JP2003080635A - Synthetic resin composite structure, bathroom constituting article, and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite structure which has enough strength to impact and is suitable as a bathroom constituting article having large rigidity. SOLUTION: By laminating a crosslinked cyclic olefin polymer molding with ribs molded integrally on one surface of an FRP molding, rigidity, strength, impact resistance, lightweight, etc., required for the bathroom constituting article, etc., are materialized.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is strong against impact,
The present invention relates to a new synthetic resin composite structure having excellent durability, light weight, and high rigidity. Specifically, it is a synthetic resin composite structure mainly used as a bathroom component such as a bathroom washroom, bathtub, waterproof pan, etc. It is about the body.

[0002]

2. Description of the Related Art Conventionally, most of bathroom washrooms, bathtubs and waterproof pans are molded by sheet molding method (SMC) using fiber reinforced plastic (FRP), and most of them are reinforced with glass fiber. It is molded using saturated polyester resin. When molding a washroom, bathtub, or waterproof pan using unsaturated polyester resin reinforced with glass fiber, for example, as the washroom area becomes wider, ribs etc. are provided on the lower surface of the washroom to suppress deformation due to foot load. Although it will be attached and reinforced, in the case of FRP, since the strength of the rib portion and the rib root portion is reduced due to the orientation of the glass fiber that is the reinforcing material, the rib height for imparting rigidity cannot be increased. There was a problem. Besides, such FR
There is also a problem that the specific gravity of P is as high as about 1.8 and the weight of the whole is large.

In the field of bathtubs, the FRP has been conventionally used.
There is a method in which a molded product and an acrylic coating layer are separately molded, and these are bonded together via an adhesive to form a composite structure, which is proposed in, for example, JP-A-2000-62044. There is also a method of vacuum forming an acrylic coating layer and performing a backup process from the back side with FRP, and a method of vacuum forming the acrylic coating layer on a backup resin and adhering it. For example, it is proposed in JP 2001-38797 A. There is.

However, such composite structures are insufficient in strength against impact and cannot be said to be sufficiently resistant to deformation. Therefore, particularly in the field of bathroom components such as bathtubs and waterproof pans, they are lightweight and have excellent impact resistance,
Moreover, products with a good surface appearance are strongly desired.

[0005]

DISCLOSURE OF THE INVENTION The present invention is a light-weight synthetic material which has a sufficient strength against impact while being capable of withstanding deformation while preventing the defects due to the orientation of glass fiber of FRP. An object of the present invention is to provide a resin composite structure, in particular, a bathroom washroom and / or bathtub, or a bathroom component such as a waterproof pan.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that the conventional FR
By attaching a cyclic olefin-based cross-linked polymer obtained by simultaneously performing polymerization and molding of a metathesis polymerizable monomer in the presence of a polymerization catalyst to a P wash basin and / or bath or a FRP waterproof pan-molded product, We found that the effect of two birds with one stone, which prevents defects in the rib-shaped part found in molded products, and is a cyclic olefin cross-linked polymer that can be integrally molded with ribs, imparts a large elastic modulus and high waterproofing ability, The following invention has been reached.

That is, the present invention provides the following composite structure,
The above objects are achieved by the bathroom components and the manufacturing method. (1) One side of an FRP (fiber reinforced plastic) molded article was joined with a cyclic olefin-based crosslinked polymer molded article obtained by simultaneously polymerizing and molding a metathesis-polymerizable cyclic olefin monomer in the presence of a polymerization catalyst. A characteristic synthetic resin composite structure. (2) In the FRP molded article, the surface different from the joint surface of the crosslinked polymer molded article has a stone-tone finish or a gel coat finish, or has a surface decoration for coloring the raw material. (1) The synthetic resin composite structure as described above. (3) The cyclic olefin-based crosslinked polymer molded product and the F
The above (1) is characterized in that the RP molded article is joined through an adhesive and / or a material having a heat insulating / buffering function.
Alternatively, the synthetic resin composite structure according to (2). (4) The synthetic resin composite structure according to any one of (1) to (3), wherein the cyclic olefin-based crosslinked polymer molded product is a molded product having an average thickness of 2 to 20 mm. (5) The above-mentioned cyclic olefin-based crosslinked polymer molded product integrally molded with at least one of vertical ribs, lattice ribs and corrugated ribs at a position other than the joint surface of the molded product with the FRP molded product. The synthetic resin composite structure according to any one of (1) to (4) above, wherein (6) A bathroom component made of the above synthetic resin composite structure. (7) (a) a step of producing an FRP molded article, and (b) a step of obtaining a cyclic olefin-based crosslinked polymerized article obtained by simultaneously performing polymerization and molding from a cyclic olefin monomer in the presence of a polymerization catalyst, (c) ) A step of filling a space between the FRP molded product and the cyclic olefin-based crosslinked polymer with an adhesive and / or a material having a heat insulating / buffering function, and joining them together, (d) the FRP molded product And a step of decorating the surface of the synthetic resin composite structure.

The term "bathroom component" as used herein means, in various bathroom systems such as a unit bath, a system toilet, and a system bath equipped with a washbasin and a toilet, a washbasin that constitutes a washbasin and a bathroom, and / or A waterproof pan for a bathtub, or a bathtub or a bathtub adjacent to the washing area, a bathtub wall forming the bathtub, a bathtub ceiling, etc.

In the following, a cyclic olefin-based crosslinked polymer forming the composite structure of the present invention, a molded product thereof, an FRP (fiber reinforced plastic) molded product, and a composite structure of the present invention in which these are bonded are in this order. A more specific description will be given.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The cyclic olefin-based crosslinked polymer (cured resin) is also referred to as a norbornene-based crosslinked polymer, and is a metathesis-polymerizable cyclic olefin monomer containing dicyclopentadiene as a main component in the presence of a metathesis catalyst system. Reaction Injection Molding (ReactionInjecti
on Molding (RIM method for short) or resin transfer molding (Resin Transfer Mo)
lding (abbreviated as RTM method) can be used for polymerization and molding with high dimensional accuracy. Since this cross-linked polymer has a liquid forming raw material, a complicated shape can be easily formed at a relatively low cost by this RIM or RTM molding method. Further, this cross-linked polymer has further improved impact resistance when an elastomer such as styrene-butadiene or ethylene-propylene-diene is added, or when fiber reinforcement such as glass fiber or carbon fiber or glass fine particles is added. Since they have a reinforcing effect, they can be added and blended as needed.

The metathesis-polymerizable cyclic olefin which is a monomer for obtaining a cross-linked polymer constituting the composite structure of the present invention, for example, a washing room and / or a bath forming a bathroom, or a structure such as a waterproof pan is Those containing 1 to 2 metathesis-polymerizable cycloalkene groups in the molecule are used. A compound having at least one cyclic olefin skeleton in the molecule is preferably used. Specific examples thereof include dicyclopentadiene, tricyclopentadiene, cyclopentadiene-methylcyclopentadiene co-dimer, 5-ethylidene cyclic olefin, cyclic olefin, norbornadiene, 5-cyclohexenyl cyclic olefin, 1,4,5,5. 8-dimethano-1,
4,4a, 5,6,7,8,8a-octahydronaphthalene, 1,4-methano-1,4,4a, 5,6,7,
8,8a-octahydronaphthalene, 6-ethylidene-
1,4,5,8-dimethano-1,4,4a, 5,6
7,8,8a-octahydronaphthalene, 6-ethylidene-1,4-methano-1,4,4a, 5,6,7,8,
8a, -octahydronaphthalene, 1,4,5,8-dimethano-1,4,4a, 5,8,8a-hexahydronaphthalene, ethylenebis (5-cyclic olefin) and the like can be mentioned. Mixtures can also be used. Particularly, dicyclopentadiene or a mixture thereof containing 50 mol% or more, preferably 70 mol% or more is suitably used.

If necessary, a metathesis-polymerizable cyclic olefin having a polar group containing a different element such as oxygen or nitrogen can be used as a copolymerization monomer.
Such a copolymerizable monomer also preferably has a cyclic olefin structural unit, and the polar group is preferably an ester group, an ether group, a cyano group, an N-substituted imide group, a halogen group or the like. Specific examples of the copolymerizable monomer include:
5-methoxycarbonyl cyclic olefin, 5- (2-ethylhexyloquine) carbonyl-5-methyl cyclic olefin, 5-phenyloxymethyl cyclic olefin, 5-cyano cyclic olefin, 6-cyano-1,4,5,8 -Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, N-butyl nadic acid imide, 5
-Chloro cyclic olefin etc. can be mentioned.

The metathesis catalyst system includes halides of metals such as tungsten, rhenium, tantalum and molybdenum as catalyst components, salts such as ammonium salts, and alkylated compounds of metals of Groups I to III of the periodic table as activator components. Organometallic compounds centered on, especially tetraalkyl tin,
Examples thereof include a composite catalyst composed of an alkylaluminum compound, an alkylaluminum halide compound or the like, or a catalyst composed of a ruthenium carbene complex. The former is generally polymerized by mixing two liquids of a monomer liquid containing a catalyst component (solution A) and a monomer liquid containing an activator component (solution B). The latter catalyst is generally polymerized by mixing the monomer liquid and the catalyst component. In the latter, the polymerization generally does not proceed instantaneously, and the polymerization reaction can be accelerated by increasing the temperature, but the former is preferably used in the present invention because the polymerization reaction is fast and the polymerization moldability is excellent. To be done.

In a preferred embodiment of the present invention, two types of monomer liquids are prepared, and one of the monomer liquids (solution A) contains the catalyst component of the metathesis polymerization catalyst system. As such a catalyst component, a halide or an ammonium salt of a metal such as tungsten, rhenium, tantalum or molybdenum is used, and a tungsten compound is particularly preferable. As such a tungsten compound, tungsten hexahalide, tungsten oxyhalide and the like are preferable, and more specifically, tungsten hexachloride, tungsten oxychloride and the like are preferable. Further, organic ammonium tungstate or the like can also be used. It has been found that when such a tungsten compound is directly added to the monomer, it immediately starts cationic polymerization, which is not preferable. Therefore, such a tungsten compound is an inert solvent such as benzene, toluene,
It is preferable to suspend it in chlorobenzene or the like in advance and solubilize it by adding a small amount of an alcohol compound and / or a phenol compound before use. Further, it is preferable to add about 1 to 5 mol of Lewis base or chelating agent to 1 mol of the tungsten compound in order to prevent the undesirable polymerization as described above. Examples of such additives include acetylacetone, acetoacetic acid alkyl esters, tetrahydrofuran, and benzonitrile. When a polar monomer is used, it may be a Lewis base itself as described above, and it may have its action even if the above compound is not added. As described above, the monomer liquid containing the catalyst component (solution A) has substantially sufficient stability.

In the other monomer solution (solution B),
It contains an activator component of a metathesis polymerization catalyst system. The activator component is preferably an organometallic compound centered on an alkylated compound of a metal of Group I to Group III of the periodic table, particularly tetraalkyltin, an alkylaluminum compound, and an alkylaluminum halide compound, and specifically, Examples thereof include diethyl aluminum chloride, diethyl aluminum chloride, trioctyl aluminum, dioctyl aluminum iodide, and tetrabutyl tin. By dissolving the organometallic compound as the activator component in the monomer, the monomer liquid (solution B)
Is formed.

Basically, a crosslinked polymer molded article can be obtained by mixing the solution A and the solution B and injecting the mixed solution into a mold.
Since the polymerization reaction is initiated very quickly, there may be a problem in that the curing may occur before it sufficiently flows into the molding die. In such a case, it is preferable to use an activity regulator. Lewis bases are generally used as the activity control agent, and ethers, esters, nitriles and the like are used above all. Specific examples of the activity regulator include ethyl benzoate, butyl ether, diglyme and the like. Such activity modifiers are generally solutions of organometallic compound activator components (Solution B).
It is used by adding to the side of. When a monomer having a Lewis base is used as described above, it can also serve as an activity regulator.

The amount of the metathesis polymerization catalyst system used is, for example, when a tungsten compound is used as the catalyst component, the ratio of the tungsten compound to the raw material monomer is
It is about 1,000 to 1 to 15,000, preferably about 2,000 to 1 on a molar basis, and when an alkylaluminum is used as the activator component, the aluminum compound to the above raw material monomer is used. The ratio of about 100: 1 to 10,000: 1, preferably 2 on a molar basis.
The vicinity of 00: 1 to 1,000: 1 is used. Further, the chelating agent and the activity controlling agent as described above can be appropriately adjusted and used depending on the amount of the catalyst system used by experiments.

In order to improve or maintain the properties of the molded product of the cyclic olefin-based crosslinked polymer in the present invention in practical use, various additives depending on its purpose can be added. Such additives include fillers, pigments,
Examples include antioxidants, light stabilizers, flame retardants, polymer modifiers, and the like. Since such an additive cannot be added after the crosslinked polymer has been molded, it is necessary to add it to the aforementioned raw material solution in advance when adding it.

The easiest method is to use the solution A described above.
And the solution B may be added in advance to either or both of them, but in this case, they do not react to a certain extent with the catalyst components and activator components having strong reactivity in the liquid and do not react to some extent in practice. , And it should not interfere with the polymerization. Inevitably, even if the reaction is unavoidable, if it does not substantially inhibit the polymerization or does not inhibit it in a short time, it is mixed with a monomer to prepare a third liquid, and immediately before the polymerization. Mixtures can also be used. A method in which the polymerization catalyst or activator is used as the third liquid and the above additives are added to solution A or solution B not containing the third liquid is also conceivable. Furthermore, in the case of a solid filler, when both components are mixed and the shape is such that the voids can be sufficiently filled immediately before starting the polymerization reaction or while polymerizing, fill the mold. It is also possible to keep it. In addition, it is preferable to add an antioxidant to the molded article according to the present invention. Therefore, it is desirable to add a phenol-based or amino-based antioxidant to the solution in advance. Specific examples of these antioxidants include 2,6-
Di-t-butyl-p-cresol, N, N'-diphenyl-p-phenylenediamine, tetrakis [methylene (3,5-di-t-butyl-4-hydroxycinnamate)] methane and the like can be mentioned.

Further, in the molding of the crosslinked polymer in the present invention, another polymer may be added as an additive in the monomer solution state. As such an additive, an elastomer is effective in enhancing the impact resistance of the molded product and controlling the viscosity of the solution. Examples of the elastomer used for this purpose include a wide range of elastomers such as styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, ethylene propylene-diene terpolymer, and nitrile rubber. You can

In the present invention, such a cyclic olefin crosslinked polymer molded article has an average thickness of 2 mm to 20 mm, especially 2 mm.
It is preferable that the sheet-like material has a size of 10 mm to 10 mm. The average thickness mentioned here refers to the thickness of the sheet in the case of a sheet without ribs or a substantial thickness change, and when the thickness of the entire sheet changes, the average value of the maximum thickness and the minimum thickness. Refers to. Further, when the sheet has a convex rib on the back surface, it means the average thickness of the portion excluding the rib portion.

In the present invention, the sheet-like material has a back surface (F
It is preferable that reinforcing ribs are integrally molded on the side opposite to the joint surface with the RP molded product) to enhance strength and rigidity. Since the rib shape and the rib arrangement can be integrally molded with the crosslinked polymer molded product, there is almost no limitation, and vertical ribs, lattice ribs, and corrugated ribs can be easily provided. In order to give the molded article sufficient rigidity, it is necessary to increase the second moment of area, but in order to effectively do this, it is effective to increase the rib height. Maximum rib height is possible up to the limit where it does not interfere with internal mounting equipment. Therefore, the rib height is 10 mm to 500 mm, preferably 15 mm regardless of vertical ribs, lattice ribs or corrugated ribs.
To 150 mm, more preferably 20 mm to 80 mm
Is. The rib interval is an interval of 20 mm to 500 mm, preferably, so as not to be largely deformed by the foot load.
A spacing of 30 mm to 300 mm is suitable, and the ribs are preferably provided on almost the entire surface of the fitting except for the internal fittings. Usually, the rib portion is integrally formed with the molded article main body (sheet-like) portion by the cross-linked polymer, but in some cases, there is no problem even if the conventional attachment of metal or wood products is used together. . At this time, it is preferable to provide the rib made of the cross-linked polymer at a position where a mounting position of metal or wood products is removed, and the rib interval is selected in consideration thereof.

On the other hand, the FRP molded product that is bonded (bonded) to the crosslinked polymer molded product is SMC, BMC, R
The curable matrix resin used here is generally an unsaturated polyester resin, vinyl ester resin, melamine resin, diallyl phthalate resin,
There are epoxy resins, polyurethane resins and the like, and unsaturated polyester resins are preferable. Examples of the reinforcing fiber constituting the FRP include glass fiber, carbon fiber, aramid fiber, polyester fiber, acrylic fiber, rock wool, steel fiber and the like, and preferably glass fiber is used.

When producing an FRP molded product, a polymerization initiator, a cross-linking agent, a diluent, a reaction accelerator, a filler such as a pigment, etc. are mixed with these and molded and cured. It is preferable to decorate the surface of the FRP molded product with a stone tone, a gel coat finish, or the like because the added value is improved and the product becomes highly functional. A stone tone is generally 1 to 3 colors
It was sprayed so as to form a granular shape of about 5 mm. In addition to stone patterns, it is possible to add patterns such as granular, geometrical, non-geometrical, and irregular yarn patterns. Further, the outermost surface of the FRP molded product may be further subjected to a clear coat or painting to improve the feel and appearance of the surface. Further, surface decoration can be performed by a stock solution coloring method in which a colorant is mixed with the constituent resin of the FRP molded product. Further, this FRP molded product can be shaped into a desired shape such as a bathtub, a washing area, and a waterproof pan by press working or the like.

In the present invention, the surface of the cross-linked polymer molding (the surface without protrusions such as ribs) is bonded to the back side of the FRP molding by bonding or the like, and thus the surface is applied by FRP. A composite structure having a decorative function and rigidity as a surface and having impact resistance and increased rigidity by rib reinforcement is formed by the crosslinked polymer. Between the FRP molded article and the crosslinked polymer molded article in the composite structure, an adhesive agent and / or heat insulation
By interposing a material having a buffer function, the rigidity is further increased and the impact resistance is improved.

The type of such an adhesive is not particularly limited, but there is a large tensile yield strain between the FRP and the crosslinked polymer that can absorb impact or the like, for example, a one-component curing type urethane polymer, a two-component curing type. Urethane polymers and epoxy polymers are preferred. Further, before applying the adhesive, it is preferable to perform cleaning and degreasing treatment (using a solvent such as isopropyl alcohol or acetone) on the applied portion. It is preferable to apply the primer after the degreasing treatment and then apply the adhesive. The type of the primer is not particularly limited, but a urethane-based primer, a polyisocyanate-based primer and the like are preferable. Adhesive and primer are applied by spray method,
Known methods such as brush coating and roll coating can be adopted. Further, the material having a heat insulating / buffering function is not particularly limited in its type, but a foam material such as urethane foam or thermoplastic resin is preferable. The injection may be carried out by a known method, and it is injected between the FRP molded product and the crosslinked polymer molded product so that both are foamed and adhered at the same time. If necessary, the cross-linked polymer molded product and / or the FRP molded product may have a roughened surface in advance, and then the surface may be bonded.

In the bonding, the surface of the crosslinked polymer molded product is usually attached to almost the entire back surface of the FRP molded product, but as long as the two are sufficiently bonded, it is not always necessary to bond them to the entire surface. Partial adhesion is also possible if the area is 100 cm ² or more, preferably 200 cm ² or more.

[0028]

According to the present invention, a crosslinked polymer obtained by a reaction injection molding method of a metathesis-polymerizable cyclic olefin in the presence of a catalyst component of a metathesis polymerization catalyst system and an activator component is provided on one surface of an FRP molded article. By joining the united molded products, it becomes a composite structure that is more resistant to collision and superior in durability, particularly lightweight and highly rigid, as compared with conventional materials. Therefore, this composite structure is used in various bathroom systems such as a unit bath, a system toilet, a system bathroom equipped with a washbasin and a toilet, a washbasin that constitutes a washbasin and a bathroom,
A waterproof pan for a washing place and / or a bathtub, or a bathtub or a bathtub adjacent to the washing place, a bathtub wall forming a bathtub,
It is useful as a bathtub ceiling.

[0029]

The contents of the present invention will be described more specifically below with reference to Examples and Comparative Examples relating to a composite structure for a bathroom washroom, but the present invention is not limited to these. The relative weight in Table 1 is
It is a relative value in which the weight of the FPR molded product of Comparative Example 1 is 100. Further, the maximum deformation amount shown in Table 1 is 1
It is a value obtained by actually measuring the maximum amount of deformation when a load is applied to the center of the composite structure for a washing place through a load plate having a diameter of 280 mm stretched with a rubber plate of 0 mm.

[Example 1 and Comparative Example] 1) Preparation of (Solution A) of one of the monomer solutions: 28 parts by weight of tungsten hexachloride was dried under a stream of nitrogen to dry toluene 80.
1 part by weight, and then a solution of 1.3 parts by weight of t-butanol dissolved in 1 part by weight is added and stirred for 1 hour. Then, a solution consisting of 18 parts by weight of nonylphenol and 14 parts by weight of toluene is added and purged with nitrogen for 5 hours. It was stirred under. Further, 14 parts by weight of acetylacetone was added. Stirring was continued overnight under a nitrogen purge while expelling by-produced hydrogen chloride gas to prepare a polymerization catalyst solution. Next, with respect to a monomer mixture consisting of 95 parts by weight of purified dicyclopentadiene (purity 99.7% by weight, the same below) and 5 parts by weight of purified ethylidene cyclic olefin (purity 99.5% by weight, the same below), 70 mol of ethylene was contained. % Ethylene-propylene-
The above catalyst solution for polymerization was added to a solution containing 3 parts by weight of ethylidene cyclic olefin copolymer rubber and 2 parts by weight of Etanox 702 as an oxidation stabilizer, with a tungsten content of 0.01M.
A monomer liquid (Solution A) containing a catalyst component was prepared so that the amount became / L.

2) Preparation of the other raw material liquid (solution B): ethylene-propylene-ethylidene cyclic with an ethylene content of 70 mol% based on a monomer mixture consisting of 83 parts by weight of purified dicyclopentadiene and 5 parts by weight of purified ethylidene cyclic olefin. A solution of 3 parts by weight of an olefin copolymer rubber was mixed with a solution of trioctylaluminum 85, dioctylaluminum iodide 15 and diglyme 100 in a molar ratio to prepare a polymerization activator mixture solution having an aluminum content of 0.03 M / L. At a certain ratio to prepare a monomer liquid (solution B) containing an activator component.

3) Using the molding solution A and solution B of the cyclic olefin-based cross-linked polymer, as a part for a washing place in a bathroom for home use, the length is 1.2 m, the width is 1.2 m, and the thickness is 3 mm. 40mm height with grid ribs spaced 100mm vertically and horizontally
Molding was performed using a mold having a rib (rib end thickness 5 mm, taper one side 2 °). As the molding conditions, the reaction solution injection molding was performed with the liquid temperature of the raw material solutions A and B being 30 ° C., the fixed mold temperature being 90 ° C., and the movable mold temperature being 60 ° C.

4) Manufacture of FRP molded product: An SMC material (trade name "Dick Matt 2400" manufactured by Dainippon Ink and Chemicals, Inc.) composed of unsaturated polyester resin, glass fiber and inorganic filler was used by a known method. The shape of the bathroom washroom,
Press molding was performed according to the dimensions. Length 1.2m, width 1.
It is 2m thick and 3mm thick and has no ribs. The surface was gel-coated.

5) Production of composite structure: FRP (SM
C) A urethane adhesive (trade name "Mighty Grip 3000") is formed on the molded product so that the rib-free side of the cyclic olefin-based crosslinked polymer molded product is in contact with the back surface (the surface opposite to the gel-coated surface) of the molded product. "E-Tech Co., Ltd.
To produce a desired composite structure. This composite structure is a laminated structure composed of a cyclic olefin-based crosslinked polymer molded product having a gel coated finish on the front surface and a rib on the back surface, and its physical properties are shown in Table 1 below.
As "Example 1".

[Comparative Example 1] A washing place was prepared only with FRP molded products. The thickness of the molded product at this time was 4 mm, and ribs were arranged in the same manner as in the crosslinked polymer molded product of Example 1 except that the rib shape was 30 mm, which was 10 mm shorter than that of Example 1. The physical properties were as shown as "Comparative Example 1" in Table 1 below.

[Example 2] The urethane-based adhesive was replaced with urethane foam (trade name "Bayjour" manufactured by Sumitomo Bayer Urethane Co., Ltd.), and between the FRP molded product and the cyclic olefin-based crosslinked polymer molded product, A composite structure was obtained in the same manner as in Example 1 except that a urethane foam layer having a thickness of 2 mm was formed. The physical properties were as shown in "Example 2" in Table 1 below.

[Example 3] A composite structure was manufactured in the same manner as in Example 1 except that the surface finish of the FRP molded product was changed to a stone tone. The physical properties were as shown in Table 1 below as "Example 3".

[Example 4] Using the same solutions A and B as in Example 1, a cycloolefin cross-linked polymer molded product having a thickness of 3 mm was molded in the same manner as in Example 1, and a high surface was formed on the back surface of the molded product. Lattice ribs having a length of 40 mm and 100 mm intervals are integrally molded, and the molded product has a height of 40 mm and a unidirectional interval of 5
A crosslinked polymer molded article provided with 0 mm lateral corrugated ribs and 200 mm vertical ribs (vertical to the corrugated direction) was prepared. On the other hand, the same thickness as in Example 1 3 mm
The FRP molded article was prepared by press molding, and this was bonded to the part of the olefin-based crosslinked polymer excluding the corrugated rib portion with the same adhesive as in Example 1 to prepare a composite structure. The physical properties of the obtained composite structure were as shown in Table 1 below as "Example 4".

[0039]

[Table 1]

As an impact test of the composite structures and FRP molded products of Examples 1 to 4 and Comparative Example 1, 7 kg was applied to each test object.
The bag filled with the sand was continuously dropped 10 times at a height of 1 m, and the test was conducted to observe the change. There was no problem in any of the laminated composite structures according to the present invention, but in the product only of FRP, slight cracks were generated in the rib portion.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hiroyuki Umeda             2-1-1 Uchisaiwaicho, Chiyoda-ku, Tokyo             Human Meton Co., Ltd. F-term (reference) 2D032 AB02 GA00                 2D061 CC11                 4F100 AK80B AR00D BA02 BA03                       BA04 BA07 BA10A BA10B                       BA10C CC00C DD04B DH02A                       EJ052 GB90 HB00C JJ02D                       JK01 JK10 JK11D JL03                       JL08B JL10C YY00B

Claims (7)

[Claims] 1. A cyclic olefin-based crosslinked polymer molded product obtained by simultaneously polymerizing and molding a metathesis-polymerizable cyclic olefin monomer in the presence of a polymerization catalyst is bonded to one surface of a fiber reinforced plastic (FRP) molded product. A synthetic resin composite structure characterized by the above. 2. The fiber reinforced plastic (FRP) molded article has a grain-like finish or a gel coat finish on a surface different from the joint surface of the cross-linked polymer molded article, or has a surface decoration for coloring the raw material. The synthetic resin composite structure according to claim 1, which comprises: 3. The cyclic olefin-based crosslinked polymer molded product and the fiber reinforced plastic (FRP) molded product are bonded together via an adhesive and / or a material having a heat insulating / buffering function. The synthetic resin composite structure according to claim 1 or 2. 4. The synthetic resin composite structure according to claim 1, wherein the cyclic olefin-based crosslinked polymer molded product is a molded product having an average thickness of 2 to 20 mm. 5. The cyclic olefin-based crosslinked polymer molded product is a fiber reinforced plastic (FRP) in the molded product.
At least one of a vertical rib, a lattice rib, and a corrugated rib is integrally molded at a position other than a joint surface with the molded product, and the molded product is any one of claims 1 to 4. Synthetic resin composite structure. 6. A bathroom component comprising the synthetic resin composite structure according to any one of claims 1 to 5. 7. (a) Fiber reinforced plastic (FRP)
(C) a step of producing a molded article; and (b) a step of obtaining a cyclic olefin-based cross-linked polymerization molded article obtained by simultaneously performing polymerization and molding from a cyclic olefin monomer in the presence of a polymerization catalyst.
A step of filling the fiber-reinforced plastic (FRP) molded product and the cyclic olefin-based cross-linked polymer with an adhesive and / or a material having a heat insulating / buffering function and integrally joining the two; (d) FRP A step of decorating the surface of a molded article, the method comprising the steps of: manufacturing a synthetic resin composite structure.