JPH09314596A - Manufacture of reaction injection molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To secure firmly an insert on the mold by fixing a support on the inner surface of a mold in use of a sticking agent, and pouring a reaction liquid in the cavity formed within the mold after stationing the insert within the mold via the support so as to be bulk polymerized. SOLUTION: The outer peripheral surface of a vessel, i.e., a melded surface in accordance with configurations of the outer peripheral surface of a covering layer is formed on the upper mold 30 and lower mold 32 respectively. Next, a support 20 is stuck on each inner peripheral surface of the upper mold 30 and lower mold 32. After that, a vessel main body 12 is set on the molds 30, 32 in order to form an interstice equal to only the height of the support body, i.e., a cavity. In this state, a reaction liquid is poured into the cavity C by means of a mixer 40 to be bulk polymerized for forming a covering layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a reaction injection molded article, and more particularly to a method for producing a molded article in which a reaction injection molded resin layer is formed around an insert.

[0002]

2. Description of the Related Art For example, a container in which the outer circumference of a container body made of a polyolefin resin is covered with a polynorbornene resin is being developed, and it is excellent in chemical resistance, load resistance and impact resistance, and therefore it is used in a wide range of fields. Is expected to be applied.

In this type of container, a container body (insert body) made of a preformed polyolefin resin is fixed in a mold, and a reaction liquid such as norbornene monomer is injected into a cavity formed in the mold. It is obtained by bulk polymerization. When manufacturing such a container, the container main body moves in the cavity due to the injection pressure of the reaction liquid, and therefore it is necessary to fix the container main body to the mold. For this reason,
It has been proposed to bond a support to the container body and thereby fix the container body to the mold.

[0004]

However, if the container body and the support body are not firmly adhered to each other, the container body to which the support body is adhered is set when the container body is conveyed to a molding machine or in a mold. At that time, the support might be peeled off from the container body.

Particularly, in the case of a polynorbornene-based resin molded product, the fusion with the reaction heat during the curing reaction is utilized to perform integral molding with the polynorbornene-based resin. Therefore,
Polyolefin resins such as polyethylene, which has a high fusion property with polynorbornene resins, are often used for the container body and the support, but the polyolefin resins are difficult to adhere to each other, and the above-mentioned problems were particularly remarkable. .

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a method for producing a reaction injection-molded article capable of firmly fixing an insert body to a mold.

[0007]

In order to achieve the above object, a method for producing a reaction injection molded article according to the present invention is to fix a support to an inner surface of a mold by using an adhesive to fix the support. After the insert is fixed in the mold via the above, the reaction solution is injected into the cavity formed in the mold to perform bulk polymerization.

In the method for producing a reaction injection molded article of the present invention,
The support is fixed to the inner surface of the mold with an adhesive, and the insert is fixed inside the mold via this support, so when the insert is transported to the molding machine or the insert is set in the mold. When doing
The insert can be firmly supported without the support coming off. Therefore, it is possible to obtain a molded product in which the cavity dimension has an appropriate value and the thickness of the resin layer is as intended.

In the present invention, the shape of the support is not particularly limited as long as it is a shape according to the purpose, and at the position where the support is attached, the gap between the insert and the inner peripheral surface of the mold is predetermined. It is sufficient that the insert can be fixed to the mold so that However, if the contact area between the support and the insert is too small, the buoyancy at the time of injecting the reaction solution and the surface pressure generated by the self-weight of the insert will be high, and the insert will be easily dented at the contact part, so It is preferable to consider the contact area between the insert body and the support body depending on the size, the mounting position of the support body, the number of support bodies mounted, the material and thickness of the insert body, and the like. For example, in the case of producing a container as the molded body according to the present invention, the internal volume is 200 liters,
When fixing a spherical container body (insert body) having a thickness of 4 mm to a mold, use a columnar support having a diameter of about 20 mm, and make sure that about 50 pieces of the circle are brought into uniform contact with the outer peripheral surface of the container body. It is preferable to stick the columnar support in the mold.

When the insert is fixed to the mold via the support, both bottom surfaces of the support, that is, the respective surfaces where the support contacts the insert and the mold, are the surface shapes of the insert and the mold, respectively. It is more preferable to have a shape corresponding to. For example, when fixing the spherical container body as an insert,
One bottom surface of the support is a concave spherical surface corresponding to the spherical surface of the outer circumference of the container body, and the other bottom surface is a convex spherical surface corresponding to the spherical surface of the inner circumference of the mold.

In the present invention, the means for attaching the support to the mold is not particularly limited, but it is preferable to use an adhesive. This is because if the adhesive is applied, it becomes difficult to release the molded product, and the adhesive remains on the surface of the molded product even after the release. The pressure-sensitive adhesive may be directly applied to the support or the mold, but a double-sided pressure-sensitive adhesive tape may be used. For the adhesive or the adhesive tape, select a material that has strong adhesiveness and does not leave an adhesive mark on the surface of the molded product.

Specific adhesives include, for example, nitrile rubber, butyl rubber, isocyanate rubber, styrene-
Examples thereof include butadiene copolymer rubber, styrene-butadiene block copolymer rubber, styrene-isoprene block copolymer rubber, synthetic rubber such as silicone rubber, natural rubber, gum arabic, vinyl acetate and poval.

The height of the support is the thickness of the cavity and the thickness of the resin layer of the target molded product. The support formed in a predetermined shape should be firmly attached to the mold. Then, even if the inflow pressure of the reaction solution is high, the support firmly fixes the insert to the mold, so that a molded product having a target thickness of the resin layer can be obtained.

The reaction stock solution used for reaction injection molding is
Although not particularly limited, urethane-based, urea-based, nylon-based, epoxy-based, unsaturated polyester-based, phenol-based, and norbornene-based, and the like, general molding conditions include a reaction solution temperature of 20 to 80 ° C. The viscosity of the reaction stock solution is, for example, 5 cps to 3 at 30 ° C.
000 cps, preferably 100 cps to 1000 cps
It is a degree.

In such molding, a reinforcing material may be previously placed in a mold, and a reinforced polymer (molded product) may be produced by supplying a reaction solution into the reinforcing material and polymerizing it. As the reinforcing material, for example, glass fiber, aramid fiber, carbon fiber, ultra high molecular weight polyethylene fiber,
Examples thereof include metal fibers, polypropylene fibers, aluminum coated glass fibers, cotton, acrylic fibers, boron fibers, silicon carbide fibers, alumina fibers and the like. Also, whiskers such as potassium titanate and calcium sulfate can be used. Furthermore, these reinforcing materials can be used in various shapes, such as those obtained by matting a long fiber or chopped strand, those woven into a cloth, and those 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 blending amount is not particularly limited, but is usually 10% by weight or more, preferably 20 to 60% by weight based on the total amount of the reaction stock solution.

Further, various additives such as an antioxidant, a filler, a pigment, a colorant, a foaming agent, a flame retardant, a sliding agent, an elastomer, a dicyclopentadiene type thermopolymerization resin and a hydrogenated product thereof are blended. Thereby, the properties of the obtained polymer can be modified. As the antioxidant, there are various antioxidants for plastics / rubbers such as phenol type, phosphorus type and amine type. Filled with milled glass,
There are inorganic fillers such as carbon black, talc, calcium carbonate, aluminum hydroxide and mica. As the elastomer, natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SB
S), styrene-isoprene-styrene block copolymer (SIS), ethylene-propylene-diene terpolymer (EPDM), ethylene vinyl acetate copolymer (EV)
A) and their hydrides.

The additives are usually mixed in advance with one or both of the reaction solutions. In the present invention, the reaction injection molding resin layer is particularly preferably composed of a polynorbornene-based resin obtained by a reaction injection molding (RIM) method. In particular, those composed of a ring-opened polymer of a norbornene-based monomer modified with an elastomer are preferable.

Examples of the elastomer include polybutadiene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SB).
S), polyisoprene, styrene-isoprene-styrene block copolymer (SIS), ethylene-propylene-diene terpolymer (EPDM) and the like.

The mixing ratio of the elastomer is 1 to 20 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the norbornene-based monomer. When the blending ratio of the elastomer is low, the flexibility decreases. Conversely, if the proportion of the elastomer is too large, the glass transition temperature decreases and the strength decreases, which is not preferable.

The norbornene-based monomer is a cycloolefin having a norbornene ring such as dicyclopentadiene, dihydrodicyclopentadiene, tetracyclododecene and tricyclopentadiene. The metathesis catalyst is not particularly limited as long as it is a known metathesis catalyst for bulk polymerization of norbornene-based monomers such as organic hexamolybdate ammonium salts such as tungsten hexachloride, tridodecyl ammonium molybdate, and tri (tridecyl) ammonium molybdate. However, ammonium ammonium molybdate is particularly preferable.

Examples of the activator (cocatalyst) include alkyl aluminum halides such as ethyl aluminum dichloride and diethyl aluminum chloride, alkoxyalkyl aluminum halides, and organic tin compounds.
As a preparation for reaction injection molding, a reaction injection molding material containing a norbornene-based monomer, a metathesis catalyst, and an activator as a main component is a liquid comprising a norbornene-based monomer and a metathesis catalyst, and the norbornene-based monomer and the activator are used. Separately into two stable liquids and separate liquids.

At the time of reaction injection molding, the two liquids are mixed, and then the mixed liquid is injected into a cavity of a mold in which the insert is fixed, and bulk polymerization is carried out in the cavity to form a poly in the insert. A molded product in which the norbornene-based resin layer is integrally formed is obtained. Since this reaction injection molding is performed by inserting the insert into the mold in advance, it is also insert molding.

The metal mold used for the reaction injection molding does not necessarily have to be an expensive metal mold having high rigidity, and it is not limited to a metal metal mold, and a resin metal mold or a simple mold can be used. This is because the reaction injection molding of the norbornene-based resin can be performed at a relatively low temperature and a low pressure using a low-viscosity reaction liquid. The inside of the mold is sealed with an inert gas, and the components used for the polymerization reaction are stored under an inert gas atmosphere such as nitrogen gas.
And it is preferable to operate.

The mold temperature for forming the norbornene-based resin layer is within a temperature range in which the polymerization reaction of the norbornene-based resin can be sufficiently maintained and the material (for example, polyolefin-based resin) forming the insert body is not thermally deformed. . It is preferably 10 ° C. or higher, more preferably 30 ° C. or higher, further preferably 50 ° C. or higher, and preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 100 ° C. or lower. If it is too low, the polymerization reaction of the norbornene-based monomer cannot be maintained, and if it is too high, the insert tends to be deformed. When the insert is made of polyethylene, for example, it is preferably 80 ° C or lower, more preferably 70 ° C or lower, and further preferably 6 ° C or lower.
Keep below 0 ° C. Mold pressure is usually 0.1-100kg
/ Cm ² . The polymerization time may be appropriately selected, but is usually 30 seconds to 20 minutes after the completion of the injection of the reaction solution.

In the present invention, the material of the support is not particularly limited, but is composed of a polyolefin resin such as polyethylene or polypropylene. In the present invention, the material of the insert is not particularly limited, and may be metal or the like. However, the following effects can be expected by forming the insert with a polyolefin resin such as polyethylene or polypropylene.

By forming the polynorbornene-based resin layer on the insert made of a polyolefin-based resin having a high fusion property with the polynorbornene-based resin, the insert and the polynorbornene-based resin layer are firmly fixed and peeled off. Can be prevented. When the support is also made of a polyolefin-based resin, the adhesion between the support and the polynorbornene-based resin layer is also enhanced. In addition to this,
Despite the low adhesiveness between the polyolefin resins, that is, the support and the insert, since the support is attached to the mold in the present invention, it is possible to prevent the support from peeling off, which is particularly effective. .

The polynorbornene-based resin molded article of the present invention is not particularly limited, but for example, the insert may be formed of a hollow container main body having a mouth portion formed therein to have a container shape. The shape and thickness of the container body are not particularly limited, but it is preferable that the container body has a uniform thickness, and it is more preferable that the container body is spherical except for the mouth portion. A uniform thickness reduces unevenness in the strength of the entire container, and a spherical shape minimizes unevenness in the strength of the entire container, increases resistance to internal pressure, and increases capacity with a minimum surface area. Become.

The thickness of the container body in the case of coating with a polynorbornene resin layer is 1 mm or more, preferably 2 mm or more, more preferably 2.5 mm, because it is not thermally deformed by the heat of polymerization during the reaction of the norbornene monomer. That is all.
Further, if the thickness of the container body is too large, the moldability is reduced. Therefore, the thickness is set to 7 mm or less, preferably 6 mm or less, more preferably 5 mm or less.

The size of the container body is not particularly limited, but the content is preferably 30 liters or more, more preferably 50 liters or more, preferably 1000 liters or less, more preferably 500 liters or less. If the content is too small, the buoyancy of the container body is small, it is difficult to deform, the container is relatively strong, and even if the thickness of the polynorbornene-based resin layer is not uniform, there may be no problem in use. If the container has a certain content or more, the buoyancy of the container body is large, so that it is easily deformed, and if the thickness of the polynorbornene-based resin layer is uneven, the strength of the container becomes uneven, causing damage. There are cases.

When it is possible to seal the inside of the container, it may be preferable to fix a metal socket, for example, to the mouth portion. In such a case, therefore, a protruding mouth portion is provided on the container body. When manufacturing such a container, it is preferable to put a weight in the container body at least when injecting the reaction liquid into the cavity. By doing so, it is possible to receive the buoyancy generated when the reaction solution is injected, maintain the fixation to the mold, and prevent the deformation of the container body caused by the buoyancy and the pressure difference between the reaction solutions. Is.

As the weight, it is preferable that the container body is not deformed by its own weight by uniformly applying a load to the inside of the container body, and it is also necessary that the container body can be taken in and out. Therefore, the weight according to the present invention is preferably a powder or a liquid. When powder or liquid is used as the weight, in order to prevent not only the floating of the container body but also the deformation of the reaction liquid injected into the mold due to the pressure difference, 50% or more of the internal volume is used. , Preferably 6
0% or more, more preferably 70% or more and 100%
Fill the container body with the following weights. If the amount is too small, the container body is likely to be deformed by the influence of buoyancy and the like. For the same reason, a weight having a specific gravity of 0.8 or more, preferably 0.9 or more, and 2.0 or less, preferably 1.5 or less, more preferably 1.2 or less is used. In addition,
The specific gravity when powder is used as the weight refers to the effective specific gravity of the weight including air and the like existing in the space between the powders. As the weight according to the present invention, other than powder or liquid can be used, but it is particularly preferable to use water because it is easy to obtain and use and can be easily disposed of.

The temperature of the weight is preferably 10 ° C. or higher, more preferably 15 ° C. or higher, and preferably 40 ° C. or lower, more preferably 35 ° C. or lower. If the temperature of the weight is too low, the heat generated by the curing reaction of the reaction liquid is absorbed by the weight, which may make it difficult to maintain the reaction or may require a long reaction time. On the other hand, if the temperature of the weight is too high, the temperature of the container main body rises due to the heat generation of the curing reaction of the reaction liquid, and the container is likely to be thermally deformed.

When a weight is put in the container body, it is necessary that the weight does not come out from the mouth of the container body, but the means is not particularly limited. For example, when powder or liquid is used as the weight, it is preferable to install the container main body in the mold so that the mouth portion is located above.

The timing at which the weight is put into the container body is not particularly limited as long as at least the reaction solution is injected into the cavity, but if the weight is put in before the container body is fixed to the mold, the mold of the container body is Since the operability of fixing to the mold decreases, it is more preferable to add a weight after fixing the container body to the mold and before clamping the mold.

As another method for preventing deformation of the container body due to buoyancy or injection of the reaction solution, the inside of the container body may be pressurized at least when the reaction solution is injected into the cavity. By doing so, the buoyancy and the pressure of the reaction liquid are received, and thus the deformation of the container body can be prevented.

The means for pressurizing the inside of the container body is not particularly limited, but it is more preferable to enclose a gas. The gas in the case where gas is sealed in the container body and pressurized is not particularly limited as long as the gas does not corrode the container body. Air or nitrogen is more preferable in consideration of easy availability, handling, and disposal. The inside of the container body is pressurized at a gauge pressure of 0.10 atm or more, preferably 0.15 atm or more, and preferably 0.30 atm or less, more preferably 0.25 atm or less.
If the internal pressure is too low, the buoyancy and the pressure of the reaction solution cannot be sufficiently received to prevent deformation of the container body, and if the internal pressure is too high, the container body may be damaged. It is preferable to set the pressing force to an appropriate value according to the strength of the main body.

The timing of enclosing and pressurizing the gas in the container main body is not particularly limited as long as it is pressurized at least when the reaction liquid is injected into the cavity, so long as it is before the injection. In addition, when the container body is filled with gas and pressurized, the weight of the container body does not increase so much, so the operability of fixing the container body to the mold is less affected, and therefore, before the injection of the reaction solution. In this case, either before or after fixing the container body to the mold, it may be either.

The gas can be sealed in the container body by using a socket provided at the mouth of the container body and attaching a lid having a check valve, for example. The molded product obtained by the present invention is a molded product that is extremely resistant to breakage, has high durability, high impact resistance, and high chemical resistance.
When applied as a container, the liquid stored in the container is pure water, tap water, sewage, kerosene, gasoline, etc.
There is no particular limitation as long as the resin constituting the container body is not dissolved. In addition, applications that may be deformed by the application of external force, such as septic tanks, water tanks, pond tanks, underground containers such as buried storage tanks, and containers installed on the ground such as tanks, or substances enclosed inside It is suitably used for various applications that need to prevent leakage and penetration into the inside. As a specific application example, it can be used as a kerosene buried storage tank, and the surface of the buried place can be used as a parking lot or the like. When storing liquid etc. in an embedded storage tank like a kerosene embedded storage tank, a plurality of sockets are attached, those sockets are attached, a liquid inflow coupler, a liquid discharge coupler, an exhaust valve, The liquid may be stored and taken out easily by attaching an intake valve or the like. Instead of attaching a socket, a liquid inflow coupler, a pipe having a coupler at one end and extending to the bottom in the container at the other end, an exhaust valve, an intake valve, or the like may be directly attached to the opening. Further, since the molded product obtained by the present invention has excellent load bearing property itself, the number of reinforcing portions such as ribs can be reduced, so that the moldability is also improved.

[0039]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for producing a polynorbornene-based resin molded article of the present invention will be described in detail based on an embodiment shown in the drawings. 1 and 2 are cross-sectional views for explaining the manufacturing method of the present invention, which is an embodiment in which a spherical container is configured as a molded product. 1 (A) and 2 (A) are sectional views showing the entire mold, FIG. 1 (B) is a perspective view showing a support, and FIG. 2 (B) is a main part showing a reaction resin injection machine. FIG.

3A and 3B are perspective views showing the container according to the above embodiment, FIG. 3A is a perspective view showing the container body, and FIG. 3B is a perspective view showing a state in which a socket is attached to the container body.
FIG. 4C is a perspective view showing the container after molding, and FIG. 4 is a sectional view showing the container according to the embodiment shown in FIG.

The container 10 shown in FIG. 3C has a container body 12 inside, a coating layer 14 outside, and a socket 16 attached to a cylindrical mouth portion 12a of the container body. In the state where the socket 16 is attached to the container body 12 that is preformed so as to have 12a, the covering layer 14
The container 10 according to the present embodiment is formed by molding. The center of the spherical portion of the container body 12 is located in the extension of the central axis of the cylindrical mouth portion 12a.

The container body 12 shown in FIG. 3 (B) is made of a polyolefin resin such as polyethylene or polypropylene which has a good fusion property with the polynorbornene resin forming the coating layer 14, and is formed by the blow molding method. It is formed into a spherical shape having a uniform thickness by a rotational molding method or the like. As in the present embodiment, by making the shape of the container body 12 a spherical shape having a uniform thickness, the strength of the entire container 10 is reduced, the pressure resistance from the inside is strong, and the minimum surface area is required. This has the advantage of increasing the capacity.

A metal socket 16 is fixed to the mouth 12a of the container body 12 so that the inside of the container 10 can be sealed. The metal socket 16 is formed to have an outer diameter that is substantially the same as the inner diameter of the mouth 12a of the container body 12, as shown in FIG.
As shown in FIG. 4 and FIG. 4, with the lower portion inserted into the mouth 12a of the container body 12, the pressure fastener 18 such as a string-shaped or band-shaped wire or band is attached to the mouth 12a of the container body 12.
It is clamped and fixed by wrapping it around the outer circumference. In this embodiment, the lower portion of the metal socket 16 is the container body 1
The metal socket 16 is inserted into the second opening 12a and fixed by the pressure fastener 18, and the upper portion of the metal socket 16 is fixed by being adhered to the polynorbornene-based resin forming the coating layer 14. It becomes difficult for the metal socket 16 to slip off, and since the upper part of the metal socket 16 is in close contact with the coating layer 14, the sealing property is also excellent.

A screw is formed on the inner peripheral surface of the metal socket 16, and when it is used as the container 10, a lid (not shown) having a screw to be screwed to the screw is attached to the container, and the container is The sealing property in 10 is secured. In the present embodiment, the covering layer 14 is provided with reinforcing ribs 14a extending in the latitude direction and the longitude direction, respectively. Incidentally, the latitude direction and the longitude direction are the cylindrical mouth portion 12
The direction of latitude and the direction of longitude when the central axis of a is viewed as the axis of rotation. The longitudinal ribs 14a are preferably present at equal intervals. When forming a leg part by a part of rib 14a so that it may mention later, three or more ribs 14a of the longitudinal direction are required, Preferably four or more are required. However, if the amount is too large, molding becomes difficult, and the amount is preferably 10 or less. FIG.
The container 10 shown in (C) has a rib 14a in the longitudinal direction of 90 °.
It has four at intervals. Further, the container 10 has one latitudinal rib 14a at the equator portion. This reinforcing rib 14a has the function of increasing the rigidity of the container 10, and the leg portion 1 is provided by the lower end of the reinforcing rib 14a extending in the longitudinal direction.
4b is formed and has a function of seating the container 10. In the container 10 shown in FIGS. 3 (C) and 4, the leg portion 14b is formed by cutting the reinforcing rib 14a at a surface orthogonal to the rotation axis and in contact with the surface of the spherical portion of the container 10. In the present embodiment, the thickness t of the general surface of the coating layer 14 is not particularly limited, but if it is too thin, the container 10 is likely to be damaged, so 2.5 mm or more, preferably 3 mm or more, more preferably 3.5 mm or more. And Further, if the thickness t of the coating layer 14 is too large, the moldability decreases and it takes time, so the thickness is set to 7 mm or less, preferably 6 mm or less, more preferably 5 mm or less. On the other hand, the height H of the rib 14a is preferably 100 to 1200% of the thickness t, and the width of the rib 14a is preferably 50 to 25% of the thickness t.
0%. However, a part of the rib 14a is the leg 1
When configuring 4b, the portions that configure the legs may deviate from this range to improve installation stability. The width of the rib 14a is the width of the root portion, and the tip of the rib may be narrower than the width.

In this embodiment, the coating layer 14 is composed of a ring-opening polymer of a norbornene-based monomer modified with an elastomer. By forming the coating layer 14 from a polynorbornene-based resin obtained by the reaction injection molding method, the container body 12 is satisfactorily coated and molded by utilizing the material characteristic that the viscosity of the material during molding is extremely low, It has an advantage that it can be easily integrally molded.

Next, the manufacturing method will be described. First, the container body 12 as shown in FIG. 3 (A) is molded by the blow molding method or the rotational molding method, and the lower portion of the metal socket 16 is inserted into the opening 12 a and fixed by the pressure fastener 18.

Further, the container body 12 is attached to the molds 30, 32.
1B, the polyolefin-made support 20 formed in a cylindrical shape as shown in FIG. 1B is provided on the inner peripheral surfaces of the molds 30 and 32 at substantially equal intervals as shown in FIG. 1A. Glue with. The support body 20 is arranged such that the distance between the outer peripheral surface of the container body 12 and the inner peripheral surfaces of the molds 30 and 32 (that is, the gap of the cavity C) has a predetermined size at the position where the support body 20 is attached. The container body 12 is fixed to the molds 30 and 32. If the contact area between the support 20 and the container body 12 is too small, the surface pressure generated by the buoyancy at the time of injecting the reaction solution, the weight of the container body 12, the weight of the weight W filled in the container body 12, and the like increases. Since the container body 12 is likely to be dented at the contact portion, the container body 12 is dependent on the size of the buoyancy, the mounting position of the support body 20, the number of the supporting body 20 mounted, the material and thickness of the container body 12, and the like.
The contact area between the support and the support 20 is taken into consideration. For example,
In the present embodiment, when the spherical container body 12 having an internal capacity of 200 liters and a thickness of 4 mm is fixed to the molds 30 and 32,
A cylindrical support 20 having a diameter of about 20 mm is used, and the dies 30, 32 are made to contact the outer peripheral surface of the container body 12 substantially uniformly.
About 50 pieces are arranged on the inner peripheral surface.

The bottom surface of the support 20, that is, the surface where the support 20 contacts the container body 12 and the molds 30 and 32 has a shape corresponding to the surface shape of the container body 12 and the molds 30 and 32, respectively. ing. That is, in the present embodiment, one bottom surface of the support 20 is a concave spherical surface corresponding to the spherical surface of the outer circumference of the container body 12, and the other bottom surface is a convex spherical surface corresponding to the spherical surfaces of the inner circumferences of the molds 30 and 32. The means for attaching the support 20 to the container body 12 is not particularly limited, but an adhesive is preferable. A liquid pressure-sensitive adhesive may be used as the pressure-sensitive adhesive, but a double-sided pressure-sensitive adhesive tape may also be used. As the adhesive, a material that has high adhesiveness to the molds 30 and 32 and has little adhesive residue is selected. In this embodiment, a double-sided pressure-sensitive adhesive tape coated with a pressure-sensitive adhesive made of a styrene-isoprene-styrene block copolymer is used.

The height of the support 20 is the thickness of the cavity C, which is the thickness of the target coating layer 14 of the container 10. The support 20 formed in a predetermined shape is attached to the container body 12. By being firmly attached, the support body 20 firmly attaches the container body 12 to the molds 30, 3 even when the reaction solution flows in.
Since it is fixed to 2, the container 10 having the target thickness of the coating layer 14 can be obtained.

After the support 20 is adhered to the inner peripheral surfaces of the molds 30 and 32, the container body 12 is set in the molds 30 and 32. Before or after setting, the container body 12 is set in the container body 12. Fill with water W. The amount of the water W filled in the container body 12 is not only to prevent the container body 12 from floating, but also to prevent the reaction liquid injected into the molds 30 and 32 from being deformed due to the pressure difference. 50% or more of the amount, preferably 60% or more, more preferably 70% or more, and 1
It is set to 00% or less. The water temperature is preferably 10 ° C or higher, more preferably 15 ° C or higher, and preferably 40 ° C.
C. or lower, more preferably 35.degree. C. or lower. If the water temperature is too low, the exothermic heat of the curing reaction of the reaction liquid is absorbed by the weight, which may make it difficult to maintain the reaction or may require a long reaction time. On the other hand, if the water temperature is too high, the temperature of the container body 12 rises due to the heat generated by the curing reaction of the reaction liquid, and the container body 12 is likely to be thermally deformed.

As shown in FIGS. 1 and 2, the molding apparatus in this embodiment has an upper mold 30 and a lower mold 32, which are provided so as to be relatively close to and away from each other. Upper mold 3
0 and the lower mold 32 respectively include an outer peripheral surface of the container 10,
That is, a molding surface corresponding to the shape of the outer peripheral surface of the coating layer 14 is formed, and after the support 20 is adhered to the inner peripheral surfaces of the upper mold 30 and the lower mold 32 as shown in FIG. When the main body 12 is set in the molds 30 and 32, as shown in FIG. 2A, a gap corresponding to the height of the support 20, that is, a cavity C is formed. Mold 30, 32
One (lower mold 32 in FIG. 1A) is provided with an injection port 34 for injecting the reaction liquid into the cavity C, and the injection port 34 is provided with a mixer 40.

The mixer 40 mixes and discharges the reaction solution A and the reaction solution B, and has an advancing / retreating rod 42 in the center. Then, in the state before the injection shown in FIG.
As the advancing / retreating rod 42 advances, the reaction liquid A and the reaction liquid B circulate in the respective circulation closed circuits and are not mixed. However, at the time of injection shown in FIG. Thereby, the reaction liquid A and the reaction liquid B are mixed in the mixer 40, and are filled into the cavity C via the injection port 34.

In the present embodiment, in order to form the coating layer 14 from the polynorbornene-based resin, a liquid composed of a norbornene-based monomer and a metathesis catalyst is used as the reaction liquid A, and the above-mentioned norbornene-based monomer and an active material are used as the reaction liquid B. A liquid consisting of the agent was used. When the norbornene-based monomer is bulk polymerized in the cavity C by such a reaction injection molding method, the container 10 as shown in FIG. 3C can be obtained. At this time, the container body 12 is moved to the mold 30,
Since the support body 20 is adhered to the molds 30 and 32 in order to fix the container body 12 to the mold 32, when the container body 12 is conveyed to the molding machine or when the container body 12 is set in the molds 30 and 32. The support body 20 does not peel off, and therefore, the molding can be performed with the container body 12 firmly fixed in the molds 30 and 32. As a result, the container 10 in which the coating layer 14 has a uniform thickness can be obtained.

Further, since water W, that is, a weight is contained in the container body 12 at least when the reaction solution is injected into the cavity C, the buoyancy generated when the reaction solution is injected is received and the molds 30, 32 are received. While maintaining the fixation to
It is possible to prevent the deformation of the container body 12 caused by the buoyancy and the pressure difference between the reaction solutions. As a result, the container 10 in which the coating layer 14 has a uniform thickness can be obtained.

The present invention is not limited to the above-mentioned embodiment, but can be variously modified within the scope of the present invention. For example, the shape and the number of forming the reinforcing ribs 14a are not limited to those in the above-described embodiment, can be variously modified, and may be omitted as necessary. The cross-sectional shape and dimensions of the container 10 are not particularly limited and can be modified in various ways.

Further, the insert body is not limited to the container shape, and may have any shape such as a flat plate shape, a curved plate shape, and a block shape. Moreover, the insert does not necessarily have to be entirely covered with the reaction injection molding resin layer, and a part of the insert may be exposed to the outside.

Furthermore, the material of the insert is not particularly limited, and may be metal, ceramic or the like other than resin.

[0058]

EXAMPLES The present invention will be described below based on more specific examples, but the present invention is not limited to these examples. Example 1 In this example, first, as shown in FIG.
An insert 12 made of an iron plate having a length of 82 mm and a length of 82 mm was produced. The insert 12 is made of metal.

Further, 18 columnar polyethylene supports 20 having a height of 4 mm and a diameter of 7 mm were prepared, and these were used with a double-sided adhesive tape (Bond Tape BT-12, manufactured by Sumitomo 3M Ltd.), as shown in FIG. Flat plate molding die 3 having a cavity with a depth of 15 mm and vertical and horizontal dimensions of 100 mm
It was pasted on 0 and 32.

Then, the insert 12 is attached to the molds 30, 32.
And the upper die 30 and the lower die 32 were clamped. The cavity is hermetically sealed except for the reaction solution inlet and the cavity air vent hole, and the distance between the outer peripheral surface of the insert 12 and the inner peripheral surfaces of the molds 30 and 32 is 4 mm.

Preparation of the reaction resin stock solution was carried out as follows. That is, dicyclopentadiene (DCP) 85%
A norbornene-based monomer comprising 15% of asymmetric cyclopentadiene trimer and styrene-isoprene-styrene block copolymer (Kreton 117
0, manufactured by Shell Co., Ltd.) and 2% of Irganox 1010 (Ciba Geigy), a phenolic antioxidant.
% Dissolved in two containers, and to one of them was added diethyl aluminum chloride (DEAC) at a concentration of 40 mmol, n-propanol at a concentration of 44 mmol, and silicon tetrachloride at a concentration of 20 mmol relative to the monomer. (Solution A). On the other hand, tri (tridecyl) ammonium molybdate was added to the monomer at a concentration of 10 mmol (Solution B).

Liquids A and B were respectively sent to the mixer 40 by a gear pump so as to have a volume ratio of 1: 1,
Then, the mold temperature was set to 55 ° C. and the injection pressure (2.0) was applied from the injection port of the mold to the cavity in which the insert 12 was set.
Injection was performed at Kg / cm ² or less. 10 in mold 30, 32
The reaction was performed for minutes.

Then, the molds 30 and 32 are opened, the molded product is taken out, the double-sided adhesive tape on the surface is peeled off, and the insert 1 is inserted.
A molded product having a polynorbornene-based resin layer formed on the outer peripheral surface of No. 2 with a thickness of 15 mm and length and width of 100 mm was obtained.
When the position where polyethylene was exposed on the surface of this molded product was observed, it was confirmed that the support 20 did not move.

Comparative Example 1 The procedure of Example 1 was repeated except that the support 20 was simply sandwiched between the molds 30 and 32 and the insert 12 to fix the insert 12 to the molds 30 and 32. , Manufactured a molded product.
Three molded products were prepared for convenience.

When the position where polyethylene was exposed on the surface of this molded product was observed, the support 20 was moved in all three, and the center of gravity of one of the three molded products was It was confirmed that it was not centered and therefore the insert 12 also moved during molding.

Example 2 A 500 mm × 300 mm × 30 mm flat plate molding die was provided with 16 polyethylene support members 20 having a diameter of 20 mm and a thickness of 10 mm at the four upper and lower corners, and a double-sided adhesive tape (bond tape BT-12, It was pasted using Sumitomo 3M). 480 mm x 28 in this mold 30, 32
A 0 mm × 10 mm iron insert 12 was set.

On the other hand, dicyclopentadiene (DCP) 9
0% and cyclopentadiene trimer (asymmetric trimer) 1
A norbornene-based monomer consisting of 0% was placed in two containers, and diethyl aluminum chloride (DEAC) was added in a molar ratio of 40 to the monomer in one container, 1,3-dichloro-
2-Propanol (dCPrOH) was added so as to have a concentration of 48 mmol (Liquid A). On the other hand, 1 (tridodecyl) ammonium molybdate for the monomer
The solution was added so as to have a concentration of 0 mmol (solution B).

The temperature of the mold is raised to about 50 ° C. by flowing hot water through the temperature control pipe that penetrates the molds 30 and 32 into the mold, and the same volumes of liquid A and liquid B are introduced into the cavity by a reaction injection molding machine. The mixture was mixed and poured in, and after about 5 minutes, the molded product was taken out from the mold. When the molded product taken out was observed, it was confirmed by an ultrasonic flaw detector that the insert was in a predetermined position without detachment of the support.

Comparative Example 2 A polyethylene support having a diameter of 20 mm and a thickness of 10 mm was attached to the four corners of the iron insert using 16 pieces of double-sided adhesive tape (bond tape BT-12, manufactured by Sumitomo 3M Limited). Was molded in the same manner as in Example 2 above.

When the molded product taken out of the mold was observed, it was confirmed by an ultrasonic flaw detector that a part of the support was peeled off from the insert and the insert was not in a predetermined position.

[0071]

As described above, according to the method for producing a reaction injection-molded article of the present invention, when the insert is conveyed to the molding machine or when the insert is set in the mold, the support is The insert can be firmly supported without coming off. Therefore, it is possible to obtain a molded product in which the cavity size has an appropriate value and the thickness of the reaction injection molding resin layer is the target.

Further, the resin layer is made of a polynorbornene resin, and the insert is made of a polyolefin resin having a high fusion property with the polynorbornene resin, whereby the insert and the polynorbornene resin layer are formed. Is firmly fixed and peeling can be prevented.

[Brief description of drawings]

1A and 1B are views for explaining a method of manufacturing a container according to an embodiment of the present invention, in which FIG. 1A is a cross-sectional view showing the entire mold, and FIG. 1B is a perspective view showing a support. It is a figure.

2A and 2B are views for explaining a method of manufacturing a container according to an embodiment of the present invention, in which FIG. 2A is a sectional view showing the entire mold, and FIG. 2B is a reaction resin mixer. It is a principal part sectional view shown.

FIG. 3 is a perspective view showing a container according to an embodiment of the present invention, (A) being a perspective view showing a container body, and (B).
Is a perspective view showing a state where a socket is attached to the container body,
(C) is a perspective view showing a container.

4 is a cross-sectional view showing a container according to the embodiment shown in FIG.

FIG. 5 is an exploded perspective view showing a mold according to an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 ... Container (molded product) 12 ... Container main body (insert body) 14 ... Coating layer (reaction injection molding resin layer) 20 ... Support 30 ... Upper mold (mold) 32 ... Lower mold (mold) C ... Cavity W … Water (weight)

Claims (1)

[Claims] 1. A support is fixed to an inner surface of a mold using an adhesive, and an insert is fixed in the mold through the support, and then is inserted into a cavity formed in the mold. A method for producing a reaction injection-molded article in which a reaction solution is injected to perform bulk polymerization.