JPH10138347A - Composite molding and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a molding having excellent airtightness and water tightness of a connected surface and a container such as a tank to be manufactured by using the method. SOLUTION: The method for manufacturing a molding 100 having the step of connecting two or more molding constituting members 100a, 100b constituted by a multilayer resin having at least inner layers 12a, 12b and reaction injection molding resin layers 14a, 14b to one another at flange connecting surfaces comprises the steps of interposing a sheet material 15 including a conductive material between connecting surfaces of the layers 12a, 12b and applying a magnetic field to the connecting surfaces.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite molded article having a double layer structure of a base material layer and a coating layer obtained by joining two or more molded article constituent members, and a method for producing the same.

[0002]

2. Description of the Related Art Containers, such as tanks, in which the outer periphery of a container body made of a polyolefin resin is coated with a reaction injection molded layer of a polynorbornene resin, etc., are being developed and have excellent chemical resistance and load resistance. Is expected to be applied to a wide range of fields.

In this type of container, a container body made of a pre-formed polyolefin resin is fixed in a mold, and a cavity formed in the mold is filled with a reaction resin stock solution such as a norbornene-based monomer to form a bulk polymerization. To be obtained.

[0004]

However, since it is difficult to integrally mold a large-capacity container, the container body is divided into two parts, and a polynorbornene-based resin layer is formed on each outer peripheral surface. After forming these, it has been attempted to join them.

[0005] In this case, a container component having a multilayer structure including at least a polyolefin-based resin layer and a polynorbornene-based resin layer is joined. Then, in order to ensure airtightness or watertightness at the joint surface, it is considered that fusion with the polyolefin-based resin layer is preferable, but it has been extremely difficult to fuse the polyolefin-based resins together.

[0006] The present invention has been made in view of such circumstances, and has as its object to provide a composite molded article excellent in air-tightness and water-tightness of a joint surface and a method for producing the same.

[0007]

In order to achieve the above object, a composite molded article according to the present invention comprises at least two molded articles each having at least a base layer and a coating layer covering the outer periphery of the base layer. The constituent members are composite molded bodies joined to each other at joint surfaces, and joints formed of the base material layers are joined by heat generated by an electromagnetic induction heating element interposed between the joint surfaces.

In the method for producing a composite molded article according to the present invention, a coating layer is formed so as to cover the outer periphery of the base material layer to form a molded article constituting member, which is located on a joint surface of the molded article constituting member. An electromagnetic induction heating element is interposed between base material layers, and the electromagnetic induction heating element is subjected to electromagnetic induction heating in a non-contact manner so that the base material layers located on the bonding surface are fused to each other or via an adhesive layer. And

Preferably, the joint surface is a flange joint surface. Substrate layer The substrate layer is preferably one of a single layer, two layers and three layers. The base layer preferably includes at least a polymer layer containing a nonpolar monomer as a main component. The base layer has at least a first polymer layer formed of a polymer mainly composed of a nonpolar monomer and a second polymer layer formed of a polymer mainly composed of a polar monomer. Is more preferred. In addition, the base material layer is formed of two first polymers formed of a polymer containing a nonpolar monomer as a main component.
It may have a three-layer structure in which a second polymer layer formed of a polymer containing a polar monomer as a main component is interposed between polymer layers.

The first polymer layer is a polymer containing a non-polar monomer as a main component.
More than 70% by weight, more preferably more than 90% by weight, more preferably more than 90% by weight of the polymer.

Examples of the non-polar monomer include olefins such as ethylene, propylene and butylene; and aromatic vinyls such as styrene.

Specific examples of the polymer forming the first polymer layer include polyolefins such as polyethylene, polypropylene and ethylene-propylene copolymer, polystyrene, and ethylene / vinyl acetate copolymer (ethylene exceeding 50% by weight). Is preferably one selected from the group consisting of

The second polymer layer is composed of a polymer containing a polar monomer as a main component, usually a polymer containing the polar monomer in an amount of more than 50% by weight, preferably 55% by weight or more, more preferably 60% by weight or more. Is done.

Examples of the polar monomer include vinyl monomers having a polar group such as vinyl chloride, vinylidene chloride, vinylidene fluoride, vinyl alcohol, acrylates and methacrylates; polycarboxylic acids, polyalcohols, polycondensation monomers And the like.

Specific examples of the polymer constituting the second polymer layer include, for example, polyamide, polyvinyl alcohol (PVA), ethylene / vinyl alcohol copolymer (more than 50% by weight of vinyl alcohol), polyester, polyvinyl chloride, It is preferably one selected from the group consisting of halides such as polyvinylidene chloride and polyvinylidene fluoride. The method of forming the base material layer composed of the multilayer film is not particularly limited, and examples thereof include a multilayer extrusion blow molding method and a multilayer injection blow molding method. Coating Layer In the present invention, the coating layer is preferably a reaction injection molded resin layer obtained by a reaction injection molding (RIM) method. This is because the base layer has an excellent reinforcing effect.

The stock solution used for the RIM is not particularly limited, but includes urethane-based, urea-based, nylon-based, epoxy-based, unsaturated polyester-based, phenol-based, and norbornene-based resins. Preferably, it is configured. Specific norbornene monomers for constituting the resin include:
For example, cycloolefin having a norbornene ring such as dicyclopentadiene, dihydrodicyclopentadiene, tetracyclododecene, and tricyclopentadiene is used.

The metathesis catalyst is a known metathesis catalyst as a catalyst for bulk polymerization of norbornene-based monomers such as organic ammonium molybdate such as tungsten hexachloride, tridodecyl ammonium molybdate and tri (tridecyl) ammonium molybdate. Although there is no particular limitation, organic ammonium molybdate is particularly preferred.

Examples of the activator (cocatalyst) include alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride, alkoxyalkylaluminum halides thereof, and organotin compounds.

Further, various additives such as an antioxidant, a filler, a pigment, a coloring agent, a foaming agent, a flame retardant, a sliding agent, an elastomer, a dicyclopentadiene-based thermopolymerized 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. Examples of the elastomer include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), and 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 hydrides thereof.

The proportion 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 monomer. If the proportion of the elastomer is small, the flexibility is reduced. Conversely, if the proportion of the elastomer is too large, the glass transition temperature decreases and the strength decreases, which is not preferable.

In order to carry out the reaction injection molding, as a preparation for the reaction injection molding, a reaction injection molding material mainly composed of a norbornene monomer, a metathesis catalyst and an activator is mixed with a liquid comprising a norbornene monomer and a metathesis catalyst. And a stable liquid consisting of the above-mentioned norbornene-based monomer and an activator, and put into another container. The additive is usually mixed in advance with one or both of the reaction solutions.

At the time of reaction injection molding, two liquids are mixed,
Next, this mixed solution is injected into a cavity of a mold in which a base material layer made of a polyolefin resin or the like is fixed, and bulk polymerization is performed in the cavity, so that a reaction injection molding layer is integrally formed outside the base material layer. To obtain a molded article. Since this reaction injection molding is performed by inserting the base material layer into the mold in advance, it is also insert molding.

As general molding conditions, the temperature of the reaction solution is 20 to 80 ° C., and the viscosity of the reaction solution is, for example, 30 ° C.
In C, 5 cps to 3000 cps, preferably 10 cps
It is about 0 cps to 1000 cps.

In such molding, a reinforcing material (molded article) can be produced by placing a reinforcing material in a mold in advance and supplying a reaction liquid therein to polymerize.

Examples of the reinforcing material include glass fiber, aramid fiber, vinylon fiber, carbon fiber, ultra high molecular weight polyethylene fiber, metal fiber, polypropylene fiber, aluminum coated glass fiber, cotton, acrylic fiber, boron fiber, and silicon carbide fiber. , 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 amount is not particularly limited, but is usually 10% by weight or more, preferably 20 to 60% by weight.

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 resin (for example, polyolefin-based resin) constituting the base material layer is not thermally deformed. is there. It is preferably at least 10 ° C, more preferably at least 30 ° C, still more preferably at least 40 ° C, and preferably at most 150 ° C, more preferably at most 120 ° C, even more preferably at most 100 ° C. If it is too low, the polymerization reaction of the norbornene-based monomer cannot be maintained, and if it is too high, there is a problem that the base material layer composed of the polyolefin-based resin is easily deformed. When the substrate layer is made of, for example, polyethylene, the temperature is preferably 90 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 70 ° C. or lower.

The temperature of the mold can be controlled by providing a passage for the heat medium in the mold and circulating the heat medium. Mold pressure is usually 0.1-100 kg / cm ²
Range. 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 reaction injection molding, a low-viscosity reaction solution is used.
Since molding can be performed at a relatively low temperature and low pressure, an expensive metal mold having high rigidity is not necessarily used, and a resin mold or a simple mold may be used. The inside of the mold is preferably sealed with an inert gas, and the components used for the polymerization reaction are preferably stored and operated under an atmosphere of an inert gas such as nitrogen gas.

The substrate layer may be disposed in contact with the inner peripheral surface of the cavity for forming the reaction injection molded layer.
It is preferable to use a support or the like so as to be arranged at a predetermined interval from the inner peripheral surface of the cavity. When the substrate layer is fixed to a mold using such a support, the shape of the support is not particularly limited as long as the shape is suitable for the purpose. That is, it is only necessary that the base material layer can be fixed to the mold such that the distance between the outer peripheral surface of the base material layer and the inner peripheral surface of the mold becomes a predetermined dimension at the position where the support is attached.

However, if the contact area between the support and the base material layer is too small, the buoyancy when filling the reaction solution, the surface pressure generated by the weight of the insert, etc. increase, and the insert tends to be dented at the contact portion. Become. Therefore, it is preferable to consider the contact area between the substrate layer and the support according to the magnitude of the buoyancy, the mounting position of the support, the number of the support mounted, the material and the thickness of the substrate layer, and the like. When fixing the base material layer to the mold using the support, the bottom surface of the support, that is, the surface where the support comes into contact with the base material layer and the mold, according to the surface shape of the base material layer and the mold, respectively. More preferably, it is shaped. For example, when fixing a container-shaped substrate layer, one bottom surface of the support is a concave curved surface corresponding to the curved surface of the substrate layer, and the other bottom surface is a convex curved surface corresponding to the curved surface of the mold inner circumference. And In addition, such a support is attached to either the base material layer or the mold, but the attaching means is not particularly limited. For example, adhesion, adhesion, fusion and the like can be mentioned. In the case of attaching with adhesive, a double-sided adhesive tape may be used instead of using an adhesive.

Thickness of Base Layer and Coating Layer In the present invention, the thickness of the base layer is not particularly limited, but is preferably uniform. This is because when the thickness is made uniform, the unevenness in the strength of the entire composite molded body is reduced.
When the coating layer is composed of a polynorbornene-based resin, the thickness of the base layer is 1 mm or more, preferably 2 mm or more, more preferably, because it is not thermally deformed by the heat of polymerization during the reaction of the norbornene-based monomer. 2.5 mm or more. Further, if the thickness of the base material layer 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.

In the present invention, the thickness of the coating layer is not particularly limited.
2.5 mm or more, preferably 3.0 mm or more, more preferably 3.5 mm or more. Further, if the thickness of the coating layer is too large, the moldability decreases and it takes time,
mm or less, preferably 13 mm or less, more preferably 1 mm or less.
2 mm or less.

Electromagnetic induction heating element As the material of the electromagnetic induction heating element according to the present invention, any material can be used as long as it generates heat by the electromagnetic induction effect. In particular, it is preferable to use a conductive material having a large calorific value because the fusion time can be reduced. As the electromagnetic induction heating element, for example, a metal wire, a metal fiber, a metal rod, a metal plate, a metal mesh, a metal powder, or the like is used. As the metal, for example, stainless steel, zirconium, iron, aluminum, copper, brass and the like are preferably used.

The method of interposing the electromagnetic induction heating element on the bonding surface composed of the base material layer is not particularly limited, but includes a method of including the material in the base material layer, a method of sticking to the surface of the base material layer as the bonding surface, A method in which a sheet material containing an induction heating element is interposed between bonding surfaces is exemplified, but a method using a sheet material is preferable.

The material of the sheet material is not particularly limited, and it is preferable that the sheet material is made of a material having a high compatibility with the base material layer. Since it becomes higher, a molded article having better airtightness and watertightness can be obtained.

The shape and structure of the sheet material are not particularly limited, and it is preferable that the shape and structure be such that the entire bonding surface can be fused. However, depending on the shape and structure of the bonding surface, the sheet material is formed on the bonding surface. It can be scattered.

Electromagnetic induction heating Electromagnetic induction heating is a method of applying a magnetic field to an electromagnetic induction heating element in a non-contact manner to cause an eddy current to flow through the electromagnetic induction heating element to generate heat. To apply a high-frequency magnetic field to the electromagnetic induction heating element. The high frequency is preferably 0.5k
Hz to several tens of MHz, more preferably 400 kHz to 5
MHz, particularly preferably 800 kHz to 2 MHz. The electric power supplied to the magnetic field generating coil is preferably 0.5 to 50 kW, more preferably 5 to 30 kW, and particularly preferably 10 to 20 kW. It is preferable that the distance between the coil that generates the magnetic field and the electromagnetic induction heating element is short (the amount of heat generation is large). Since a magnetic field is applied from outside the coating layer, it is preferable that the coil be in contact with the coating layer. Preferred conditions for electromagnetic induction heating using a coil vary depending on conditions such as the outer diameter of the coil, the material of the electromagnetic induction heating element, the distance from the coil to the electromagnetic induction heating element, and the power supplied to the coil. As the outer diameter of the coil increases, the area that can be fused at one time increases, but the power consumption tends to increase because the magnetic flux density decreases with the same power. Further, the shorter the distance from the coil to the electromagnetic induction heating element, the smaller the power consumption, the more fusing is possible. Furthermore, if an electromagnetic induction heating element made of a material having a large electromagnetic induction effect is used, electromagnetic induction heating can be performed with low power consumption.

In the present invention, it is preferable to pressurize the joint surfaces at the time of or immediately after the electromagnetic induction heating. Pressing can be performed with a pressure roller or the like. A heating means for heating the coating layer and the substrate layer may be used in combination with the electromagnetic induction heating. Examples of the heating unit include a planar heating element and a heating element such as a heater. However, since this heating is performed from the outside of the coating layer,
It is necessary to perform at a temperature that does not damage the coating layer.

[0039]

According to the composite molded article and the method of manufacturing the same according to the present invention, an electromagnetic induction heating element is interposed between the joint faces when two or more molded article members are joined to each other at the joint faces formed on the base material layer. Then, a magnetic field is externally applied to the joint surface to perform induction heating. For this reason, an electric current flows through the electromagnetic induction heating element due to the electromagnetic induction effect to generate heat, thereby melting the bonding surface formed of the base material layer, so that fusion of the bonding surface can be easily achieved. Conventionally, especially in the case of a large molded body,
Since it was difficult to heat the bonding surfaces to each other, it was difficult to fuse the bonding surfaces.

In particular, when the substrate layer is composed of the first polymer layer and the second polymer layer, the first polymer layer mainly has excellent water resistance, and the second polymer layer mainly has the gas barrier. sex,
Since it is excellent in alcohol resistance, oil resistance, and organic solvent resistance, it is suitable when a composite molded article is used as a container. That is, as a content of the container, for example, an organic solvent such as chloroform, alcohol, xylene, MEK, gasoline, and kerosene can be favorably stored. The substrate layer itself composed of such a multilayer film has low rigidity and strength, and cannot be used as a large container or a container buried underground, but in the present invention, the outermost periphery has excellent impact resistance and mechanical strength. Since a coating layer made of a reaction injection molding resin such as a polynorbornene-based resin is formed, it can be used as a large container or an underground container.

In the present invention, when the base material layer has a three-layer structure of a first polymer layer / a second polymer layer / a first polymer layer, the base layer has an adhesive property with a polynorbornene resin. It is preferable because it is excellent in excellent organic solvent resistance and water resistance (water resistance to water containing an organic solvent).

In the method of manufacturing a molded article of the present invention, fusion of the bonding surface can be achieved only by applying a magnetic field to the bonding surface from the outside. However, when the magnetic field is applied to the bonding surface, the bonding surface can be crimped. Since the bonding surface can be more firmly fused during the melting, the airtightness and the watertightness are further improved. The specific means for crimping is not particularly limited, and it is preferable to apply a constant pressure to the entire periphery of the joint surface, but it is preferable to crimp the joint surface at predetermined intervals according to the shape or structure of the molded body or the joint surface. Can also.

The method for producing a composite molded article of the present invention can be applied to various molded articles. However, if the present invention is applied to a method for producing a container, it is extremely durable, has high durability, high impact resistance, and high resistance to damage. A chemical container can be obtained. The liquid that can be stored in such a container is not particularly limited as long as it does not dissolve the polyolefin-based resin constituting the base material layer, such as pure water, tap water, sewage, kerosene, and gasoline.
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. Since the container itself obtained by the manufacturing method of the present invention is excellent in load-bearing properties, the number of reinforcing portions such as ribs can be reduced, so that moldability is also improved.

[0044]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a molded article (container) according to the present invention and a method for producing the same will be described in detail based on an embodiment shown in the drawings.

First Embodiment FIGS. 1A to 1D are cross-sectional views for explaining an embodiment of a method for producing a composite molded article according to the present invention, and FIG. 2 is a method for producing a composite molded article according to the present invention. FIG. 2A is a cross-sectional view showing the entire mold, and FIG.
(B) is a sectional view of a main part showing a mixer for the reaction resin, and FIG.
(A) And (B) is principal part sectional drawing which shows other embodiment of the sheet material containing the electromagnetic induction heating element which concerns on this invention.

As shown in FIG. 1, the present embodiment is an example in which a two-piece spherical container is formed as a composite molded article according to the present invention. This container 100 is, as shown in FIG.
The hemispherical container components 100a, 100b are
a, 16b. For example, a port 18 is formed in one container component 100a, and a socket (not shown) or the like is attached here.

As shown in FIG. 1 (B), each of the hemispherical container constituent members 100a and 100b
2a, 12b and coating layers 14a, 14b covering the outer periphery thereof
And The base layers 12a, 12b are formed by coating layers 14a,
14b is made of, for example, a polyolefin-based resin such as polyethylene or polypropylene having a good fusion property with the polynorbornene-based resin constituting the resin 14b, and is formed to have a uniform thickness by a vacuum forming method or the like. By making the thicknesses of the base material layers 12a and 12b uniform as in the present embodiment,
There is an advantage that the strength of the entire container 100 is less uneven, that the container 100 is resistant to internal pressure, and that the capacity is increased with a minimum surface area. The forming method of the base layers 12a and 12b is not limited to the vacuum forming method, and other known forming methods can be applied.

Bonding surfaces 16a, 16b are formed on the respective base layers 12a, 12b, and a tape 15 containing an electromagnetic induction heating element described later is interposed therebetween so that they are fused to each other. It has become.

On the other hand, coating layers 14a and 14b are formed on the outer peripheral surfaces of the respective base layers 12a and 12b, and the coating layers 14a and 14b are made of a reaction injection molded article of a norbornene-based monomer. The coating layers 14a, 14b
By using a polynorbornene-based resin obtained by the reaction injection molding method, the base material layers 12a and 12b can be coated and molded satisfactorily by utilizing the material characteristic that the viscosity of the material at the time of molding is extremely low. It has the advantage of being easy to do.

In this embodiment, the coating layers 14a and 14b are formed on the outer peripheral surfaces of the base layers 12a and 12b by the following steps.

First, the base layers 12a and 12b as shown in FIG. 1A are formed by a vacuum forming method, and a metal socket or the like is inserted into the opening 18 and fixed thereto (not shown). Such base material layers 12a and 12b are set in dies 30 and 32 as shown in FIG. Note that FIG.
(A) shows a step of forming a coating layer 14b on the outer peripheral surface of the base material layer 12b.

In this embodiment, in order to form a cavity C to be a coating layer between the base layer 12b and the inner peripheral surface of the mold 32, in the present embodiment, a circle is formed on the inner peripheral surface of the mold 32. The columnar support 20 is attached. The support 20 is made of polyethylene which is highly fusible with a reaction injection molded article to be formed into a coating layer.

As shown in FIG. 2A, the distance between the outer peripheral surface of the base material layer 12b and the inner peripheral surface of the mold 32 (ie, at the position where the support 20 is attached) So that the gap between the cavities C) has a predetermined size.
The base material layer 12b is fixed to the mold 32, and the support 20
If the contact area between the substrate layer 12b and the substrate layer 12b is too small, the buoyancy when filling the reaction solution, the surface pressure generated by the weight of the substrate layer 12b, and the like increase, and the substrate layer 12b is easily depressed at the contact portion. The contact area between the base material layer 12b and the support 20 is taken into consideration according to the magnitude of the buoyancy, the mounting position of the support 20, the number of the support 20 mounted, the material and thickness of the base material layer 12b, and the like. I have.

The bottom surface of the support 20, that is, the surface where the support 20 comes into contact with the base layer 12b and the mold 32 has a shape corresponding to the surface shape of the base layer 12b and the mold 32, respectively. . That is, in the present embodiment, the support 2
0 has a concave spherical surface corresponding to the outer spherical surface of the base material layer 12b, and the other bottom surface has a convex spherical surface corresponding to the inner spherical surface of the mold 32. Such a support 20 is placed in a mold 32.
The means for attaching to is not particularly limited, for example, adhesion,
Adhesion, fusion and the like can be mentioned. In the case of attaching with adhesive, a double-sided adhesive tape may be used instead of using an adhesive. Note that the height of the support 20 is the thickness of the cavity C, and the coating layer 1 of the intended container constituent member 100b.
4b, the support 2 formed in a predetermined shape.
Since the support 20 firmly fixes the base material layer 12b to the molds 30 and 32 even by inflow of the reaction liquid, by firmly attaching the substrate layer 0 to the mold 32, the thickness of the target coating layer 14b is reduced. Can be obtained. In the present embodiment, the support 20 is attached to the mold 32, but may be attached to the base layer 12b.

FIG. 2 shows a state in which the support 20 is used.
As shown in (A), after setting the base material layer 12b in the molds 30 and 32, the coating layer 14b made of polynorbornene-based resin is formed by a reaction injection molding method using the following molding apparatus.

As shown in FIGS. 2A and 2B, the molding apparatus according to the present embodiment has an upper mold 30 and a lower mold 32, which are provided so as to be relatively close to and separated from each other. . Each of the upper mold 30 and the lower mold 32 has a molding surface corresponding to the shape of the outer peripheral surface of the container constituent member 100b, that is, the outer peripheral surface of the coating layer 14b. Is set in the molds 30 and 32, a gap corresponding to the height of the support 20, that is, a cavity C is formed as shown in FIG. An injection port 34 for injecting the reaction liquid into the cavity C is formed in one of the molds 30 and 32 (the lower mold 32 in FIG. 2A), and a mixer 40 is provided in the injection port 34. Have been.

The mixer 40 mixes and discharges the reaction liquid A and the reaction liquid B, and has a moving rod 42 at 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 this embodiment, since the coating layers 14a and 14b are made of polynorbornene resin, the reaction solution A
As the reaction liquid B, a liquid composed of the norbornene monomer and the activator is used.

As a result, the container members 100a and 100b shown in FIG. 1B are obtained, respectively. Next, these container members 100a and 100b are
a and 16b are joined to form the container 100.

At this time, in this embodiment, as shown in FIG. 1C, a tape 15 made of a polyolefin-based resin into which stainless steel fibers are kneaded as an electromagnetic induction heating element is entirely bonded to one of the joining surfaces 16a and 16b. Paste around. The tape 15 is preferably made of the same material as the polyolefin-based resin constituting the base layers 12a and 12b, and more preferably the same grade among the same materials. For example, in the present embodiment, since the base layer is made of polyethylene, the tape 15 is also made of polyethylene of the same grade as this polyethylene.

Incidentally, an electromagnetic induction heating element other than stainless steel fiber can be mixed into the tape 15. The tape 15 is bonded to the bonding surfaces 16a, 16b using an adhesive or the like.
However, as shown in FIG. 3 (A) or (B), it may be embedded when forming the base material layers 12a and 12b. Alternatively, the base material layers 12a, 12b
When forming the container, a concave portion corresponding to the tape is formed in one of the joining surfaces 16a and 16b, and the container constituting members 100a and 100b are formed.
When joining b, the tape 15 may be fitted into this recess. Further, the tape 15 is bonded to the bonding surface 16 using an adhesive.
In addition to attaching to one of a and 16b, partial fusion may be performed by heating. Further, although there is a possibility that the adhesiveness may decrease, the tape 15 made of polyolefin resin may be used.
May be attached to the entire periphery of both of the joining surfaces 16a and 16b.

As shown in FIG. 1 (C), after a polyethylene-made tape 15 containing stainless steel fiber is adhered to the joining surface 16b of one container constituting member 100b, the joining surfaces 16a, 100b of the two container constituting members 100a, 100b are joined. 1B, the magnetic field generating coil 19 is brought close to the entire periphery of the joining surfaces 16a, 16b from outside the flange portion, and as shown in FIG. 1D, the joining surfaces 16a, 16b
A magnetic field is applied to.

Due to the action of the magnetic field, a current due to the electromagnetic induction effect flows through the stainless fibers of the tape 15 provided between the joining surfaces, and heat is generated by self-resistance. As a result, the tape 15 and the joining surfaces 16a, 16b begin to melt, and the joining surfaces 16a, 16b are fused.

As described above, according to the method of manufacturing a composite molded article of the present embodiment, the fusion is performed by electromagnetic induction, so that the bonding between polyolefin resins, which is conventionally considered to be difficult, is performed. Even in the case of a surface, fusion can be performed easily and with excellent air-tightness and water-tightness, and this is particularly preferable when applied to joining a large-sized molded component.

Second Embodiment In this embodiment, a cylindrical embedded kerosene tank 200 as shown in FIG. 4 is manufactured by using the method for manufacturing a composite molded body according to the present invention. In this kerosene tank 200, the tank constituent members 200a, 200b are connected to the flanges 202a, 2b.
For example, a nozzle seat 201 is formed on one of the tank constituent members 200a, and a nozzle (not shown) or the like is attached thereto. In addition, each tank constituent member 200a, 200b has
Reinforcing ribs 204a, 204b, 205a, 205b are integrally formed.

As shown in FIG. 5A, the tank constituent members 200a and 200b are made of base material layers 212a and 21b, respectively.
2b and covering layers 214a and 214b covering the outer periphery thereof. In the present embodiment, as shown in FIG. 6A, the base material layers 212a and 212b are first polymer layers 208a and 212b.
The second polymer layer 208b is laminated directly or via another layer (for example, an adhesive layer) on the outside of the first polymer layers 208a and 208b and is not compatible with the first polymer layers 208a and 208b.
It is composed of a multilayer film having at least polymer layers 209a and 209b.

The first polymer layers 208a and 208b are preferably one selected from the group consisting of polyolefin, polystyrene, and ethylene / vinyl acetate copolymer (ethylene content exceeding 50% by weight). The first polymer layers 208a and 208b are mainly excellent in water resistance. As the second polymer layers 209a and 209b, polyamide, polyvinyl alcohol (PVA), ethylene / vinyl alcohol copolymer (vinyl alcohol content 50
Exceeding by weight: EVOH), polyester, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, and other halides. The second polymer layers 209a and 209b mainly have excellent gas barrier properties and oil resistance. Especially E
VOH is suitable for use as the second polymer layers 209a and 209b because it has a small humidity dependency and a fairly good gas barrier property.

The thicknesses of the first polymer layers 208a and 208b and the second polymer layers 209a and 209b are not particularly limited, but are 25 μm to 3 mm and 10 to 500 μm, respectively.
m is preferable.

When there is a problem in the adhesiveness between the first polymer layers 208a, 208b and the second polymer layers 209a, 209b, a method of blending a resin having a heat-fusing property into at least one of the layers, An adhesive resin may be interposed between the layers. An example of the former is multilayer extrusion blow molding using, for example, a blend of LDPE (bottom density polyethylene) and EVOH. In this case, a blend layer is formed between LDPE and EVOH. In the blend layer,
It is preferable to add an ionomer for improving the adhesion between LDPE and EVOH. As an example of the latter, there is a method using a maleic anhydride-modified polyolefin as an adhesive. The polyolefin and the maleic anhydride-modified polyolefin are compatible and have good adhesion. In addition, between EVOH and the maleic anhydride-modified polyolefin, it is considered that the hydroxyl group of EVOH and the grafted maleic anhydride are chemically bonded, and the adhesion is good.

The base layer 2 composed of such a multilayer film
12a and 212b are formed by a multilayer extrusion blow molding method or a multilayer injection blow molding method. In the present embodiment, the thickness of the general surfaces of the coating layers 214a and 214b is not particularly limited.
Since 00 is easily broken, the thickness is set to 2.5 mm or more, preferably 3.0 mm or more, and more preferably 3.5 mm or more. Further, if the thickness of the coating layers 214a and 214b is too large, the moldability decreases and it takes time, so the thickness is 15 mm or less, preferably 13 mm or less, more preferably 12 mm.
The following is assumed. On the other hand, ribs 204a, 204 shown in FIG.
The height of b, 205a, 205ba is preferably 100-1200% of the thickness, and the width of the rib is preferably 50-250% of the thickness.

In this embodiment, the coating layers 214a, 214
b is composed of a ring-opened polymer of a norbornene-based monomer modified with an elastomer. Covering layers 214a, 21
4b is made of a polynorbornene-based resin obtained by a reaction injection molding method, so that the base material layers 212a, 212a,
212b has an advantage that it is easily covered and molded, and it is easy to integrally mold.

Next, a method of manufacturing the tank 200 will be described. However, description of the same parts as in the first embodiment is partially omitted. In the present embodiment, first, the base layers 212a and 212b formed of a multilayer film are formed by a blow molding method or the like. Next, the base material layers 212a, 21
2b is placed in a mold in the same manner as in the first embodiment, and reaction injection molding is performed to form coating layers 214a and 214b outside the base layers 212a and 212b. However, in the present embodiment, the adhesion between the second polymer layers 209a and 209b (see FIG. 6A) located on the outer peripheral surfaces of the base material layers 212a and 212b and the coating layers 214a and 214b made of polynorbornene-based resin. If there is a difficulty in the properties, an adhesive layer may be applied to the outer peripheral surfaces of the second polymer layers 209a and 209b of the multilayer film.

The adhesive layer in this case is not particularly limited, but an adhesive polyolefin resin or the like is used. As the adhesive polyolefin resin, specifically,
For example, Nisseki N polymer manufactured by Nippon Petrochemical Co., Ltd. is exemplified.

In this way, each tank component 200
a, 200b, the flange 20 of each component
2a and 202b are put together, and a tape 15 is interposed between them as shown in FIG. Tape 15
It is for fusing between the flanges 202a and 202b, and is made of a polyolefin resin tape into which stainless steel fibers are kneaded as an electromagnetic induction heating element.

The joining surfaces of the flanges 202a and 202b of the two constituent members 200a and 200b are aligned with each other, and in this state, as shown in FIG.
Outside of the flange (around both sides) around the entire circumference of 202b
, The magnetic field generating coil 19 is brought closer, and a magnetic field is applied to the joint surface.

Due to the action of this magnetic field, a current due to the electromagnetic induction effect flows through the stainless fibers of the tape 15 provided between the joining surfaces, and heat is generated by self-resistance. As a result, the tape 15 and the first polymer layers 208a and 208b forming the joining surface start to melt, and the joining surface of both flanges is fused well. Note that, in the present embodiment, as shown in FIG.
2b, a bolt 206 and a nut 207 may be further used to assist in joining the two flanges 202a and 202b. Furthermore, in the present embodiment, as shown in FIG. 7, a convex piece 220 may be provided at the tip of one of the flanges 202a so that the joint surface between the flanges 202a and 202b is hidden from the outside. . With this configuration, even when a pressure or the like acts from the outside, the pressure does not directly act on the joining surface, and the strength of the joining surface is further improved.

Third Embodiment In the present embodiment, as shown in FIG. 6B, similarly to the second embodiment, the base layers 212a and 212b are formed of a multilayer film. The difference from the embodiment shown in FIG. 6A is that the second polymer layer 209a and the coating layers 214a, 21
4b, the third polymer layers 210a and 210b are laminated. Third polymer layers 210a, 210b
Is preferably one selected from the group consisting of polyolefin, polystyrene, and ethylene / vinyl acetate copolymer (ethylene content exceeding 50% by weight), like the first polymer layers 208a and 208b. It is preferred to be composed of polyolefin. Third polymer layer 210
Since a coating layer made of a polynorbornene-based resin is formed outside of the first and second polymer layers 2a and 210b,
By composing 10a, 210b with polyolefin,
The fusion with the coating layer can be achieved without using an adhesive layer. Note that the thickness of the third polymer layers 210a and 210b may be approximately the same as the thickness of the first polymer layers 208a and 208b.

Fourth Embodiment FIG. 8 shows, for example, a tank component 200a shown in FIG.
It is a figure which shows an example of the electromagnetic induction heating apparatus used in order to perform electromagnetic induction heating between the flanges 202a and 202b of 200b.

As shown in FIG. 8, the electromagnetic induction heating device of the present embodiment has a moving frame 230. This moving frame 2
30 includes a coil 19 for generating a magnetic field for electromagnetic induction.
Is mounted, and the coil 19 is connected to one of the flanges 202.
b can be moved while being in contact with the coating layer 214b. The coil 19 may be arranged also on the side of the coating layer 214a.

In order to be located on both sides of the coil 19,
Moreover, so as to sandwich the flanges 202a and 202b,
The feed roller 232 and the pressure roller 234 are held by the movable frame 230. These rollers 232 and 234
Are respectively connected to the flange 202 by a spring or the like.
a, 202b is preferably pressed against the coating layers 214a, 214b. In particular, the pressing force of the pressure roller 234 is preferably greater than the pressing force of the feed roller 232.

The moving frame 230 includes rollers 232 and 234
8 along with the coil 19 at a predetermined speed in the direction of arrow X in FIG. Therefore, by generating a high-frequency magnetic field by the coil 19 while moving the moving frame 230, the sheet materials 15 including the electromagnetic induction heating elements can be sequentially heated and melted. Further, the base material layer 2 of the flange portion is
12a and 212b can be brought into close contact with each other, and they fuse well.

The present invention is not limited to the above-described embodiment, but can be variously modified within the scope of the present invention.

[0083]

EXAMPLES Hereinafter, the present invention will be described based on examples that further embody the present invention, in comparison with comparative examples. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, parts and percentages are by weight unless otherwise specified.

Example 1 In this example, first, the hemispherical base material layers 12a and 12b shown in FIG. 1A were formed by vacuum forming. The base layers 12a and 12b were made of polyethylene resin (Matec 0368R, manufactured by Idemitsu Petrochemical Co., Ltd.). Base material layer 1
The inner radius of 2a, 12b is 600 mm, the thickness is 1.2 mm on average, the thickness of the flange on which the joint surfaces 16a, 16b are formed is 2 mm, and the radial width of the joint surfaces 16a, 16b is Was 100 mm.

As shown in FIG. 2, the base layers 12a and 12b are placed in dies 30 and 32, respectively, and a 4 mm-thick polynorbornene-based resin is placed on the outer peripheral surfaces of the base layers 12a and 12b. Was formed by reaction injection molding.

At the time of reaction injection molding, a norbornene-based monomer composed of 90% of dicyclopentadiene (DCPD) and 10% of an asymmetric cyclopentadiene trimer is placed in two containers, one of which is diethylaluminum chloride with respect to the monomer. (DEAC) at 40 molar concentration, 1,
3-dichloro-2-propanol (dcPrOH) 48
It was added so as to have a molar concentration (solution A). On the other hand, tri (tridecyl) ammonium molybdate was added to the monomer at a concentration of 10 mmol (B
liquid). These A liquid and B liquid were stored in A tank and B tank, respectively.

The temperature of the mold is set at 30 ° C. by flowing hot water through the temperature control pipe mounted inside the mold, and the same volumes of the solution A and the solution B are placed in the mold cavity. After about 5 minutes have passed after mixing and pouring, the base material layer 12a,
The container constituent members 100a and 100b having the coating layers 14a and 14b in which 12b was integrated were taken out.

Next, as shown in FIG. 1 (C), a polyethylene tape 15 into which stainless steel fibers were kneaded was attached to one entire circumference of the joining surfaces 16a and 16b. Tape 1
5 is 20 mm wide and 1 mm thick, and the total weight is 100
A fiber containing 20% by weight of stainless steel fibers (fiber diameter 50 μm) in terms of% by weight was used.

Next, the two container constituent members 100a, 10a
1b, the magnetic field generating coil 19 is brought close to the entire periphery of the joining surfaces 16a and 16b from outside the flange portion, as shown in FIG. 1 (D). A magnetic field was applied to the surfaces 16a and 16b.
The power supplied to the coil 19 is 10 kW and 1 MH
A high frequency voltage of z was applied. The outer diameter of the coil 19 was 50 mm. The distance from the coil 19 to the sheet material 15 was 5 mm. Since the range that can be fused by one electromagnetic induction heating is the outer diameter of the coil 19 times the width of the tape 15, the coil 19 is moved along the longitudinal direction of the joining surface, and the entire periphery of the joining surface is fused by electromagnetic induction heating. I wore it.

Water having a pressure of 6.9 × 10 ⁴ Pa was sealed in the inside of the container 100 thus obtained.
When leakage from a and 16b was observed, no leakage was observed.

Embodiment 2 In this embodiment, the base material layers 12a and 12b shown in FIG.
Was composed of a multilayer film composed of a first polymer layer and a second polymer layer. As the first polymer layer, a polyethylene resin (Matic 0368R) was used, and as the second polymer layer,
EVAL, EVOH (registered trademark of Kuraray Co., Ltd.)
EF XL (ethylene 32 mol% product) was used. In order to achieve adhesion between the first polymer layer and the second polymer layer, Nisseki N-polymer R1200 (M
FR (JIS-K-6760) 2.0 g / 10 min)
Was used.

The thickness of the first polymer layer is 70 μm,
The thickness of the second polymer layer was 30 μm. Multilayer extrusion blow molding was used for molding into the shape of the container body. Using the base layers 12a and 12b thus formed, a container 100 was formed in the same manner as in Example 1 and a similar test was performed. When leakage from the joint surface was observed, no leakage was observed.

[0093]

As described above, in the method for manufacturing a composite molded body according to the present invention, when two or more molded body constituent members are joined to each other at the joint surface formed on the base material layer, An electromagnetic induction heating element is interposed therebetween, and a magnetic field is externally applied to this joint surface. For this reason, a current flows through the electromagnetic induction heating element due to the electromagnetic induction effect to generate heat, thereby melting the sheet material and the bonding surface, so that the bonding of the bonding surface can be easily achieved. Therefore, even when the composite molded body is composed of a plurality of molded body constituent members, a composite molded body with high airtightness and watertightness can be obtained.

In particular, when the base material layer is composed of the first polymer layer and the second polymer layer, the first polymer layer constituting the base material layer mainly has excellent water resistance, Since the polymer layer mainly has excellent gas barrier properties, oil resistance, and organic solvent resistance, the composite molded article according to the present invention can be suitably used as a container. That is, organic solvents such as alcohol, chloroform, xylene, MEK, gasoline, and kerosene can be well stored as the contents of the container. The substrate layer itself composed of such a multilayer film is
Although it has low rigidity and strength and cannot be used as a large container or underground container, in the present invention, a coating made of a reaction injection molding resin such as a polynorbornene resin having excellent impact resistance and mechanical strength is provided on the outermost periphery. Since the layer is formed, it can be used as a large container or an underground container.

In the method for producing a composite molded article of the present invention,
Fusion of the bonding surface can be achieved only by applying a magnetic field to the bonding surface from the outside, but if the bonding surface is crimped when applying a magnetic field to the bonding surface, the bonding surface can be more firmly fused during melting. Therefore, the airtightness and the watertightness are further improved.

The method for producing a composite molded article according to the present invention can be applied to various molded articles. However, if the present invention is applied to a method for producing a container, it is extremely resistant to breakage and has high durability, high impact resistance and high impact resistance. A chemically resistant container can be obtained. The liquid that can be stored in such a container is not particularly limited as long as it does not dissolve the polyolefin resin constituting the base material layer, such as pure water, tap water, sewage, kerosene, and gasoline. 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. Especially,
Since the joint surface is rich in airtightness and watertightness, it is preferable to apply to a large-sized molded body that is difficult to integrally mold. Also,
Since the material itself is excellent in load resistance, the number of reinforcing portions such as ribs can be reduced, so that moldability is also improved.

[Brief description of the drawings]

FIGS. 1A to 1D are cross-sectional views illustrating an embodiment of a method for producing a composite molded article according to the present invention.

FIG. 2 is a view for explaining an embodiment of the method for producing a composite molded article according to the present invention, in which (A) is a cross-sectional view showing the entire mold, and (B) is a mixer of the reaction resin. It is an important section sectional view shown.

FIGS. 3A and 3B are cross-sectional views of a main part showing another embodiment of a sheet material including an electromagnetic induction heating element according to the present invention.

4 (A) to 4 (C) are a plan view, a front view and a side view showing an example of a tank obtained by the production method of the present invention.

FIGS. 5A and 5B are cross-sectional views of a main part showing an example of a flange shown in FIG. 4;

6 (A) and 6 (B) are cross-sectional views showing a main part of a joining portion of a flange shown in FIG.

FIG. 7 is a cross-sectional view of a main part showing another example of a joint portion of a flange portion.

FIG. 8 is a diagram illustrating an example of an electromagnetic induction heating device used for performing electromagnetic induction heating.

[Explanation of symbols]

Reference Signs List 100 container (composite molded article) 100a, 100b container component (molded component) 12a, 12b base layer 14a, 14b coating layer (reaction injection molded resin layer) 15 polyethylene tape containing stainless steel fiber ( 16a, 16b ... joining surface 19 ... coil for generating magnetic field 20 ... support 30 ... upper die (die) 32 ... lower die (die) C ... cavity 200 ... tank (composite molding) 200a, 200b ... tank constituent member (molded member) 208a, 208b ... first polymer layer 209a, 209b ... second polymer layer 210a, 210b ... third polymer layer 212a, 212b ... base material layer 214a , 214b ... coating layer (reaction injection molded resin layer)

Claims (4)

[Claims] 1. A composite molded article in which two or more molded article constituent members having at least a base layer and a coating layer covering the outer periphery of the base layer are joined to each other at a joint surface, A composite molded article in which joining surfaces made of material layers are joined by heat generated by an electromagnetic induction heating element interposed between these joining surfaces. 2. The composite molded article according to claim 1, wherein the joining surface is a joining surface of a flange. 3. The composite molded article according to claim 1, wherein the base material layer is one of a single layer, two layers, and three layers. 4. A molding member is formed by forming a coating layer so as to cover the outer periphery of the substrate layer, and an electromagnetic induction heating element is interposed between the substrate layers located at the joining surface of the molding member. And heating the electromagnetic induction heating element in a non-contact manner by electromagnetic induction heating, thereby fusing the base material layers located on the bonding surface to each other or via an adhesive layer.