JP2002144487A - Tubular body and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tubular body excellent in heat resistance, chemical resistance, internal pressure strength and durability. SOLUTION: The tubular body 10 is composed of an inner layer 11 constituted of a thermoplastic resin and an outer layer 12 constituted of a fiber-reinforced (or particle-reinforced) norbornene-series polymer. The tubular body is obtained by a method wherein, a tubular body of the thermoplastic resin is used as an inner mold, a resin composition constituted mainly of a norbornene-series monomer, a particle and a metathetical polymerization catalyst is filled in a gap part formed by disposing the inner mold inside an outer mold and the outer mold is removed after polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a tubular body made of plastic and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, plastic tubular bodies made of vinyl chloride resin have been widely used. Recently, a tubular body made of an olefin resin such as polyethylene has been used.

However, since a tubular body composed of only a thermoplastic resin has insufficient internal pressure strength and heat resistance, as described in Japanese Patent Publication No. 24655/1990, the surface of a vinyl chloride resin tube is covered with a fiber. A tubular body having improved internal pressure strength and heat resistance by forming a reinforcing layer made of a reinforced thermosetting resin via a primer layer has been proposed.

[0004]

However, the unsaturated polyester resin, epoxy resin, etc. used for the reinforcing layer made of fiber reinforced thermosetting resin has a large volume shrinkage upon curing. Interlaminar peeling (interfacial peeling) with the base resin tube is likely to occur. Further, even when peeling does not occur, large residual stress is generated at the interface with the vinyl chloride resin tube.

Specifically, if interfacial peeling occurs in a use for a long period of time, an application to which cold heat is repeatedly applied, or an application in which heat resistance is required, the internal pressure strength is reduced and the performance of the pipe is significantly reduced. .

Further, since the reinforcing layer made of the fiber-reinforced thermosetting resin is hard and brittle, there is also a problem that the reinforcing layer is liable to be broken due to a drop during transportation or an impact during construction.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a tubular body having excellent heat resistance, chemical resistance, internal pressure strength, and durability, and a method for producing the same.

[0008]

First, the tubular body referred to in the present invention is defined to include all of the rod-shaped objects such as pipes, joints and hoses.

[0009] The tubular body of the present invention is characterized by comprising an inner layer made of a thermoplastic resin and an outer layer made of a fiber-reinforced norbornene-based polymer.

Further, the tubular body of the present invention is characterized by comprising an inner layer made of a thermoplastic resin and an outer layer made of a particle-reinforced norbornene-based polymer.

[0011] In the tubular body of the present invention, the thermoplastic resin is preferably a vinyl chloride resin. Further, the norbornene-based polymer is preferably polydicyclopentadiene.

In the tubular body of the present invention, an intermediate layer (adhesive layer) made of an acrylic primer may be formed between the inner layer and the outer layer.

[0013] In the production method of the present invention, a norbornene monomer, a norbornene monomer, is formed in a void formed by using a tubular body made of a thermoplastic resin as an inner mold and disposing the inner mold in an outer mold.
It is characterized by filling a resin composition containing particles and a metathesis polymerization catalyst as main components, and removing the outer mold after polymerization.

In the production method of the present invention, it is preferable to use a resin composition containing at least one kind of particles among calcium carbonate, aluminum hydroxide talc and fly ash. Further, it is preferable to use a resin composition obtained by mixing 50 parts by weight or more of particles with respect to 100 parts by weight of a norbornene-based monomer. Further, the norbornene-based monomer is preferably dicyclopentadiene.

In the production method of the present invention, a resin composition containing a norbornene-based monomer, particles and a metathesis polymerization catalyst as main components while controlling the surface temperature of an inner mold made of a thermoplastic resin to be equal to or lower than a heat distortion temperature. May be employed.

Next, details of the tubular body of the present invention will be described.

As an example of the tubular body of the present invention, as shown in FIG. 1, there is a tubular body 10 composed of an inner layer 11 made of a thermoplastic resin and an outer layer 12 made of a fiber-reinforced norbornene-based polymer. it can.

The norbornene-based polymer used for the outer layer of the tubular body of the present invention can be obtained by subjecting a norbornene-based monomer to metathesis polymerization using a polymerization catalyst.

The norbornene-based polymer is a polymer having excellent chemical resistance and heat resistance. By reinforcing with a reinforcing fiber, rigidity is increased, and an inner layer made of a thermoplastic resin can be effectively reinforced.

Further, the fiber-reinforced norbornene-based polymer reinforced with reinforcing fibers has an excellent impact resistance, and thus has an advantage that it is not broken by an unexpected impact during transportation or construction. Further, since the norbornene-based polymer undergoes ring-opening polymerization, the volume shrinkage due to the reaction is small and residual stress is hardly left as compared with the unsaturated polyester resin or epoxy resin, that is, the residual stress is hardly left at the interface of the tubular body.

The reinforcing fibers may be continuous fibers such as roving, roving cloth, or chopped strand mat, or long or short fibers such as chopped strands and milled fibers. Examples of the fiber type include glass fiber, carbon fiber, inorganic fiber such as metal fiber, or aramid fiber, nylon fiber, jute fiber, kenaf fiber, bamboo fiber, polyethylene fiber, drawn polyethylene fiber, polypropylene fiber, drawn polypropylene fiber, etc. Organic fibers.

As a method for forming an outer layer made of a fiber-reinforced norbornene-based polymer, for example, an inner layer made of a thermoplastic resin is laminated while impregnating a reinforcing fiber with a resin composition containing a norbornene-based monomer and a polymerization catalyst as main components. Method. In addition, an outer mold is set so as to surround an inner layer (tubular body) made of a thermoplastic resin, reinforcing fibers are set in voids formed between the inner layer and the outer mold, and then polymerized with a norbornene-based monomer. A method in which a resin composition containing a catalyst as a main component is filled in a void portion and polymerized and integrated.

As another example of the tubular body of the present invention, as shown in FIG. 2, there is a tubular body 20 composed of an inner layer 21 made of a thermoplastic resin and an outer layer 22 made of a norbornene-based polymer reinforced with particles. be able to.

The reason why the particles are used to reinforce the norbornene-based polymer is that the reinforcing effect as high as that of fiber reinforcement cannot be obtained with the same thickness, but even if it is blended with the norbornene-based monomer, it can be used as a fibrous reinforcing material having a high aspect ratio. This is due to the fact that it is injectable because it is less likely to thicken. Therefore, the molding process can be simplified. For these reasons, the particles preferably have a low aspect ratio.

The particles include calcium carbonate, aluminum hydroxide talc, magnesium carbonate, sodium hydrogen carbonate, clay, talc, mica, kaolin, fly ash, montmorillonite and the like.

When a surface treatment agent such as a silane coupling agent or a titanate coupling agent is used in order to secure adhesion between the particles and the norbornene-based polymer,
It can be reinforced more effectively.

As another example of the tubular body of the present invention, as shown in FIG. 3, an inner layer 31 made of a thermoplastic resin, an outer layer 32 made of a fiber-reinforced or particle-reinforced norbornene-based polymer, A tubular body 30 constituted by an acrylic primer layer 33 as an intermediate layer that adheres to the outer layer 32 can be given.

In the tubular body of the present invention, it is preferable to use a primer as shown in FIG. 3 for bonding the thermoplastic resin constituting the inner layer and the norbornene-based polymer constituting the outer layer.

In addition to the adhesive strength, the characteristics of the primer may require a short curing time or excellent chemical resistance in some cases. The acrylic primer satisfies such a requirement, and in particular, can bond the vinyl chloride resin and the norbornene-based polymer well. The primer may be applied using a brush or a spatula, or may be applied using a coater or a special gun.

The thermoplastic resin used for the tubular body of the present invention includes vinyl chloride, vinylidene chloride, chlorinated vinyl chloride resin, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (H
DPE), polypropylene (PP), polybutene, polyisoprene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ionomer, terpolymer of ethylene-propylene-diene, tetrafluoroethylene, polyethylene terephthalate, polybutylene Resins such as terephthalate and polycarbonate are exemplified.

Among the above thermoplastic resins, olefin resins such as high-density polyethylene and polypropylene can be fused and integrated by heat generated during polymerization of norbornene-based monomers. When sufficient adhesion cannot be obtained by integration by fusion, a primer may be used. The type of the primer may be appropriately selected depending on the combination of the thermoplastic resin and the norbornene-based polymer. As specific examples, urethane-based, epoxy-based, acrylic-based primers and the like can be suitably used.

Of the above thermoplastic resins, vinyl chloride resin is excellent in chemical resistance, mechanical properties and heat resistance and has high cost performance. Therefore, the vinyl chloride resin is reinforced by a fiber-reinforced or particle-reinforced norbornene-based polymer. A tubular body having excellent physical properties, heat resistance, and chemical resistance can be provided.

As the norbornene-based polymer used for the tubular body of the present invention, polydicyclopentadiene has excellent balance of physical properties such as easy availability, reactivity and heat resistance, and is excellent in impact resistance. It is preferable because it is difficult to crack.

Next, the details of the method for producing a tubular body of the present invention will be described.

As an example of the manufacturing method of the present invention, there is a method shown in FIG.

In the manufacturing method shown in FIGS. 4A and 4B, an outer mold (split) 42 is set so as to surround an inner mold (tubular body) 41 made of a thermoplastic resin, and the inner mold 41 is formed. And outer mold 4
2 is filled with a resin composition R containing a norbornene-based monomer, particles and a metathesis polymerization catalyst as main components, cured and integrated to form an outer mold 4 after polymerization.
2 is removed to obtain a desired tubular body (cheese tube) 4
0 is obtained.

According to the production method of the present invention, since the inner layer (tubular body) made of a thermoplastic resin is used as the inner mold, there is no need to prepare an inner mold, and it is a buried mold that does not require demolding. The greatest advantage is that a high quality tubular body can be provided with good productivity. Furthermore, since the particles are previously blended into the resin composition, there is no need to separately set the reinforcing fibers into a predetermined shape and set them in a mold as in the related art, and there is an advantage that molding and reinforcement can be performed simultaneously, Productivity is greatly improved.

In the production method of the present invention, the inner layer (tubular body) made of a thermoplastic resin may be preheated in order to make the resin composition easier to cure. Further, after-curing may be performed after the production in order to reduce the residual monomer.

By performing the sanding treatment on the outer peripheral surface of the inner layer (tubular body) made of a thermoplastic resin, it is possible to improve the adhesion reliability with the outer layer.

Examples of the norbornene-based monomer used in the production method of the present invention include bicyclics such as 2-norbornene and norbornadiene, tricyclics such as dicyclopentadiene and dihydrodicyclopentadiene, and tetracyclododecene. , Ethylidenetetracyclododecene, tetracyclic ring such as phenyltetracyclododecene, pentacyclic ring such as tricyclopentadiene, heptacyclic ring such as tetracyclopentadiene, and alkyl-substituted thereof (for example, methyl, ethyl, Propyl, butyl substituent, etc.), alkylidene substituent (eg, ethylidene substituent), aryl substituent (eg, phenyl, tolyl substituent), epoxy group, methacryl group, hydroxyl group, amino group, carboxyl group, Including cyano group, halogen group, ether group and ester bond It includes derivatives having a substituent such as groups. These may be used alone or as a mixture of two or more.

Cyclobutene, cyclopentene, and ring-opening polymerizable with one or more of norbornene monomers.
Monocyclic cycloolefins such as cyclopentadiene, cyclooctene and cyclododecene or cyclic monomers such as indene, coumarone, and coumarone-indene comonomer can be used within a range that does not impair the object of the present invention. A crosslinkable cyclic monomer such as tetrahydroindene may be used in combination.

Examples of the metathesis polymerization catalyst include halides such as tungsten, molybdenum, tantalum, ruthenium, rhenium, osmium and titanium, oxyhalides, oxides, and organic ammonium salts, which are stable against air and moisture. It is advantageous when a catalyst having excellent properties is compounded with reinforcing fibers or particles as in the present invention. Specifically, a ruthenium carbene catalyst represented by the following general formula [I] and a ruthenium vinylidene catalyst represented by the following general formula [II] are preferable.

[0043]

Embedded image

Wherein R 1 and R 2 independently of one another are hydrogen, C 2 -C 20 -alkenyl, C 1 -C 20 -alkyl, aryl, C 1 -C 20 -carboxylate, Cl 2
-C20-alkoxy, C2-C20-alkenyloxy, aryloxy, C2-C20-alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsilyl, arylsilyl, thioaryl, thioalkyl (alkyl portion is C1-C20), oxyaryl ,
Oxyalkyl (the alkyl part is C1-C20) (these are C1-C5-alkyl, halogen, C1-C5-
It may be optionally substituted by alkoxy, or Cl-C5-alkyl, halogen, Cl-
Optionally substituted by phenyl substituted by C5-alkoxy), means a ferrocene derivative, wherein X1 and X2 are, independently of one another, any desired anionic ligand And L1 and L2 independently of one another represent any desired neutral electron donor. And, then, two or three of X1, X2, L1 and L2 may together form a multidentate chelating ligand.

A more preferred structure of the catalyst is represented by the general formula [I]
And in the formula of general formula "II", R1 and R2 are
Independently of one another, hydrogen, methyl, ethyl, phenyl, ferrocenyl, or vinyl or silyl optionally substituted by methyl, ethyl, phenyl or ferrocenyl, Xl and X2 independently of one another
l, Br and L1 and L2 independently of one another are trimethylphosphine, triethylphosphine, triphenylphosphine, triisopropylphosphine or tricyclohexylphosphine, a ruthenium carbene catalyst or a ruthenium vinylidene catalyst.

Since the amount of the metathesis catalyst to be added varies depending on the activity of the catalyst, it cannot be specified unconditionally, but is preferably 1/5 to 1 / 500,000 molar equivalents with respect to all the monomers. If it is more than 1/5 equivalent, the obtained polymer molecular weight does not increase, and if it is less than 1 / 500,000 equivalent, the polymerization rate is undesirably reduced. A more preferable addition amount is 1/100 to 1 with respect to all monomers.
/ 100,000 molar equivalents. The mixing ratio of the catalyst may be set based on the necessary pot life and curing time in this range.

The resin composition used in the production method of the present invention includes an antioxidant, a filler, a foaming agent, a defoaming material, a thixotropic agent, an antistatic agent, a molecular weight regulator, a polymer modifier, Various additives such as a fuel, a plasticizer, a pigment, a dye, a colorant, and an elastomer may be blended.

Examples of the filler include calcium carbonate, aluminum hydroxide, magnesium carbonate, sodium hydrogen carbonate, clay, talc, mica, kaolin, fly ash, montmorillonite, glass balloon, silica balloon, and thermally expandable vinylidene chloride particles. .

Examples of the elastomer include natural rubber, polybutadiene, polyisoprene, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block co-aggregate, EPDM, ethylene-vinyl acetate co-aggregate and hydrides thereof. No.

According to the production method of the present invention, the smaller the aspect ratio of the particles is, the more the increase in viscosity with respect to the added amount of the resin composition can be suppressed.
It is preferable to use calcium carbonate, aluminum hydroxide talc, or fly ash.

It is preferable to add 50 parts by weight or more of the particles to 100 parts by weight of the norbornene-based monomer. If the amount is less than 50 parts by weight, the rigidity is insufficiently improved, and the reinforcing effect of the tubular body made of a thermoplastic resin becomes poor.

In the production method of the present invention, by controlling the surface temperature of the inner mold (tubular body) made of a thermoplastic resin so as to be equal to or lower than the thermal deformation temperature, the tubular body made of the thermoplastic resin becomes a resin composition. A good tubular body can be obtained without being deformed by the heat generated by polymerization. When the tubular body made of a thermoplastic resin has a temperature equal to or higher than the thermal deformation temperature, the tubular body is deformed due to residual stress during molding or the like, and a good tubular body cannot be obtained.

The method of controlling the temperature to be equal to or lower than the heat deformation temperature is not particularly limited, but a method of previously cooling a tubular body made of a thermoplastic resin, a method of lowering the reaction temperature of the resin composition with a retarder or the like, and a method of cooling a mold. And the like.

The norbornene-based monomer used in the production method of the present invention is preferably a crosslinkable one in order to exhibit rigidity, and specifically, a tricyclic or higher norbornene-based monomer is preferred. Among them, dicyclopentadiene is preferable because it is easily available, has excellent balance of physical properties such as reactivity, impact resistance and heat resistance.

<Operation> Since the tubular body of the present invention is composed of an inner layer made of a thermoplastic resin and an outer layer made of a fiber-reinforced or particle-reinforced norbornene-based polymer, rigidity, internal pressure strength, impact resistance, Excellent heat resistance. Further, when the inner layer made of a thermoplastic resin is made of a resin having excellent chemical resistance, for example, a vinyl chloride resin, good chemical resistance can be exhibited.

Further, since the norbornene-based polymer constituting the outer layer is polymerized by ring-opening polymerization of the norbornene-based monomer using a metathesis polymerization catalyst, the volume shrinkage is smaller than when a normal thermosetting resin is used. It is difficult for residual stress to remain in the tubular body,
Interfacial separation hardly occurs when used under cold and hot conditions. Further, the norbornene-based polymer is excellent in vibration damping properties, and even if an impact is applied to the tubular body by vibration such as an earthquake, defects such as interfacial peeling are unlikely to occur, so that stable quality can be secured.

The norbornene-based monomer used in the production method of the present invention has a low viscosity.
A tubular body having a high surface smoothness can be obtained.

[0058]

EXAMPLES Examples of the present invention will be described below along with comparative examples.

Example 1 Norbornene-based monomer: dicyclopentadiene metathesis polymerization catalyst: bis (tricyclohexylphosphine) benzylidene ruthenium dichloride Particles: calcium carbonate (particle diameter: 12 μm) First, a φ75 vinyl chloride resin tube (5. (0 mm) was subjected to sandblasting, and then a methacrylate resin as a primer was applied to the outer peripheral surface with a brush. The vinyl chloride resin tube was placed in a tubular aluminum mold (outer mold) divided into two parts and a clearance (gap) was 4.0.
mm and set the aluminum mold only to 60 mm.
The temperature was adjusted to ° C.

Next, 100 parts by weight of dicyclopentadiene heated to 40.degree.
m) was blended in an amount of 100 parts by weight. In addition, toluene 200
A solution obtained by dissolving 10 parts of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride in a part thereof is added so that the molar ratio of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride to dicyclopentadiene becomes 1/10000. Was prepared.

Then, the resin composition is filled in the space between the vinyl chloride resin tube and the aluminum mold, and after 10 minutes, the outer mold is removed from the mold, whereby the calcium carbonate reinforced polydicyclopentadiene (thickness 4) is removed. .0 mm) was obtained on the surface of the vinyl chloride resin tube. The total molding time was 20 minutes.

A drop test from a height of 2 m was performed on the ten pipes obtained in Example 1 above.
No peeling was observed in any of the 10 pipes. For 10 pipes, [60 ° C x 30 minutes] +
When the cooling and heating at [0 ° C. × 30 minutes] was repeated 10 times, no interface peeling was observed in any of the pipes.

Example 2 Norbornene-based monomer: dicyclopentadiene metathesis polymerization catalyst: ruthenium vinylidene complex represented by the following structural formula [III] Reinforcing fiber: glass cloth (# 250)

[0064]

Embedded image

First, an outer peripheral surface of a vinyl chloride resin cheese tube (thickness: 5.0 mm) of φ75-75 was subjected to sandblasting, and then a methacrylate resin as a primer was applied to the outer peripheral surface with a brush. The cheese tube made of a vinyl chloride resin was set in a two-piece aluminum mold (outer mold) for forming a cheese tube so that the clearance (gap) was 2.5 mm.

Next, a solution prepared by dissolving the above ruthenium vinylidene complex in 200 parts of toluene was mixed with a ruthenium vinylidene complex having a molar ratio of 1 / dicyclopentadiene.
A resin composition was prepared by blending so as to obtain 10,000. Then, after setting the glass cloth of # 250 in the gap between the vinyl chloride resin tube and the aluminum mold, the resin composition was filled in the gap, and then placed in a heating furnace at 60 ° C. By removing the outer mold after minutes, a φ75-75 cheese tube in which glass fiber reinforced polydicyclopentadiene (2.5 mm in thickness) is integrated with the surface of a cheese tube made of a vinyl chloride resin can be obtained. Was. The total molding time was 25 minutes.

A drop test from a height of 2 m was performed on the 10 cheese tubes obtained in Example 2 above, and no peeling was observed in any of the 10 cheese tubes. In addition, about 10 cheese tubes, [60 ° C. × 30
Min] + [0 ° C. × 30 minutes] was repeated 10 times, and no interfacial peeling was observed in any of the cheese tubes.

Comparative Example 1 An outer peripheral surface of a φ75 vinyl chloride resin tube (thickness: 5.9 mm) was subjected to sandblasting.

Next, an unsaturated polyester resin containing a styrene monomer (Yupika 8671: Nippon Yupika Co., Ltd.) 5
0 parts by weight, 30 parts by weight of an unsaturated polyester resin containing a styrene monomer (Yupika 4521PT: Nippon Yupika Co., Ltd.), 20 parts by weight of an isocyanate compound (trimer of hexamethylene diisocyanate: Nippon Polyurethane Co., Ltd.), radical curing agent (Kayamek A) A primer consisting of 1.5 parts by weight and 0.5 part by weight of a 6% solution of cobalt naphthenate was applied to the outer peripheral surface of the vinyl chloride resin tube with a brush.

Next, an unsaturated polyester resin (Yupika 4)
521PT: A 2.7 mm-thick FRP layer comprising two layers of glass chopped strands, one layer of glass roving cloth and one layer of glass yarn cloth impregnated with Nippon Yupika Co., Ltd. was laminated, and then placed in a 60 ° C. heating furnace. It was put in and taken out after 30 minutes to obtain an FRP-reinforced vinyl chloride resin tube. The total molding time was 50 minutes.

The ten FRPs obtained in Comparative Example 1 above
When a drop test from a height of 2 m was performed on the reinforced vinyl chloride resin tube, nine of the tubes showed interface peeling. Also, for 10 FRP reinforced vinyl chloride resin tubes,
When the cooling and heating of [60 ° C. × 30 minutes] + [0 ° C. × 30 minutes] were repeated 10 times, interfacial peeling was observed in seven of them.

[0072]

As described above, since the tubular body of the present invention is constituted by the inner layer made of thermoplastic resin and the outer layer made of fiber-reinforced or particle-reinforced norbornene-based polymer, rigidity and internal pressure strength are improved.・ Excellent in shock resistance and heat resistance.

Further, since the norbornene-based polymer constituting the outer layer is polymerized by ring-opening polymerization of the norbornene-based monomer using a metathesis polymerization catalyst, the volume shrinkage is smaller than when a normal thermosetting resin is used. Residual stress hardly remains in the tubular body, and the durability is excellent. Therefore, interfacial peeling is less likely to occur during long-term use, or under heat or cold conditions. Further, even when dropped during transportation or construction, the interface is hardly peeled off, thereby improving construction reliability.

Further, when the inner layer is made of a resin having excellent chemical resistance such as a vinyl chloride resin, it can be applied to, for example, a lining material of a piping of a chemical plant. Furthermore, since the norbornene-based polymer has excellent vibration damping properties and good seismic resistance after construction, it leads to high durability of the pipeline and can contribute to resource saving in the long term. In particular, the crosslinked norbornene-based polymer containing dicyclopentadiene is difficult to break, so that the tubular body does not easily break or crack.
Product reliability can be improved.

According to the production method of the present invention, since the tubular body made of a thermoplastic resin is used as the inner mold, there is an advantage that there is no need for investment in the mold of the inner mold. There is no production cost.

[Brief description of the drawings]

FIG. 1 is a perspective view showing an example of a tubular body of the present invention.

FIG. 2 is a perspective view showing another example of the tubular body of the present invention.

FIG. 3 is a perspective view showing another example of the tubular body of the present invention.

FIG. 4 is a perspective view showing an example of the method for producing a tubular body of the present invention.

[Explanation of symbols]

10, 20, 30 Tubular body 11, 21, 31 Inner layer (thermoplastic resin) 12 Outer layer (fiber-reinforced norbornene-based polymer) 22 Outer layer (particle-reinforced norbornene-based polymer) 32 Outer layer (fiber-reinforced or particle-reinforced norbornene-based polymer) 33 Acrylic Base primer layer 40 Tubular body 41 Inner mold (Tubular body: thermoplastic resin) 42 Outer mold 43 Void R resin composition

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // B29K 45:00 B29K 45:00 105: 06 105: 06 B29L 9:00 B29L 9:00 23:00 23:00 F-term (reference) 4F100 AA00B AA08 AA08B AA08H AA19B AA19H AC10B AC10H AG00 AK01A AK02 AK02B AK15 AK15A AK25C AK25G BA03 BA07 CA23B DA11 DE01B DG01 DG01B EH31 EJ65CGB90 A01 AD02 A01 A03A JA01 JB12 JF01 JF05 JL02 JN25 JQ06 4J002 BB032 BB122 CE001 CF002 CL002 CL062 DA016 DA066 DE146 DE236 DJ006 DJ036 DJ046 DL006 DM006 FA042 FA046 FD012 FD016

Claims (10)

[Claims] 1. A tubular body comprising an inner layer made of a thermoplastic resin and an outer layer made of a fiber-reinforced norbornene-based polymer. 2. A tubular body comprising an inner layer made of a thermoplastic resin and an outer layer made of a norbornene-based polymer reinforced with particles. 3. The tubular body according to claim 1, wherein the thermoplastic resin is a vinyl chloride resin. 4. The tubular body according to claim 1, wherein an intermediate layer made of an acrylic primer is formed between the inner layer and the outer layer. 5. The method according to claim 1, wherein the norbornene-based polymer is polydicyclopentadiene.
Or the tubular body according to 4. 6. A tubular body made of a thermoplastic resin is used as an inner mold, and voids formed by arranging the inner mold in an outer mold mainly include a norbornene-based monomer, particles, and a metathesis polymerization catalyst. A method for producing a tubular body, comprising filling a resin composition and removing an outer mold after polymerization. 7. The method for producing a tubular body according to claim 6, wherein a resin composition containing at least one kind of particles among calcium carbonate, aluminum hydroxide talc and fly ash is used. 8. The method for producing a tubular body according to claim 6, wherein a resin composition obtained by mixing 50 parts by weight or more of particles with respect to 100 parts by weight of a norbornene-based monomer is used. 9. A method for polymerizing a resin composition containing a norbornene-based monomer, particles and a metathesis polymerization catalyst as main components while controlling the surface temperature of an inner mold made of a thermoplastic resin to be equal to or lower than a heat distortion temperature. The method for producing a tubular body according to claim 6, 7, or 8. 10. The method for producing a tubular body according to claim 6, wherein the norbornene-based monomer is dicyclopentadiene.