
And 22 and 24 and 25, one of these reservoirs
Contains about 1% by weight of carbon black as a colorant
Was. The contents of the storage tanks of each RIM machine are
Mixers 23 and 25, and the mixture
The mixture is guided by the whirl mixing mixer 27 and poured into the mold 28.
Was entered. Storage tanks 22 and 25 are used as a common component for molding.
Contains monomer liquid and catalyst components, and is stored in storage tanks 21 and 24
Contains a molding monomer liquid and an activator component as common components.
I was out. Carbon black is added to storage tank 25
Was done. Table 4 shows examples of these compositions. Storage tanks 21 and 2
4 was filled with the A composition, and the storage tanks 22 and 25 were put with the B composition. Saving
In the tanks 21 and 22, the composition 1 (that is, the composition A 1 and the composition B)
1) is stored in storage tanks 24 and 25 in composition 2 (ie, A composition
No. 2 and B) 2) were added. For this type of combination
This will be described in more detail in Examples 37 to 40. Table 4
RDCPD monomer is 93.5% dicyclopen
Tadiene (DCPD), 3.5% EPDM (ethylene
Propylene diene) elastomer and 3.0% E
A solution consisting of NB (ethylidene norbornene),
WOOD catalyst component is 0.139M WOCl_Two(2,6-
Dichloro-4-t-octylphenoxy)_TwoAnd 0.139
M diglyme (dissolved in DCPD; diglyme is
Tylene glycol dimethyl ether, stable catalyst
Agent). The TOTH activator component is water
Trioctyl tin (TOTH) is a reaction rate regulator
Is tributyl phosphite (TBP), and WOT
The R catalyst component is WCl ₆, T-butanol and nonylph
WOXR activation synthesis
Minutes are tri-n-octyl aluminum and dioctyl aluminum
Based on minium and used in US Patent 5,268,232
It is the same as what was done. Carbon black is 7.
Used as a 5 wt% DCPD solution.

The injection speed was about 100 ml / sec. The mold is an 8 ″ × 4 ″ × 1/8 ″ plate, and the gate is provided over the entire length of the end having a width of 4 ″. And a length of 1/8 ". The mold was heated and maintained on one side (A-side) at 80 ° C and the other side (B-side) at 60 ° C.

In a series of RIM molding tests, the monomer liquid containing carbon black was injected in the first half of the injection time, and then the injection was stopped. The amount ratio of the colored monomer liquid was changed stepwise with respect to the total injection amount as shown in the column of the colored monomer liquid amount ratio in Table 5. For example, in Examples 21 to 22, the material containing carbon black is injected from the start of the total injection time to the time corresponding to 30% of the total injection time, and the material containing no carbon black is subsequently injected. Injected only during 70% of the injection time. Table 5 shows the obtained results. In the table, the percentage of black part, which means the amount of the material containing carbon black, refers to the front end, the middle, and the deepest end of the molded article (either A-side or B-side according to the above definition). A) from the surface to the center of the plate-shaped molded article. For example, in Example 19, the cross section of the plate-shaped molded product is A at a position 1 inch before the innermost end.
-12/1000 inch from side to center, B
-The 14/1000 inch layer was black from side to center and the 99/1000 inch inside was uncolored.

In Table 5, for example, the numeral 50% of the black portion means that all positions from each side of A and B toward the center line are black. In these examples, the front end means the end on the side where the gate is located in the plate-like molded product, and the innermost end means the end on the opposite side of the front end.

[0111]

[Table 4]

[0112]

[Table 5]

Examples 37-40 Two compositions, defined in Table 6 as composition A or composition B, were prepared using a base material consisting of dicyclopentadiene (DCPD), ethylidene norbornene (ENB) and an elastomeric liquid. (This is referred to as a base composition). Here, this elastomer liquid is a 3.6% ethylene propylene diene elastomer (abbreviated as EPDM,
ROY from Uniroyal Chem. Co., Inc. Middlebury CT
ALENE), 93.5%
DCPD and 2.9% ENB.

In the preparation of the composition A, trioctyltin hydride (TOTH, WITCO / Schering, WITCO GmbH, Berg
kamen, released from Germany) and tributyl phosphite (TBP) were added to the base composition. In preparing the B composition, 0.139M WOCl ₂ (2,6-dichloro-4) described in US Pat. No. 5,082,909 is used.
A catalyst solution, a DCPD solution of -t-octylphenoxy) ₂ and 0.139 M diglyme, was added to the base composition. TOTH is an activator component, and when the composition A and the composition B are mixed, the reaction rate regulator (TBP) functions to adjust the reaction rate.

Further, according to the description in Table 6, A composition and B composition
A colorant (7.5% by weight of carbon black dispersed in a base composition) in one or both of the compositions;
Antioxidants (2,6-di-t-butyl-p-cresol, BHT) and / or copolymerized monomers (tricyclopentadiene, TCPD) were added.

Each composition was prepared and transferred under a nitrogen atmosphere in order to cut off contact with air and water, and stored in a storage tank having a rubber cap and a metal cap. "SEMPAK" with multi-component injection gun for molding
A 200 system (obtained from SEMCO, Glendale, CA) was used. Each of these multi-component injection guns
Two separate reservoirs, A composition and B at the time of injection from the gun
A static mixer for mixing the composition was included. A solution A having a composition A and a solution B having a composition B according to the composition shown in Table 6 were respectively placed in a container attached to one of the injection guns, and a solution A having a composition A and a solution B having a composition B were respectively placed. With the liquid
Each was placed in a container attached to the other injection gun. The liquid mixture mixed by the static mixers of the two injection guns was mixed by the third static mixer and introduced into the mold. These mixers have "SEMMIX"
An ER "mixer (obtained from SEMCO, Glendale, Calif.) Was used. Therefore, in each of these examples, a liquid A of composition A and a liquid B of composition B according to the composition shown in Table 6 were used. To one of the injection guns, A liquid of composition A and B
Liquid B of composition 2 will be associated with the other injection gun.

In these injections, equal amounts of the mixture from each injection gun were mixed again by a third mixer and then led to the mold. The flow of the A liquid of the A composition 2 and the B liquid of the B composition 2 is stopped after a predetermined amount is injected, and the mixture thereafter becomes the A liquid of the A composition 1 and the B liquid of the B composition 1 Only a mixture of by this,
The surface portion is composed of the A liquid of the A composition 1, the B liquid of the B composition 1, the A liquid of the A composition 2 and the B liquid of the B composition 2, and the inside is the A liquid of the A composition 1 and the B composition. A molded product consisting only of the liquid B of Example 1 was able to be molded. Example 39D and Example 4
In 0B, in the method described above, the mixture stopped halfway is A
A liquid mixture of liquid A having composition 1 and liquid B having composition 1 was prepared.

In Example 37, the surface was colored black.
The inside is an example of a molded article that is not colored. A of 1 of A composition
The liquid, the B liquid of the B composition 1, the B liquid of the A composition 2 and the B liquid of the B composition 2 are simultaneously injected at the same flow rate, and 20% of the amount that can completely fill the mold is injected. Continued until. Next, the injection of the A liquid of the A composition 2 and the B liquid of the B2 of the B composition is stopped, and only the injection of the A liquid of the A composition 1 and the B liquid of the 1 B composition is filled in the mold. Continued until As a result, it was recognized that about 25% (both sides) of the molded article in the cross-sectional direction contained carbon black. This layer was colored black, and easily distinguished from the uncolored interior with the naked eye.

Example 38 provided a molded article in which the antioxidant in the surface portion was selectively increased. As can be seen in Table 6, 2 of the B composition contains 10% by weight of BHT, and therefore 5 wt.% Of the mixture consisting of the 2nd liquid of the A composition and the 2nd liquid of the B composition. % BHT, and thus 2.5% by weight of the antioxidant BHT in the surface part of the molding. BHT in the molded article was detected by preparing a sample on a slice from a section of the molded article and measuring the infrared absorption spectrum of the hydroxy group attributable to BHT at 3640 cm ^-1 by FTIR measurement. The surface portion showed this absorption, but the interior did not.

Example 39 illustrates the use of two different monomers, DCPD and TCPD.
Specifically, changing the amounts of these monomers changed the thermal properties such as impact resistance and heat distortion temperature. Example 39 was repeated essentially as described above, except that the combination of amounts of dicyclopentadiene (DCPD) and tricyclopentadiene (TCPD) was varied. The resulting molded article is Gardner
An impact test, a notched impact test, and a test of heat deformation temperature were performed, and the results of Examples 39A to 39D in Table 7 were obtained.

Example 40 shows that by realizing a high catalyst concentration at a specific location in a molded article, the toughness of the entire molded article, for example, the bending modulus, can be changed. In the case of this example, the catalyst concentration on the surface of the molded product was increased. If the catalyst concentration in the composition as a raw material is high, the reactivity of the monomer increases, and the toughness of a molded article molded using this composition is increased.
It has been found that this can be achieved only by increasing the catalyst concentration on the surface of the molded article and increasing the reactivity of the monomer only on the surface of the molded article.

Example 40 was repeated essentially as described above, except that various mono ratios of catalyst component / activator component were used per 1000 moles of monomer. . The obtained molded product was measured for flexural modulus and flexural strength. Table 8 shows the results.

As described above, the catalyst component used in the reaction injection molding, other necessary components, and the components desirably used may be extremely expensive as compared with the main component. Table 6
As shown in the figure, the catalyst component /
Typical values for the molar ratio of activator components are 0.40 / 0.60
It is. From the comparison between Example 40A and Example 40B in Table 8, the amount of the catalyst component / activator component used inside the molded article of Example 40B is about 1% of the amount used outside the molded article. / 3, about 20 of the amount used in Example 40A
%, But the bending modulus was shown to change little, albeit much less.

[0124]

[Table 6]

[0125]

[Table 7]

The above Examples 39A and 39B are reference examples. In Example 39A, only the liquid A having composition A 2 and the liquid B having composition 2 were injected, and in Example 39B, liquid A having composition A 1 was injected. Only liquid B and liquid B of composition B were injected.

[0127]

[Table 8]

Embodiments 40A and 40C are reference examples. In Example 40A, the injection of the A liquid having the A composition of 1 and the B liquid having the B composition of 1 was carried out.
Injection was performed using only the liquid A of composition 2 and the liquid B of composition 2.

[0129]

According to the present invention, in a molded article obtained by a reaction injection molding method of a metathesis polymerizable cyclic olefin in the presence of a catalyst component of a metathesis polymerization catalyst system and an activator component, a desired additive component is obtained. Can be mainly incorporated into the skin layer or the inner layer of the molded article. Therefore, it can be effectively blended according to the purpose of the additive component, the effect of the additive component can be further enhanced, and the cost of the additive component can be reduced.

[Brief description of the drawings]

FIG. 1 shows a schematic view of an apparatus showing an example of an embodiment of the present invention and a partially enlarged view of a cross section of a molded article.

FIG. 2 shows a schematic diagram of an apparatus showing another embodiment of the present invention.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Komoriya, 2-1, Hinode-cho, Iwakuni-shi, Yamaguchi Teijin-Meton Co., Ltd. Technical Center (72) Inventor Dennis Earl Fitzgibbon Signal Hill Dry, 1970 Hockesin, Delaware, United States of America (11) JP-A-3-223310 (JP, A) JP-A-3-164216 (JP, A) JP-A-1-221415 (JP, A) JP-A-63-241008 (JP, A) JP-A-63-222824 (JP, A) JP-A-7-102043 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B29C 45/00-45/84 C08G 61 / 06-61/08

Claims (15)

(57) [Claims] 1. A monomer solution A (solution A) comprising a metathesis polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst system and a monomer comprising a metathesis polymerizable cyclic olefin containing an activator component of a metathesis polymerization catalyst system A liquid B (solution B) is mixed, the raw material mixture is poured into a mold, and a polymerization and cross-linking reaction is performed in the mold. Means that (1) formed of at least two different crosslinked polymer phases, and (2) one crosslinked polymer phase forms a skin layer on 40 to 100% of the entire surface of the molded article. A crosslinked polymer molded article characterized by the following. 2. The molded article according to claim 1, wherein the molded article is substantially formed of a crosslinked polymer phase forming a skin layer and another crosslinked polymer phase forming an inner layer. 3. A monomer solution A (solution A) comprising a metathesis polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst system and a monomer comprising a metathesis polymerizable cyclic olefin containing an activator component of a metathesis polymerization catalyst system A liquid B (solution B) is mixed, the raw material mixture is poured into a mold, and a polymerization and cross-linking reaction is performed in the mold. Are (1) formed from at least two different crosslinked polymer phases, (2) each crosslinked polymer phase is substantially distinguished by the presence, absence, type or content of additive components, and (3) 1) A crosslinked polymer molded article characterized in that one crosslinked polymer phase forms a skin layer on 40 to 100% of the entire surface of the molded article. 4. The molded article according to claim 3, which is substantially formed from a crosslinked polymer phase forming a skin layer and another crosslinked polymer phase forming an inner layer. 5. The molded article according to claim 3, wherein the additive component is non-reactive with the metathesis polymerizable cyclic olefin. 6. The method according to claim 3, wherein the additive component is a function improving agent.
The molded article as described. 7. An additive component comprising a filler, a reinforcing agent, an antioxidant, a heat stabilizer, a pigment, a light stabilizer, an ultraviolet absorber, a lubricant,
Antistatic agent, flame retardant, foaming agent, softener, tackifier,
The molded article according to claim 3, wherein the molded article is at least one selected from the group consisting of a plasticizer, a release agent, a deodorant, a fragrance, and an extender. 8. The average thickness of the skin layer is 0.05 mm or more and 1/5 or less of the average thickness of the molded product.
The molded article as described. 9. The molded article according to claim 3, wherein the metathesis polymerizable cyclic olefin contains at least 50 mol% of dicyclopentadiene. 10. A monomer solution A (solution A) comprising a metathesis polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst system and a monomer comprising a metathesis polymerizable cyclic olefin containing an activator component of a metathesis polymerization catalyst system A method for producing a crosslinked polymer molded article by mixing a liquid B (solution B), injecting the raw material mixture into a mold, and causing polymerization and crosslinking reaction in the mold. 4. The molded article according to claim 3, wherein a raw material mixture further mixed with an additive component is used as a raw material mixture to be injected into the mixture for a certain period from the start of injection to the completion of injection. Manufacturing method. 11. A monomer solution A comprising a metathesis polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst (solution A) and a monomer comprising a metathesis polymerizable cyclic olefin containing an activator component of a metathesis polymerization catalyst A liquid B (solution B) is mixed, the raw material mixture is poured into a mold, and a polymerization and cross-linking reaction is performed in the mold. Is formed from (1) at least two different crosslinked polymer phases, (2) each crosslinked polymer phase comprises (i) a copolymerizable metathesis polymerizable cyclic olefin, (ii) a catalyst component, and (iii) The activator component, (iv) an activity regulator, (v) a reaction rate regulator, and (vi) at least one additive component selected from the group consisting of a catalyst activator is substantially distinguished in type or content ratio. It is, and (3) 1
The two crosslinked polymer phases comprise 40 to 10 of the entire surface of the article.
A crosslinked polymer molded article having a skin layer formed at 0%. 12. The molded article according to claim 11, which is substantially formed from a crosslinked polymer phase forming a skin layer and another crosslinked polymer phase forming an inner layer. 13. The molded article according to claim 11, wherein the average thickness of the skin layer is 0.05 mm or more and 1/5 or less of the average thickness of the molded article. 14. The molded article according to claim 11, wherein the metathesis polymerizable cyclic olefin contains at least 50 mol% of dicyclopentadiene. 15. A monomer solution A (solution A) comprising a metathesis polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst system and a monomer comprising a metathesis polymerizable cyclic olefin containing an activator component of a metathesis polymerization catalyst system A method for producing a crosslinked polymer molded article by mixing a liquid B (solution B), injecting the raw material mixture into a mold, and causing polymerization and crosslinking reaction in the mold. As a raw material mixture to be injected into a certain period between the start of injection and the completion of injection,
(i) a copolymerizable metathesis polymerizable cyclic olefin, (i
(i) catalyst component, (iii) activator component, (iv) activity regulator, (v)
12. The method for producing a molded article according to claim 11, wherein a raw material mixture in which at least one additive component selected from the group consisting of a reaction rate regulator and (vi) a catalyst activator is mixed.