JPH11262924A - Reactive polymerization molding method and bottomed cylindrical molded object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To expand the configurational variation of a molded object and to produce a bottomed cylindrical molded object reduced in voids and having a smooth inner surface shape. SOLUTION: The reactive raw soln. in a mold 2 is subjected to reactive polymn. in such a state that centrifugal force is applied to the reactive raw soln. by rotating the mold 2 in such a state that the center-of-rotation S of the mold 2 is inclined by an angle θ(e.g. 2-5 deg.) with respect to a horizontal surface H. For example, a cylindrical molded object 10 having a bottom 10b, for example, a flowerpot or a bottomed container can be produced. The bottomed cylindrical molded object 10 produced by this method is reduced in the content of voids and has a smooth inner surface shape.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reactive polymerization molding method and a molded article. In the following, the present invention relates to a reactive polymerization molding method in which an undiluted reaction solution is reacted and polymerized, and a molded article obtained by the method.

[0002]

2. Description of the Related Art In the present specification, the term "reactive polymerization molding method" broadly means a method in which a reaction stock solution is reacted and polymerized in a mold.
As an embodiment, there is a reaction injection molding (RIM) method. The RIM method is a manufacturing method in which two or more reaction stock solutions are mixed in a mixing chamber, fed into a cavity of a mold device, and injection-molded while reacting in the mold device. This RIM method is suitably used for forming a polymer (molded article) from a norbornene-based monomer.

[0003] RIM molded articles are considered to be used in various technical fields because of their excellent impact resistance, low molding pressure and easy molding.

[0004]

However, in the conventional reaction injection molding, bubbles may be mixed in the injection of the reaction stock solution into the cavity of the mold, and as a result, voids and the like are formed in the molded body. And the quality of the molded body was degraded.

[0005] Further, in the case of forming a bottomed cylindrical molded body such as a flowerpot or a bottomed container by conventional reaction injection molding, it is necessary to insert a nest type or the like in a portion corresponding to a hollow portion. It was very difficult. In addition, when a nesting mold or the like is placed in a portion corresponding to the hollow portion, the reaction injection molded resin that comes into contact with the nesting mold is cooled during molding, and there is a possibility that poor curing may occur. Since the inner surface of this type of molded article is required to be smooth, it is necessary to minimize the occurrence of defects on the inner surface.

In US Pat. No. 4,808,364, a mold that rotates about a horizontal rotation axis is provided inside a mold.
A centrifugal molding method is disclosed in which a reaction stock solution is mixed and charged, and a reaction stock solution is reacted and polymerized inside a mold while applying a centrifugal force to the reaction stock solution.

Further, Japanese Patent Application Laid-Open No. 3-69357 discloses that
A technology is used in which a polyethylene tube having an adhesive property to a molded body is used as a mold, a reactive polymerization reaction is performed while rotating the polyethylene tube around a horizontal axis, and the obtained molded body is integrated with the polyethylene tube. It has been disclosed.

However, in the centrifugal molding method described in these publications, a centrifugal force is applied to the internal reaction stock solution by setting a central axis of the cylindrical mold horizontally and rotating the central axis about the central axis. In addition, a tube-shaped molded body having both ends opened is obtained. For example, a bottomed cylindrical molded body, such as a flowerpot, having one end face substantially closed and the other end face open. Cannot be formed, and there are few variations in the shape of the obtained molded body.

An object of the present invention is to provide a reactive polymerization molding method which has been made in view of the above situation and can expand the variation in the shape of the obtained molded article. It is another object of the present invention to provide a bottomed cylindrical molded body in which voids are less likely to be generated in the molded body and the inner surface of a hollow portion formed in the molded body is smooth.

[0010]

According to the reactive polymerization molding method of the present invention for achieving the above-mentioned object, a method is provided in which a rotation center axis of a mold is rotated while being inclined with respect to a horizontal plane. Characterized in that the reaction stock solution is subjected to a reaction polymerization under acceleration.

The present inventors have conducted intensive studies on a method for performing a reactive polymerization reaction while applying a centrifugal force to a reaction stock solution by rotating a mold. As a result, the rotation center axis of the mold was inclined with respect to the horizontal. The reaction stock solution is reacted and polymerized in a state of being rotated by rotation, so that a wall (hereinafter, also referred to as a bottom) is formed at the lower end in the direction of gravity among the ends along the rotation center axis.
Was formed, and the present invention was completed.

The inclination angle of the rotation center axis of the mold with respect to the horizontal is not particularly limited, and is the maximum inclination angle with respect to the horizontal.
Although it can be 0 °, it is preferable to select the length within a range of 1 to 10 ° from the viewpoint of forming the length of the hollow cylindrical portion into a desired shape and forming a bottom having a uniform thickness as much as possible. It is preferable to select from the range of ５5 °.

According to the method of the present invention, for example, it is possible to form a bottomed cylindrical molded body having one end opened and the other end closed, so that a flowerpot, a planter (a decorative container for potting), a compost (a fertilizer storage container) ) And other bottomed containers and the like can be easily manufactured.

Further, unlike the conventional method, it is not necessary to insert a nested mold into a bottomed cylindrical molded body manufactured by using the method of the present invention. There are few obstacles due to poor curing of the resin. In addition, since bubbles contained in the reaction stock solution are removed by centrifugal force or the like, voids are reduced, the mechanical strength and durability of the molded body are improved, and the surface of the molded body (the inner surface of the hollow portion is removed). Including) is smooth. Note that the “cylindrical” is not necessarily limited to a cylindrical shape, and the “bottom” does not necessarily mean a completely closed bottom.

In the present invention, the viscosity of the undiluted reaction solution is not particularly limited, but is preferably 500 to 100,000 c.
ps, more preferably 700 to 10,000 cps,
Particularly preferably, about 900 to 3,000 cps is good.
The higher the viscosity of the reaction stock solution, the easier it is for the bottom to be formed.However, if the viscosity is too high, it tends to be difficult to form a free form using acceleration, while if the viscosity is too low, the reaction will occur. Since the stock solution tends to stay at the lower part, it is necessary to select in consideration of these viewpoints. The viscosity can be adjusted by mixing, for example, an elastomer, a filler, a fiber, or the like into the reaction solution.

In the present invention, the acceleration based on the centrifugal force is not particularly limited, but is preferably 0.5 to 3.
A gravitational acceleration of 0 G, more preferably 0.7 to 2.0 G, and particularly preferably about 1 G is good. If the acceleration is too low, the undiluted reaction solution is difficult to uniformly adhere to the inner peripheral surface of the mold, and a molded body having a uniform thickness tends to be hardly obtained.If the acceleration is too high, the bottom tends to be hardly formed. It is necessary to select in consideration of these viewpoints.

It is preferable that the molding method of the present invention is carried out under a condition in which the mold is filled with an inert gas such as nitrogen gas and the pressure is kept positive. This is because the reaction solution is prevented from being oxidized by filling with an inert gas, and air is prevented from entering by setting the pressure to positive, so that oxidation of the reaction solution can be further prevented and bubbles contained in the reaction solution are also contained. This is because the effect of removing is increased.

The pressure to be applied only needs to be higher than the atmospheric pressure.
Preferably 0.1 to 1.0 kg at gauge pressure (the same applies hereinafter)
/ Cm ² , more preferably 0.3 to 0.8 kg / cm
² , particularly preferably 0.5 to 0.7 kg / cm ² for good efficiency.

Also, by injecting a plurality of undiluted reaction solutions into the mold with a time lag, a molded article having a multilayer structure and a bottomed cylinder can be manufactured. Can be manufactured in a superimposed manner.

A filler can be mixed into the reaction stock solution. In this case, before the centrifugal force of a predetermined acceleration is obtained, the mold is rotated with a centrifugal force such that the acceleration becomes 1 G or less. (Preparation rotation) is preferable. This is for sufficiently mixing the filler and the reaction solution before molding by the polymerization reaction. From such a viewpoint, the time required for the preparation rotation is
The time is preferably before the reaction with the reaction stock solution starts.

In the present invention, the undiluted reaction solution is placed in a mold in advance, and then the centrifugal force is applied by rotating the mold, or the undiluted reaction solution is rotated after the mold is rotated. Can be injected.

Reaction stock solution The reaction stock solution is not particularly limited.
Examples include urea-based, nylon-based, epoxy-based, unsaturated polyester-based, phenol-based, and norbornene-based ones, with the norbornene-based being particularly preferred. The temperature of the reaction solution before it is put into the mold is preferably 20 to 80 ° C.

In such molding, a reinforced polymer (molded body) can be produced by placing a filler in a mold in advance and supplying a reaction liquid into the filler for polymerization.

Examples of the filler include glass fiber, aramid fiber, carbon fiber, ultra high molecular weight polyethylene fiber, metal fiber, polypropylene fiber, aluminum coated glass fiber, cotton, acrylic fiber, boron fiber, silicon carbide fiber, and alumina fiber. And the like. These reinforcing materials can be used in various shapes, such as those obtained by forming a long fiber or chopped strand into a mat, woven into a cloth, or remaining in a chopped shape. It is preferable that the surface of these reinforcing materials is treated with a coupling agent such as a silane coupling material in order to improve the adhesion to the resin. The amount to be used is not particularly limited, but is usually 10% by weight or more, preferably 20 to 60% by weight of the total weight of the molded article.

The reaction stock solution contains various additives such as an antioxidant, a pigment, a colorant, a foaming agent, a flame retardant, a slide imparting agent, an elastomer, a dicyclopentadiene-based thermopolymerized resin, and a hydrogenated product thereof together with the filler. Additives may be blended. The properties of the resulting polymer can be modified by adding additives.

As the antioxidant, there are various antioxidants for plastics / rubbers such as phenol type, phosphorus type and amine type. Examples of the elastomer include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and ethylene- Examples include propylene-diene terpolymer (EPDM), ethylene vinyl acetate copolymer (EVA) and hydrides thereof. The additive is usually mixed in advance with one or both of the reaction solutions.

Mold The present invention has a structure in which after the reaction stock solution is put into the mold, acceleration can be applied to the reaction stock solution inside the mold. The mold is rotatable around one axis or multiple axes inclined with respect to the horizontal. By rotating the mold, an acceleration due to centrifugal force acts on the reaction solution inside the mold.

The temperature of the mold is preferably between 10 and 150
° C, more preferably 20 to 120 ° C, still more preferably 30 to 100 ° C. Before injecting the unreacted solution into the mold, warm air is circulated inside the mold, and at least the inside of the cavity of the mold is heated to a predetermined temperature. The molding may be performed by pouring the unreacted solution into the cavity.

The material of the mold used in the present invention is as follows.
Although not particularly limited, a material having good adhesiveness to the mold and a material that is non-adhesive to the molded body is preferable in order to obtain a molded body having a smooth outer peripheral surface, for example, cast iron,
Metals such as iron, stainless steel, aluminum and nickel electroformed are preferred. However, as long as the material is non-adhesive to the molded body, a synthetic resin or another material may be used. This is because reactive polymerization can be performed at a relatively low pressure, and it is not necessary to use a highly rigid mold.

When the mold is made of a synthetic resin, the synthetic resin is made of a non-adhesive polar resin such as fiber reinforced plastic (FRP), phenol, polyester, etc. Since it is not integrated with the reactive polymer molding, the mold apparatus can be removed and used repeatedly for each reactive polymerization molding, which is preferable.

The mold is preferably a split mold that can be formed into a free shape, but may be a mold that is not split. In the case of a cylindrical mold, since it is necessary to pull out the obtained molded body, in order to improve the releasability, a wax, a lubricant or the like is required in advance along the inner peripheral surface of the mold before the injection of the stock solution. Is preferably applied. Further, when the molded body is pulled out, it is possible to start drawing out the molded body after the temperature of the molded body reaches a temperature equal to or lower than the glass transition temperature (Tg) of the molded body, preferably equal to or lower than (Tg-50) ° C. preferable. This is because the shape of the molded body does not collapse and the workability is good.

[0032]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments shown in the drawings.

FIGS. 1A and 1B are schematic perspective views of a mold used in a reactive polymerization molding method according to one embodiment of the present invention.
FIG. 2 is a side view of a driving device for rotating the mold, and FIG.
4 is a plan view of a driving device, FIG. 4 is a cross-sectional view of a main part of a mold during molding, FIG. 5 is a schematic perspective view showing an example of a molded product, and FIG. 6 is a mold during molding according to another embodiment of the present invention. FIG. 7 is a view showing an example of a molded product when the inclination angle of the mold is maximized, and FIG. 8 is a view for explaining the timing of injecting the reaction stock solution into the mold. is there.

First Embodiment In the present embodiment, a predetermined acceleration (for example,
The reaction solution containing norbornene-based monomer is reacted and polymerized under the condition of adding
A method for producing a cylindrical molded body with a bottom of m or more will be described. In this embodiment, a mold 2 shown in FIGS. 1A and 1B is used to apply a predetermined acceleration to the reaction stock solution.

The mold 2 is attached to the outer periphery of both ends of the mold 4 from the axial direction in a state in which the mold 4 can be divided into two along the dividing surface 3 in the vertical direction, and the divided molds 4 are combined. And a pair of rolling rings 8. The split mold 4 is made of, for example, an aluminum casting, and the rolling ring 8 is made of cast iron.

It is preferable that a sealing material is mounted on the split surface 3 of the split mold 4. By installing the sealant, it is possible to prevent inconvenience such as leakage of the undiluted reaction solution from the split surface 3. Suitable sealing materials used in the present embodiment include:
There is no particular limitation, and a silicone rubber sealing material or the like can be used.

An inner peripheral surface is formed inside the split mold 4 combined with the split surface 3, and a reaction stock solution having a predetermined viscosity is pressed against the inner peripheral surface by centrifugal force having a predetermined acceleration. It is supposed to be. End plates 6 and 6 are formed at both ends in the axial direction of the split mold 4 so that the through holes 5 are formed.
A nozzle for supplying the undiluted reaction solution is inserted from the through hole 5, so that the undiluted reaction solution can be supplied into the mold 2.

As shown in FIGS. 2 and 3, a pair of flanged drive rollers 12 is engaged with one rolling ring 8 of the mold 2, and a pair of flangeless driving rollers 12 is engaged with the other rolling ring 8. Drive rollers 14 are engaged with each other. These drive rollers 12 and 14 are connected to a transmission 16 and a constant torque inverter motor 18 and all rotate at substantially the same rotational speed. When these drive rollers 12 and 14 are all rotated at substantially the same rotational speed, the rolling ring 8 engaged with them is also rotated around its axis, and the mold 2 composed of the split dies 4 and 4 is also rotated. At the same time, it rotates around the axis. The drive rollers 12 and 14, the transmission 16 and the motor 18 are mounted on a base 20.

The base 20 is supported on a floor 21 by supporting members 20a and 20b. These support members 20
Although a detailed illustration is omitted, a and 20b are provided with mechanisms for arbitrarily adjusting the height, respectively, and by adjusting the respective height adjustment mechanisms, the base 20 is attached to the floor surface 21. It can be inclined with respect to it. The inclination angle of the base 20 is determined by the rotation center axis S of the mold 2.
Is set to be an angle θ with respect to the horizontal plane H. The inclination angle θ of the rotation center axis S of the mold 2 with respect to the horizontal plane H is
0 <θ ≦ 90 ° can be selected, but in this embodiment, from the viewpoint of forming a bottom having a uniform thickness as much as possible, from 2 to 5
° range.

Further, one drive roller 12 in the axial direction is provided with a flange. This is because, since the mold 2 is inclined, the flange limits the axial movement of the rolling ring 8 to limit the axial movement (movement to the right in FIG. 2) of the rolling ring 8. It is. Drive roller 1 in both axial directions
The flanges 2 and 14 may be provided, but only one of them can sufficiently restrict the axial movement of the mold 2.

Next, a method of molding a bottomed cylindrical molded body (for example, a container with a bottom) by the reactive polymerization molding method using the mold 2 will be described.

First, as shown in FIG.
Then, as shown in FIG. 1A, the rolling rings 8, 8 are attached to both ends of the combined split dies 4, 4, and the mold 2 is assembled. Next, the mold 2 is rotatably mounted on the drive rollers 12 and 14 shown in FIGS. In this state, the mold 2 has its rotation center axis S inclined by an angle θ with respect to the horizontal plane H.

Thereafter, reactive polymerization molding is performed. The reactive polymerization molding performed in the present embodiment is a molding using a norbornene-based monomer. Specific examples of the norbornene-based monomer to be used include bicyclics such as norbornene and norbornadiene; dicyclopentadiene (cyclopentadiene dimer). ), Tricyclics such as dihydrodicyclopentadiene; tetracyclics such as tetracyclododecene; pentacyclics such as cyclopentadiene trimers; heptacyclics such as cyclopentadiene tetramers; methyl, ethyl, Substituents such as alkyl such as propyl and butyl, alkenyl such as vinyl, alkylidene such as ethylidene, and aryl such as phenyl, tolyl and naphthyl; and further having polar groups such as ester group, ether group, cyano group and halogen atom. Substitutes are exemplified. These monomers may be used in combination of one or more kinds. It is easy to obtain, excellent in reactivity,
From the viewpoint of excellent heat resistance of the obtained resin molded body, tricyclic,
Tetracyclic or pentacyclic monomers are preferred.

The resulting ring-opening polymer is preferably of a thermosetting type. For this purpose, among the above norbornene-based monomers, it has two or more reactive double bonds such as cyclopentadiene trimer. Those containing at least a crosslinkable monomer are used. The proportion of the crosslinkable monomer in all the norbornene monomers is preferably from 2 to 30% by weight.

It should be noted that, within a range not to impair the object of the present invention,
Monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene and cyclododecene, which can be ring-opening copolymerized with norbornene monomers,
It may be used as a comonomer.

The metathesis catalyst which can be used in molding using a norbornene-based monomer is a norbornene-based catalyst such as tungsten hexachloride or an organic ammonium molybdate such as tridodecyl ammonium molybdate or tri (tridecyl) ammonium molybdate. There is no particular limitation as long as it is a known metathesis catalyst as a catalyst for bulk polymerization of monomers, but an organic ammonium molybdate is preferred.

As the activator (cocatalyst), JP-A-58-1983
127728, JP-A-4-226124,
JP-A-58-129003, JP-A-4-1452
There is no particular limitation as long as it is a known activator as disclosed in Japanese Patent No. 47, for example, alkyl aluminum halides such as ethyl aluminum dichloride and diethyl aluminum chloride, organic aluminum compounds such as alkoxyalkyl aluminum halides, and organic tin. And the like.

As preparations before molding, a molding material mainly composed of a norbornene monomer, a metathesis catalyst and an activator was mixed with a liquid B composed of a norbornene monomer and a metathesis catalyst, and the above-mentioned norbornene monomer and activator. The liquid is divided into two stable liquids and the liquid A, each of which is placed in a separate tank.

To start molding, control the mixer,
The solution A and the solution B from the tank are mixed, and the mixed solution is used as a reaction stock solution by using a nozzle or the like to form the through-hole 5 of the mold 2.
From the mold 2.

The viscosity of the undiluted reaction solution was 9 ° C. at 30 ° C.
It is about 00 to 3,000 cps. In this state, by rotating the mold 2 about the axis S, as shown in FIG. 4, the undiluted reaction solution adheres to the inner peripheral surface of the mold 2 in a cylindrical shape due to centrifugal force accompanying the rotation. A wall (bottom) is formed near the lower end in the direction of gravity (the right end in FIG. 4) of both ends of the cylindrical portion. Although the reason is not clear, according to experiments by the present inventors, this bottom is not always formed in close contact with the end plate 6 of the mold 2, and is formed in a state that the bottom is slightly floated. It turned out that there is. This means that, for example, when a flower pot is formed and the flower pot is installed with the bottom part down, the seat is good and the drainage is convenient.

In the present embodiment, the mold 2 does not necessarily need to be heated, but may be heated using a heat medium or warm air from the viewpoint of facilitating the polymerization reaction.

The number of revolutions of the mold 2 is 1 G or more and 5
G or less, and it depends on the diameter of the inner peripheral surface of the mold 2.
When the thickness is set to about 600 mm, the rotational speed of the mold 2 around the axis is preferably about 80 to 150 rpm. Mold 2
The initial startup time required to rotate at a constant rotation speed around the axis is about several seconds to 30 seconds. After that, rotation is possible at a constant rotation speed. The mold 2
May be rotated around the axis at a constant rotational speed, and then a reaction solution may be supplied by inserting a nozzle through the through hole 5.

By rotating the mold 2 around the axis thereof at a constant rotational speed, the unreacted solution supplied to the inside of the mold 2 becomes cylindrical on the inner peripheral surface of the mold 2 by centrifugal force. At the same time, a wall (bottom) is formed near the lower end in the direction of gravity among the two ends of the cylindrical portion. By maintaining this state for, for example, 1 to 10 minutes, the reaction in the undiluted reaction solution proceeds, bulk polymerization is performed, and a bottomed cylindrical molded body is obtained.

Then, after the rotation of the mold 2 is stopped and the mold 2 is cooled, the rolling ring 8 is removed from the state shown in FIG. 1 (A) to the state shown in FIG. 1 (B). , Split mold 4,4
When opened, the bottom 10b having an opening 10a at one end (the left end in the drawing) as shown in FIG. 5 and being closed near the other end (the right end in the drawing) is removed. Thus, a molded article 10 having the same can be obtained. The bottomed cylindrical molded body 10 is formed of a reactive polymer molded body of a norbornene-based monomer.

According to the present embodiment, a bottomed cylindrical molded body 1
0 can be easily molded, so that flower pots, planters, composts, and other bottomed containers having a shape in which one end is closed and the other end is open can be manufactured. Can be varied. In the case where it is necessary to form a drainage hole in the bottom like a flowerpot, such a hole can be formed by providing a projection or the like on the inner surface of the corresponding end plate 6 of the mold 2. is there. However, it is preferable that such a hole be provided at the center as much as possible.

Since a centrifugal force is applied to the undiluted reaction solution, bubbles are separated from the undiluted reaction solution by the centrifugal force during molding, and voids are eliminated in the obtained molded body.

The inner peripheral surface of the bottomed cylindrical molded body 10 obtained by the method of this embodiment shown in FIG. 5 does not touch anything during the molding process. There is no inconvenience such as poor curing, and the inner peripheral surface is smooth. The obtained bottomed cylindrical molded body is also used, for example, as a storage container (tank) for a fluid or the like, and since the fluid may flow therethrough, it is convenient that the inner peripheral surface is smooth.

Further, since the bottomed cylindrical molded product obtained by the method according to the present embodiment is a polymer obtained by utilizing a bulk polymerization reaction of a norbornene-based monomer, the impact resistance and the durability are improved. Excellent mechanical properties such as properties. Further, according to this method, it is possible to relatively easily mold even a relatively small-diameter cylindrical molded body having a bottom.

Further, in the present embodiment, the split dies 4, 4 are used, and rolling rings 8, 8 are mounted on the outer periphery thereof, and the dies 2 are mounted on the shaft center by using the rolling rings 8, 8. Since it is rotated around, it is possible to realize both the free-form molding of the molded body by using the split mold and the rotation using the ring with little rotational fluctuation. In addition, if rotational blur occurs, the rotational blur can be suppressed by shaving the outer circumference of the rings 8 during rotation. Further, replacement of the rings 8, 8 is also easy.

The angle θ of the rotation center axis S of the mold 2 with respect to the horizontal plane H is set to 2 to 5 °, and the viscosity of the undiluted reaction solution is set to 900.
3,000 cps, acceleration applied to the reaction stock solution is 1.5
4 to 3.5 G, the thickness t1 of the cylindrical portion of the cylindrical body having a bottom, the thickness t2 of the bottom, and the height t3 (θ, t1 to t3 of the bottom outer surface from the end surface of the molded body are shown in FIG. T2 / t1 is 3 to 1 and t3 / t1 is 1 /
It was confirmed by experiments by the present inventors that the ratio was 2/5.

Second Embodiment In this embodiment, except that the mold 2a shown in FIG. 6 is used,
In the same manner as in the first embodiment, the mold 2 is rotated while its rotation center axis S is inclined by an angle θ with respect to the horizontal plane H, so that the reaction stock solution containing the norbornene-based monomer is reacted and polymerized. .

In this embodiment, the mold 2a is composed of a pair of split dies 4a, 4a and rings 8a,
8a. In the present embodiment, the outer diameters of the split dies 4a, 4a are not uniform in the axial direction, and the outer diameter is increased at one end 22 in the axial direction. The enlarged diameter portion 26 can be integrally formed with the end of the opening 24 on the opening side. This enlarged diameter portion 26
Is suitable, for example, when manufacturing flower pots. In addition, by inserting the small-diameter side end of another similar bottomed cylindrical molded body into the enlarged diameter portion 26, the molded body can be stacked in multiple stages.

Even a bottomed cylindrical molded body having such an enlarged portion can be easily molded by the method of the present embodiment. Further, the small diameter portion is cylindrical, but may be tapered. In addition, the end face on the enlarged diameter part side can be a closed face, and the end face on the small diameter part side can be an open face,
Such a molded product cannot be molded by the nesting molding method, and the present invention is a very useful technique.

Third Embodiment In this embodiment, a mold 2 is prepared in the same manner as in the first embodiment, except that a filler is mixed into the reaction stock solution to carry out the reaction polymerization.
Is rotated in a state where its rotation center axis S is inclined by an angle θ with respect to the horizontal plane H, and the reaction stock solution containing the norbornene-based monomer is reacted and polymerized.

Prior to molding, a filler such as silica sand and a reaction solution are put in the mold 2 in advance, and the mold 2 is initially started (preparation rotation) with the mold 2 inclined. The initial startup time required to rotate the mold 2 around the axis at a constant rotation speed is about several seconds to about 30 seconds. During the preparation rotation time, an acceleration of 1 G or less is applied to the reaction solution and the filler, and the reaction solution and the filler are uniformly mixed. Thereafter, the rotation speed of the mold 2 is increased to a constant rotation speed, and 1G
A degree of acceleration is applied to the reaction stock solution and the filler in the mold 2. After the mold 2 is rotated around the axis thereof at a constant rotation speed, a nozzle may be inserted through the through-hole 5 to supply the reaction solution.

After the lapse of a predetermined time, the rotation of the mold 2 is stopped, and after the mold 2 is cooled, the mold 2 is rolled from the state shown in FIG. 1A to the state shown in FIG. If the ring 8 is removed and the split dies 4 and 4 are opened, a bottomed cylindrical molded body can be obtained. This bottomed cylindrical molded body is formed of a reactive polymer molded body of a norbornene-based monomer, and a filler is uniformly dispersed in a resin layer. In the present embodiment, the properties (mechanical strength, flame retardancy, etc.) of the bottomed cylindrical molded body can be improved by filling the filler.

Fourth Embodiment In this embodiment, except that a plurality of reaction stock solutions are injected into a mold with a time lag, a multilayered bottomed cylindrical molded body is manufactured. In the same manner as in the embodiment, the mold 2 is rotated in a state where the rotation center axis S is inclined by an angle θ with respect to the horizontal plane H, and the unreacted solution containing the norbornene-based monomer is reacted and polymerized.

As preparation for molding, two kinds of reaction stock solutions, a first reaction stock solution and a second reaction stock solution, are prepared. First
As a reaction stock solution, a molding material mainly composed of a norbornene-based monomer, a metathesis catalyst and an activator, a solution B comprising a norbornene-based monomer and a metathesis catalyst, and a solution A comprising the aforementioned norbornene-based monomer and an activator And put them in separate tanks.

As a second unreacted solution, a molding material mainly composed of a norbornene-based monomer, a metathesis catalyst and an activator was used. The liquid is divided into two stable liquids, the liquid A and the activator, each of which is placed in a separate tank.

The same or different first reaction stock solution can be used for the first reaction stock solution and the second reaction stock solution. In this embodiment, the same reaction solution is used, and only the first reaction stock solution is used for the third reaction stock solution. Fillers such as forms shall be mixed.

To start molding, control the mixer,
The solution A and the solution B from the tank corresponding to the first reaction stock solution are mixed, and the mixed solution is used as the first reaction stock solution through the through hole 5 of the mold 2 and the inside of the mold 2 using a nozzle or the like. To supply. Thereafter, at a predetermined timing described later, the mixer is similarly controlled to mix the solution A and the solution B from the tank corresponding to the second reaction stock solution, and the mixed solution is used as the second reaction stock solution, and the nozzle or the like is used. The metal is supplied from the through hole 5 of the mold 2 to the inside of the mold 2.

The timing of injecting the second reaction stock solution into the mold 2 will be described with reference to FIG. In FIG. 8, the horizontal axis indicates the passage of time (t), and the vertical axis indicates the change in the temperature (T) of the reaction stock solution. In the figure, the curve shown by the solid line shows the first undiluted solution, and the curve shown by the one-dot chain line shows the second undiluted solution. PL is the pot life of the first undiluted solution (liquid flow pot life, PL), SMT
1 is the smoke time of the first reaction solution (time when the polymerization reaction starts rapidly), SMT2 is the smoke time of the second reaction solution (time at which the polymerization reaction starts rapidly), and Tg is the time of the first reaction solution. The glass transition temperature is shown.

In this embodiment, the injection of the second undiluted solution into the mold 2 starts at the time of the pot life of the first undiluted solution, and the smoke time (SMT) of the second undiluted solution is reduced.
2) almost coincides with the time when the glass transition temperature (Tg) of the first reaction stock solution is reached. In this embodiment, the first
The glass transition temperature of the undiluted reaction solution is Tg = 140 to 150 ° C.
And the smoke times (SMT1, SMT2) of the first reaction stock solution and the second reaction stock solution are each 7 minutes from injection (mixing of solution A and solution B).

However, this is only an example, and the timing of injecting the second unreacted solution into the mold 2 may be any time after the pot life of the first unreacted solution. May be any time after the time when the smoke time (SMT2) reaches the glass transition temperature (Tg) of the first undiluted reaction solution.

The smoke time of the first undiluted reaction solution and the second undiluted reaction solution can be freely adjusted by mixing the undiluted reaction solution with a reaction modifier or the like. Can be adjusted, and the injection start timing of the second reaction stock solution can be adjusted in relation to this.

According to the present embodiment, a bottomed cylinder having a two-layer structure in which a resin layer in which a filler is not mixed is disposed inside a resin layer in which the filler is uniformly dispersed with good adhesiveness and adhesion. A shaped article can be obtained. This bottomed cylindrical molded body is formed by an outer resin layer in which the filler is uniformly dispersed.
It is a molded article that exhibits excellent properties of mechanical strength and flame retardancy, and also has effective properties of inner and outer layers, such as a smooth inner surface formed by an inner resin layer in which no filler is mixed.

In this embodiment, the first undiluted reaction solution and the second undiluted reaction solution are injected at different times in a state where the inclination angle of the mold is kept constant. The interior space is completely isolated from the outside by changing the tilt angle of the mold so that a wall is formed at the other end before, during or after the injection of the stock solution. It is possible to manufacture a hollow molded article, and the variation of the molded article can be further expanded.

Other Embodiments The present invention is not limited to the above-described embodiments, but can be variously modified within the scope of the present invention. For example, in the first embodiment, only two rolling rings are mounted on the outer periphery of the combined split dies 4, 4, but three or more rolling rings may be mounted in the axial direction.
Further, the drive rollers 12, 14 are provided for all the rolling rings.
Need not be engaged, and a ring with which the drive rollers 12 and 14 do not engage may be mounted on the outer periphery of the split dies 4 and 4.

In the above-described embodiment, the split dies 4, 4
Although a is divided into two, it may be divided into three or more. However, when the molded body has a shape that can be pulled out from the mold in the axial direction, the mold does not necessarily have to be a split mold.

Further, in the embodiment described above, the mold is
Although rotated about the axis, it may be rotated about two or more multi-axes.

In addition, the horizontal plane H of the rotation center axis S of the mold 2
May be changed during the reaction molding.

[0082]

EXAMPLES Hereinafter, the present invention will be described based on more detailed examples, but the present invention is not limited to these examples.

Example 1 A mold 2 shown in FIG. 1A was prepared and set on drive rollers 12 and 14 of a mold rotating device shown in FIGS. The pair of split molds 4 and 4 were made of an aluminum casting, had an outer diameter of 500 mm, an inner diameter of 400 mm, and an axial length of 1200 mm. The inner diameter of the through hole 5 of the end plate 6 formed at both ends of the split dies 4 and 150 was 150 mm.

The rolling rings 8, 8 were attached with the split surfaces 3 of the split dies 4, 4 sealed. Rolling ring 8,8
Was made of cast iron, its outer diameter was 700 mm, and its axial thickness was 50 mm.

The inclination angle θ of the rotation center axis S of the mold 2 with respect to the horizontal plane H was 3 °. The rolling rings 8, 8 were placed on the driving rollers 12, 14, and the reaction stock solution was supplied to the inside of the mold 2 by using a nozzle from the axial through hole 5 of the split mold.
The preparation of the reaction stock solution was performed as follows. 100 parts by weight of a mixed monomer composed of 85% by weight of dicyclopentadiene (DCP) and 15% by weight of tricyclopentadiene was used.
4.5 parts by weight of EPT-3012P (manufactured by Mitsui Petrochemical) and 2 parts by weight of Irganox 1010 (manufactured by Ciba Geigy), which is a phenolic antioxidant, are placed in two containers. On the other hand, 40% of diethyl aluminum chloride (DEAC) was added to the mixed monomer.
A millimolar concentration (a millimolar equivalent relative to 1 mol of the mixed monomer is hereinafter referred to as "mmol concentration"), n-propanol was added to a concentration of 44 mmol, and silicon tetrachloride was added to a concentration of 20 mmol (solution A). On the other hand, tri (tridecyl) ammonium molybdate was added to the mixed monomer at a concentration of 10 mmol (solution B).

The liquid A and the liquid B are respectively sent to the mixer by a gear pump so as to have a volume ratio of 1: 1 and then supplied from the through hole 5 of the mold 2 to the inside of the mold 2 using a nozzle. did. The temperature of the reaction stock solution was 30 ° C., and its viscosity was 1750 cps at 30 ° C.

Immediately after the supply of the undiluted reaction solution, the drive rollers 12 and 14 were rotated, and the mold 2 was rotated about its axis. In 15 seconds, the rotation speed of the mold 2 becomes 140 rpm
And maintained that speed. The calculated acceleration acting on the undiluted solution was 3.5 G.

After maintaining this state for 10 minutes, the rotation was stopped, the mold 2 was taken out, the rolling rings 8, 8 were removed, and the split dies 4, 4 were opened. A bottom cylindrical molded body 10 was obtained.

When the dimensions of each part of the bottomed cylindrical molded body 10 were measured, the thickness of the side wall (cylindrical part) (t1 in FIG. 4)
4) was 6 mm, and the thickness of the bottom (see t2 in FIG. 4) was 5 mm. The dimension from the lowermost end of the bottom (see t3 in FIG. 4) was 2 mm.

For confirmation, the bottomed cylindrical molded body 10 was cut at a plurality of locations and the cross-sectional state was examined, but no void was found. In addition, when the inner peripheral surface of the molded body 10 was observed, it was confirmed that the molded body 10 was smooth without defects such as poor curing. Further, when the roundness of the hollow section of the bottomed cylindrical molded body was measured, it was close to a perfect circle, and it was confirmed that favorable roundness was obtained.

Example 2 A molded body was obtained by performing a reactive polymerization reaction in the same manner as in Example 1 except that a filler was mixed into the reaction stock solution. Silica sand (RS-silica made by Tatsumori, average particle size 1 mm) as filler
Then, 5 kg in total of the reaction stock solution was supplied into the inside of the mold 2 using a nozzle from the axial through hole 5 of the split mold to obtain a bottomed cylindrical molded body.

For confirmation, the bottomed cylindrical molded body was cut at a plurality of locations and the cross-sectional state was examined. No void was confirmed, and silica sand as a filler was uniformly dispersed in the resin layer. Was confirmed. In addition, when the inner peripheral surface of the bottomed cylindrical molded body was observed, it was confirmed that the molded body was smooth without defects such as poor curing. Further, when the roundness of the hollow section of the bottomed cylindrical molded body was measured, it was close to a perfect circle, and it was confirmed that favorable roundness was obtained.

Example 3 A reaction solution containing a norbornene monomer was reacted in the same manner as in Example 1 except that the inclination angle θ of the rotation center axis S of the mold 2 with respect to the horizontal plane H was set to the maximum, that is, 90 °. And polymerized. In addition, as the inclination angle θ was set to 90 °, a different rotation mechanism from that shown in FIG. As a result, a bottomed cylindrical molded body 28 having a shape as shown in FIG. 7 was obtained. In this case, the viscosity of the reaction stock solution is 900 to 300.
It was 0 cps.

[0094]

As described above, according to the reactive polymerization molding method of the present invention, for example, it is possible to easily produce a bottomed cylindrical molded article such as a flowerpot. The shape variations can be expanded. Further, the bottomed cylindrical molded body produced using the reactive polymerization molding method of the present invention has few voids in the molded body, and the shape of the inner surface of the molded body is smooth, and excellent quality is obtained. Have.

[Brief description of the drawings]

FIGS. 1A and 1B are schematic perspective views of a mold used in a reactive polymerization molding method according to one embodiment of the present invention.

FIG. 2 is a side view of a driving device for rotating a mold.

FIG. 3 is a plan view of a driving device.

FIG. 4 is a sectional view of a main part of a mold during molding.

FIG. 5 is a schematic perspective view showing an example of a molded product.

FIG. 6 is a sectional view of a main part of a mold during molding according to another embodiment of the present invention.

FIG. 7 is a schematic sectional view showing an example of a molded product when the mold is rotated at a maximum inclination angle.

FIG. 8 is a diagram for explaining a timing of injecting a reaction stock solution into a mold.

[Explanation of symbols]

 2, 2a ... Mold 3 ... Split surface 4, 4a ... Split die 8, 8a ... Rolling ring 10, 24 ... Molded body 12, 14 ... Driving roll S ... Mold rotation center axis H ... Horizontal plane θ ... Mold Angle of inclination

Claims (2)

[Claims] 1. An unreacted reaction solution in a mold is subjected to a reaction polymerization under a condition where acceleration is applied to the reaction solution in a mold by rotating the mold while inclining a rotation center axis of the mold with respect to horizontal. A reactive polymerization molding method, comprising: 2. A bottomed cylindrical molded product obtained by the reactive polymerization molding method according to claim 1.