JP2002036435A - Laminated molded object and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated molded object excellent in design effect, quality, rigidity and productivity. SOLUTION: A crosslinked norbornene resin polymer excellent in mechanical strength and elastic modulus is integrally laminated on a surface layer comprising an acrylic resin molded object to impart sufficient rigidity to the surface layer. The acrylic resin molded object 1 is arranged in a casting mold 12 so as to provide a predetermined gap 13 with respect to the molding surface of the mold and the gap 13 between the acrylic resin molded object and the molding surface is filled with a polymerizable composition with a viscosity of 10,000 cps or less comprising a composition containing a norbornene monomer and a metathesis polymerization catalyst, and this polymerizable composition is cured to obtain the laminated molded object wherein the crosslinked norbornene resin layer 2 is integrally laminated on the acrylic resin molded object 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated molded article used for, for example, a bathtub, a waterproof pan, a kitchen counter, a washbasin, a toilet bowl, an exterior material, a deck material, a wall material and the like, and a method for producing the same.

[0002]

2. Description of the Related Art A molded article of an acrylic resin sheet has properties such as weather resistance, water resistance, moldability, surface gloss, and excellent design, and is therefore suitable for the surface of a bathtub, a wash bowl, or the like. It is suitably used as a material. However, since the mechanical strength and rigidity of the acrylic resin sheet alone are insufficient, the back surface needs to be backed up. As a method of reinforcing the acrylic resin sheet, for example, there is a method of backing up an acrylic resin sheet with an unsaturated polyester resin (FRP) reinforced with glass fiber (for example, Japanese Patent Application Laid-Open No. 9-1092).
No. 87).

[0003]

In the above-described backup reinforcing method, glass fibers and unsaturated polyester are sprayed on the back surface of the acrylic resin molded body, and then defoamed and impregnated using a roll or the like. In general, a method of performing lamination and integration is generally adopted.

[0004] However, since these series of operations are performed manually, there is a large variation in quality due to the skill of the operator and the physical condition during the operation. In addition, there are many problems such as high labor costs and adverse effects on the human body due to the styrene monomer contained in the unsaturated polyester resin.

In addition, much time is required for laminating work and curing of the resin. For example, in the case of an acrylic bathtub, a resin and glass fiber are laminated on the back surface of an acrylic resin vacuum formed body by a spray-up method, and then heated and cured to reinforce the backup. When laminated, the resin undergoes large curing shrinkage, which causes cracks and poor appearance such as sink marks. For this reason, the backup reinforcement layer must be laminated several times, and conventionally, it took about 2 hours per body to produce a backup-reinforced acrylic bathtub.

[0006] It is an object of the present invention to provide a laminated molded article excellent in design, quality, rigidity and productivity, and to produce such a laminated molded article with good quality, productivity and working environment. It is an object of the present invention to provide a method for producing a laminated molded article that can be performed.

[0007]

Means for Solving the Problems The laminated molded article of the present invention comprises:
It is characterized in that a crosslinked norbornene-based resin layer is laminated and integrated on the acrylic resin molded body.

In the laminate of the present invention, the crosslinked norbornene resin is preferably a dicyclopentadiene resin. Further, the crosslinked norbornene-based resin layer is preferably a crosslinked norbornene-based resin containing an inorganic filler.

In the method of manufacturing a laminated molded article according to the present invention, an acrylic resin molded article is disposed with a predetermined gap provided with respect to a mold surface of a casting mold, and the acrylic resin molded article and the mold surface are separated from each other. By filling the gap with a polymerizable composition having a viscosity of 10,000 cps or less with a composition containing a norbornene-based monomer and a metathesis polymerization catalyst, and curing, the crosslinked norbornene-based resin layer was integrally laminated on the acrylic resin molded article. It is characterized by obtaining a laminated molded article.

In the method for producing a laminated molded article according to the present invention,
The crosslinked norbornene-based resin is preferably a dicyclopentadiene-based resin. Further, it is preferable that the polymerizable composition to be filled in the gap between the acrylic resin molded body and the mold surface is a mixture of a norbornene-based monomer and an inorganic filler.

The details of the laminated molded article of the present invention will be described.

First, the crosslinked norbornene-based resin used in the laminated molded article of the present invention is not particularly limited.
A resin obtained by subjecting one or more norbornene-based monomers to ring-opening metathesis polymerization using a metathesis polymerization catalyst and cross-linking them can be used.

Examples of the norbornene-based monomer include bicyclics such as 2-norbornene and norbornadiene, tricyclics such as dicyclopentadiene and dihydrodicyclopentadiene, tetracyclododecene, ethylidenetetracyclododecene, and phenyltetrane. Tetracyclics such as cyclododecene, pentacyclics such as tricyclopentadiene,
Seven-rings such as tetracyclopentadiene, and their alkyl-substituted (eg, methyl, ethyl, propyl, butyl-substituted, etc.), alkylidene-substituted (eg, ethylidene-substituted), aryl-substituted (eg, phenyl, Derivatives having a polar group such as an epoxy group, a methacryl group, a hydroxyl group, an amino group, a carboxyl group, a cyano group, a halogen group, an ether group, and an ester bond-containing group, as well as a tolyl-substituted compound. These norbornene-based monomers may be used alone, or 2
More than one species may be used in combination.

The norbornene-based monomer may be copolymerized with another monomer capable of ring-opening copolymerization with the norbornene-based monomer, if necessary, as long as the object of the present invention is not hindered.

Examples of other monomers capable of ring-opening copolymerization with the norbornene-based monomer include monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene and cyclododecene, and indene, cumarone and coumarone-indene comonomer. And a cyclic monomer having metathesis polymerization activity.

These other monomers capable of ring-opening copolymerization with the norbornene-based monomer may be used alone,
More than one species may be used in combination.

As a catalyst for ring-opening metathesis polymerization of a norbornene-based monomer, tungsten,
Examples include metal halides such as molybdenum, tantalum, ruthenium, rhenium, osmium, and titanium, oxyhalides, oxides, and organic ammonium salts.
These metathesis polymerization catalysts may be used alone or in combination of two or more.

When the ring-opening metathesis polymerization of a norbornene-based monomer needs to be carried out in air as a process, it is preferable to select a catalyst having excellent stability with time in air among the above-mentioned metathesis polymerization catalysts. Specifically, a ruthenium carbene catalyst represented by the following general formula [I] and a ruthenium vinylidene catalyst represented by the general formula [II] are preferable. These ruthenium carbene catalysts and ruthenium vinylidene catalysts may be used alone or in combination of two or more.

[0019]

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Wherein R1 and R2 independently of one another are hydrogen, C2-C20-alkenyl, C1-C20-alkyl, aryl, C1-C20-carboxylate, C1
-C20-alkoxy, C2-C20-alkenyloxy, aryloxy, C2-C20-alkoxycarbonyl, C1-C20-alkylthio (these are
It may be optionally substituted by C5-alkyl, halogen, C1-C5-alkoxy or optionally substituted by C1-C5-alkyl, halogen, phenyl substituted by C1-C5-alkoxy. ), A ferrocene derivative,
In the formula, X1 and X2 each independently represent any anionic ligand, and L1 and L2 each independently represent any neutral electron donor. And X
Two or three of 1, X2, L1 and L2 may together form a polydentate chelating ligand.

More preferably, in the formulas (I) and (II), R1 and R2 independently of one another are hydrogen, methyl, ethyl, phenyl, ferrocenyl,
Or vinyl optionally substituted by methyl, ethyl, phenyl or ferrocenyl;
And X2 are independently Cl and Br, and L1 and L2 are independently trimethylphosphine, triethylphosphine, triisopropylphosphine, triphenylphosphine or tricyclohexylphosphine, a ruthenium carbene catalyst or ruthenium vinylidene It is a catalyst.

The amount of the above-mentioned metathesis polymerization catalyst used in the ring-opening metathesis polymerization of the norbornene-based monomer varies depending on the activity of the metathesis polymerization catalyst. Preferably it is 500,000 molar equivalents. If the amount of the metathesis polymerization catalyst to all monomers is more than 1/5 equivalent, the molecular weight of the obtained resin will not be sufficiently increased, and if it is less than 1 / 500,000 equivalent, the polymerization rate will be low.

Further, the crosslinked norbornene resin includes:
If necessary, a filler, a reinforcing material, an antioxidant (antioxidant), a foaming agent, an antifoaming agent, a thixotropic agent, an antistatic agent, a molecular weight modifier, as long as the object of the present invention is not hindered. One or more of various additives such as a polymer modifier, a flame retardant, a softener, a plasticizer, a surfactant, a pigment, a dye, a colorant, and an elastomer may be added.

Examples of the filler include calcium carbonate, aluminum hydroxide, magnesium carbonate, sodium bicarbonate, clay, talc, mica, silica, kaolin, fly ash, montmorillonite, glass balloon, silica balloon, thermally expandable vinylidene chloride particles and the like. No. These fillers may be used alone or in combination of two or more. These fillers may be used after being subjected to a surface treatment with a coupling agent, a surface treatment agent, or the like, if necessary.

Examples of the reinforcing material include fibers such as glass fiber, carbon fiber, and aramid fiber. The form of these fibers is not particularly limited, and may be short fibers or long fibers, or may be processed into a cloth, mat, nonwoven, or the like. These fibers may be used alone or in combination of two or more. Further, these fibers may be used after being subjected to a surface treatment with a coupling agent, a surface treatment agent or the like as necessary.

Examples of the elastomers include natural rubber, polyisoprene, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, chloroprene, styrene-isoprene-styrene block copolymer, and styrene-butadiene-styrene block copolymer. Copolymers, ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, ethylene-vinyl acetate copolymers, and hydrides thereof. These elastomers may be used alone or in combination of two or more.

Known acrylic resins can be used for the acrylic resin molded article used for the laminated molded article of the present invention.
A typical example is an acrylate, and methyl methacrylate is mentioned as a specific example. It is desirable that such an acrylic resin is crosslinked particularly when used in applications requiring mechanical strength and heat resistance.

The acrylic resin molded product itself has a dye,
It may be colored with a pigment, a coloring agent, or the like, or may be given a design such as stone-grain or woodgrain by any method. Further, the rear surface of the transparent acrylic resin may be decorated with printing, a sheet, a resin containing a pattern material, or the like.

The acrylic resin molded body may further include a filler, if necessary, as long as the achievement of the object of the present invention is not hindered.
Reinforcing materials, antioxidants (antiaging agents), foaming agents, defoamers,
One or more of various additives such as a thixotropic agent, an antistatic agent, a molecular weight modifier, a polymer modifier, a flame retardant, a softener, and a plasticizer elastomer may be added.

The method of molding the acrylic resin molded article is not particularly limited, and a molding method most suitable for the intended use, such as extrusion molding, injection molding, compression molding, cast molding, vacuum molding, pressure molding, or gel coating, is used. be able to. Above all, vacuum molding is preferable when molding a large molded body having a curved surface with high production efficiency and low equipment investment, but vacuum molding has a limit to the shape that can be handled, so when a molded body with a more complicated shape is obtained. Is preferably a gel coat in terms of shape.

The thickness of the acrylic resin molded product is not particularly limited, but is preferably about 0.05 mm to 10 mm.

The shape of the acrylic resin molded body is not particularly limited, and can be any desired shape such as a bathtub, a waterproof pan, a kitchen counter, a wash bowl, a toilet bowl, an exterior material, a deck material, a wall material, and the like. .

The crosslinked norbornene-based resin used in the laminated molded article of the present invention has high strength and high rigidity without fiber reinforcement using glass fibers or the like. Therefore, the acrylic resin molded article reinforced with the crosslinked norbornene-based resin is used. Is the strength
The rigidity is dramatically improved. In particular, it is effective for large-sized molded products such as bathtubs, waterproof pans, kitchen counters, washbasins, etc., which require strength and rigidity. Further, since the crosslinked norbornene-based resin is a material having a high heat distortion temperature, it can impart heat resistance to the acrylic resin, and is particularly effective when the laminated molded article of the present invention is used for heat-resistant applications such as a bathtub and a waterproof pan. It is.

The thickness of the crosslinked norbornene resin layer is not particularly limited, and may be appropriately designed according to the strength and rigidity required for the intended use.

It is essential that the acrylic resin molded body is laminated and integrated with the crosslinked norbornene-based resin layer. If necessary, the acrylic resin molded body may have a multilayer structure of three or more layers.
In this case, layers other than the acrylic resin layer and the crosslinked norbornene-based resin layer are not particularly limited, and the material, shape, lamination position, and the like can be arbitrarily selected.

As for the lamination position, it can be provided between the acrylic resin layer and the crosslinked norbornene resin layer.
By providing such a third layer, the laminated molded article of the present invention can have higher added value.

For example, by laminating with a foam, the heat insulating performance of the molded body can be improved. The material of the foam is not particularly limited, but a foam of a urethane resin or a crosslinked norbornene-based resin is preferable. When a transparent acrylic resin molded body is used, a colored layer made of paint as an intermediate layer between the acrylic resin layer and the crosslinked norbornene-based resin layer, a sheet containing a pattern such as stone-grain or woodgrain, By providing the resin layer, it is possible to obtain a molded article having higher designability.

The laminated molded article of the present invention may be subjected to some treatment in order to increase the bonding strength of each layer. Examples of the method include a method of providing an intermediate layer having good adhesion to both layers, bonding by an anchor effect by primer treatment or sanding treatment, and the like.

Further, the laminated molded article of the present invention may be used by being joined and integrated with another member. In this case, the material and shape of the member to be used and the joining site are not particularly limited, and an optimum member may be selected according to the intended use. Examples of such a member include steel and wood, and by joining with such a member, the rigidity of the laminated molded article of the present invention can be further increased or a dimensional change due to a temperature change can be reduced. .

Further, in the laminated molded article of the present invention, the backup portion made of the crosslinked norbornene resin may have a rib structure. By providing the rib, both lightness and rigidity can be achieved. In this case, the shape, number, and position of the ribs may be appropriately designed according to the strength and rigidity required for the intended use.

In the laminated molded article of the present invention, the crosslinked norbornene-based resin layer may be laminated on the entire surface of the acrylic resin molded article, or may be laminated only on a necessary portion.

The laminated molded article of the present invention will be described more specifically.

The crosslinked norbornene resin used in the laminated molded article of the present invention is preferably a dicyclopentadiene resin.

The dicyclopentadiene resin is defined as the dicyclopentadiene monomer alone or the other monomer capable of ring-opening copolymerization with the dicyclopentadiene monomer and the dicyclopentadiene monomer in the presence of the metathesis polymerization catalyst. And a polymer obtained by subjecting the compound to ring-opening metathesis polymerization.

The crosslinked dicyclopentadiene resin is
Since the crosslinked norbornene-based resin is particularly tough and has high heat resistance, the acrylic resin molded article laminated and integrated with the dicyclopentadiene-based resin has excellent strength, rigidity and heat resistance. Further, the dicyclopentadiene monomer is preferable because it is inexpensive and easily available.

The crosslinked norbornene-based resin layer used in the laminated molded article of the present invention may be a crosslinked norbornene-based resin containing an inorganic filler.

The crosslinked norbornene-based resin has sufficient strength, rigidity, heat resistance, etc., even when used alone, but is particularly useful in applications where high strength, high rigidity, high heat resistance, etc. are required. By combining with an inorganic filler, the physical properties can be further enhanced.

Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium carbonate, sodium hydrogen carbonate, clay, talc, mica, silica, kaolin, fly ash, montmorillonite, glass balloon, silica balloon and the like. Among them, calcium carbonate, aluminum hydroxide, and fly ash are particularly preferred because of good cost and good physical properties of the molded product.

The crosslinked norbornene-based resin composited with the inorganic filler has high rigidity, so it is effective not only in strength design in applications requiring rigidity, but also has a low coefficient of linear expansion. It is also preferred in terms of dimensional stability of the body. Further, the crosslinked norbornene resin filled with aluminum hydroxide becomes flame-retardant. Further, the crosslinked norbornene-based resin filled with a glass balloon and a silica balloon has good heat insulating properties.

These inorganic fillers may be used alone or in combination of two or more. In addition, these inorganic fillers may be used after being subjected to a surface treatment with a coupling agent, a surface treatment agent, or the like, if necessary.

The filling amount of the inorganic filler is not particularly limited, but if the filling amount is too small, great expectation cannot be expected in terms of physical properties such as rigidity and linear expansion. Conversely, if the filling amount is too large, the strength may decrease. . The filling amount of the inorganic filler is preferably 30 parts by weight or more and 300 parts by weight or less based on 100 parts by weight of the crosslinked norbornene-based resin.

Next, the method for producing the laminated molded article of the present invention will be described in detail.

According to the production method of the present invention, an acrylic resin molded body is arranged in a state where a predetermined gap is provided from a mold surface of a casting mold, and a norbornene monomer is placed in a gap between the acrylic resin molded body and the mold surface. By filling and curing a polymerizable composition having a viscosity of 10,000 cps or less with a composition containing and a metathesis polymerization catalyst, a laminated molded body in which a crosslinked norbornene-based resin layer is laminated and integrated with an acrylic resin molded body is obtained. It is characterized by the following.

The material of the casting mold used in the manufacturing method of the present invention is not particularly limited, and a metal material such as aluminum or steel, a hard plastic material such as epoxy resin or hard vinyl chloride resin, silicon rubber, Rubber materials such as fluorine rubber, ceramic materials, wood, and the like are given as examples. The surface of the casting mold may be subjected to surface treatment such as release treatment or plating treatment for the purpose of improving the releasability with the crosslinked norbornene resin or improving the durability of the mold. You may give it.

The casting mold may be arranged on the entire surface of the acrylic resin molded body, or may be arranged only on a necessary portion. When the polymerizable composition to be filled in the gap between the acrylic resin molded body and the casting mold flows out from the gap between the two, an appropriate seal may be performed.

A specific example of the manufacturing method of the present invention will be described with reference to FIG.

First, as shown in FIG. 1 (A), the acrylic resin deformed body 1 is arranged in a state where a predetermined gap 13 is provided with respect to the mold surface of the casting mold (concave mold) 12.

Next, a composition containing a norbornene-based monomer and a metathesis polymerization catalyst having a viscosity of 1000
A polymerizable composition of 0 cps or less is filled through the injection hole 12 a of the casting mold 12.

After the resin is cured, the laminated molded body (FIG. 1B) in which the acrylic resin deformed form 1 and the crosslinked norbornene resin 2 are laminated and integrated is removed from the casting mold 12. Take out.

According to the manufacturing method of this example, since the acrylic resin heteromorphic shaped body 1 is used as one of the casting molds, and the polymerization of the crosslinked norbornene-based resin is joined and integrated at that time, the casting molding mold is used. Is advantageous in that the production cost of the casting mold is small.

Here, when the acrylic resin irregularly formed body is formed by vacuum forming, there are portions that are greatly elongated and thinned during vacuum forming depending on the shape.
In this case, since the thin portion may be deformed by the pressure of the polymerizable composition or the like, it is preferable to reinforce the thin portion with some member.

In the manufacturing method shown in FIG. 1, the acrylic resin irregularly shaped body 1 may be fixed to the casting mold 12 so that the acrylic resin irregularly shaped body 1 does not shift from the casting mold 12. . In addition, since the gap 13 between the mold surface of the casting mold 12 and the acrylic resin shaped body 1 becomes the thickness of the crosslinked norbornene-based resin layer after molding, the physical properties and the like required for the target product The design should be based on the following conditions.

Another embodiment of the manufacturing method of the present invention will be described with reference to FIG.

First, the acrylic resin deformed body 1 is placed in contact with the surface of one casting mold (convex mold) 11 (FIG. 2A). The shape of the casting mold 11 does not necessarily have to be the same as that of the acrylic resin deformed body 1 as a whole, and may be such that only a part thereof contacts the acrylic resin deformed body 1.

Next, in a state where the acrylic resin deformed form 1 is attached to one casting mold 11, while maintaining a predetermined gap 13 with respect to the acrylic resin deformed form 1, the other casting form 1 is formed. Set the mold (concave mold) 12 (FIG. 2)
(B)).

Acrylic resin deformed shaped body 1 and casting mold 1
The composition containing a norbornene-based monomer and a metathesis polymerization catalyst having a viscosity of 10,000 cp
s or less of the polymerizable composition is injected into the injection hole 12 of the casting mold 12.
Fill from a.

After the resin has hardened, the laminated molded body in which the acrylic resin deformed form 1 and the crosslinked norbornene resin 2 are laminated and integrated is removed from the casting molds 11 and 12 and taken out.

In the manufacturing method shown in FIG. 2, the interval of the gap 13 between the acrylic resin irregularly formed body 1 and the casting mold 12 is equal to the thickness of the dicyclopentadiene resin layer after molding. What is necessary is just to design from the physical properties etc. required in a product.

Another specific example of the manufacturing method of the present invention will be described with reference to FIG.

First, an acrylic resin gel coat layer is provided on one casting mold (convex mold) 11 to obtain an acrylic resin irregularly formed body 1 (FIG. 3A).

The other casting mold (concave mold) 12 is arranged with a predetermined gap 13 left between the acrylic resin deformed body 1 (FIG. 3B).

Next, in the gap between the acrylic resin molded body 1 and the casting mold 12, a composition containing a norbornene-based monomer and a metathesis polymerization catalyst having a viscosity of 10,000 cps
The following polymerizable composition is filled through the injection hole 12a of the casting mold 12.

After the resin is cured, the molded laminate (FIG. 3 (C)) in which the acrylic resin deformed form 1 and the crosslinked norbornene-based resin 2 are integrally laminated is removed from the casting mold 12 and taken out. .

In the manufacturing method shown in FIG. 3, the interval of the gap 13 between the acrylic resin irregularly formed body 1 and the casting mold 12 becomes the thickness of the crosslinked norbornene resin layer after molding. May be designed based on the physical properties required in the above.

The polymerizable composition containing the norbornene-based monomer and the metathesis polymerization catalyst used in the production method of the present invention needs to have a viscosity of 10,000 cps or less at the operating temperature. If the viscosity exceeds 10,000 cps, the fluidity becomes poor, so that the polymerizable composition hardly penetrates into narrow gaps, and the object of the present invention cannot be achieved.

Here, since the polymerizable composition of the norbornene-based monomer can be made into a very low-viscosity compounding liquid, it has good permeability into narrow gaps even at a low pressure.
Therefore, the resin can be poured into every corner of a large product even in normal pressure molding or low pressure molding by cast molding.

Since the crosslinked norbornene-based resin generates heat during polymerization and curing, if there is a possibility that the acrylic resin molded article may be deformed by the heat generation, the molding may be performed by suppressing the heat generation by any method. As a method of suppressing heat generation, for example, a method of suppressing the heat of reaction of the resin by cooling the casting mold with a cooling pipe, a method of performing molding in a curing room controlled at a low temperature, or a type and addition of a catalyst. Examples of the method include a method in which heat generation is suppressed depending on the amount.

The norbornene monomer used in the production method of the present invention is preferably dicyclopentadiene.

The dicyclopentadiene monomer means a dicyclopentadiene monomer alone or a mixture of a dicyclopentadiene monomer and the other monomer capable of ring-opening copolymerization with the dicyclopentadiene monomer.

The dicyclopentadiene monomer has a particularly low viscosity among norbornene-based monomers, so that it has good permeability into narrow gaps even at a low pressure. Therefore,
Even in normal pressure molding or low pressure molding by casting molding,
The resin can be poured into every corner of the large product, and a good laminated molded article free from voids and insufficient penetration of the resin can be obtained.

The dicyclopentadiene monomer is
Since the polymerization reactivity is particularly excellent among the norbornene-based monomers, the laminated molded article of the present invention can be produced in a short time with high working efficiency. Further, the dicyclopentadiene monomer is preferable in that it is inexpensive and easily available.

The norbornene monomer used in the production method of the present invention may contain an inorganic filler. The liquid mixture of the norbornene-based monomer has very good fluidity even when the inorganic filler is highly filled, and has good permeability into the gap even when a large amount of the inorganic filler is filled.

The amount of the inorganic filler to be filled is not particularly limited, but may be 30 to 100 parts by weight of the crosslinked norbornene resin.
It is preferable that the amount is not less than 300 parts by weight and not less than 300 parts by weight.
By filling a large amount of the inorganic filler, the curing shrinkage of the resin is reduced, and deformation or peeling due to the shrinkage is less likely to occur, so that a good laminated structure can be manufactured. Although it differs depending on the type and shape of the filler, it is not preferable that the filling amount is 300 parts by weight or more, since the fluidity deteriorates.

Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium carbonate, sodium hydrogen carbonate, clay, talc, mica, silica, kaolin, fly ash, montmorillonite, glass balloon, silica balloon and the like. Among them, calcium carbonate, aluminum hydroxide and fly ash are particularly preferred in view of cost and fluidity of the polymerizable composition.

These inorganic fillers may be used alone or in combination of two or more. These inorganic fillers can be used after being subjected to a surface treatment with a coupling agent, a surface treatment agent, or the like, if necessary.

Here, an application example of the present invention is, for example, an acrylic bath, which can be used for the purpose of backing up a vacuum-formed deformed acrylic resin such as PMMA with a crosslinked norbornene resin polymer. .

<Function> According to the present invention, a crosslinked norbornene-based resin polymer having high mechanical strength and elastic modulus is laminated and integrated on the surface layer made of an acrylic resin molded article, so that sufficient rigidity is imparted. Can be. Moreover, since the surface is made of an acrylic resin, it is possible to obtain a laminated molded article having excellent design properties such as weather resistance, water resistance and surface gloss.

Further, since the crosslinked norbornene resin has a very low viscosity, it is possible to reinforce the back-up by casting even in the case of a laminated molded article having a complicated shape, and the curing of the resin is completed in a very short time. It is superior in quality and productivity to conventional hand lay-up and reinforcement by spray-up.

According to the method for producing a laminated molded article of the present invention,
Since the acrylic resin molded body and the crosslinked norbornene-based resin are integrally laminated by casting, good backup reinforcement can be performed. In other words, since casting can be performed at low pressure, when the resin is poured into the casting mold, the acrylic resin molded article is less likely to be deformed or displaced from the installation position. The resin layer (backup reinforcing layer) can be formed in a good state.

Further, when an acrylic resin molded body is used as one of the casting molds and is laminated and integrated together with the polymerization of the norbornene-based monomer, there is an advantage that the initial investment can be reduced because only one mold is required for the production of the mold. There is.

[0091]

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

<Example 1> Acrylic resin deformed form Polymethyl methacrylate (PMMA) vacuum formed body Shape: Bath tub Thickness: about 1 mm Backup material Material: Crosslinked norbornene resin Monomer: Dicyclopentadiene monomer Metathesis polymerization catalyst : Bis (tricyclohexylphosphine) benzylidene ruthenium dichloride Filler: unused Dicyclopentadiene was used as a monomer, and 10 parts of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride of the following structural formula [III] was dissolved in 200 parts of toluene. The solution was mixed and stirred at 40 ° C. so that the molar ratio of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride to dicyclopentadiene was 1/10000 to obtain a polymerizable composition.

[0093]

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As shown in FIG. 4, the acrylic resin deformed body 10 having a bathtub shape is placed in contact with the convex mold 21 of the casting mold, and the concave mold 22 of the casting mold is replaced with the acrylic resin deformed body. 10 with a predetermined gap 23 left between them. The gap 23 between the concave mold 22 and the acrylic resin deformed body 10 was set to about 5 mm on both the side surface and the bottom surface. The convex mold 21 and the concave mold 22 of the casting mold were both made of vinyl chloride resin.

Next, the polymerizable composition was poured into the gap 23 between the concave mold 22 and the acrylic resin deformed body 10 from the injection hole 22a of the concave mold 22, and then heat-cured at 60 ° C. for 10 minutes to form an integrated body. And removed from the casting mold to obtain a laminated molded body. The total molding time from setting the acrylic resin irregularly shaped body 10 on the convex mold 21 of the casting mold to removing the mold and obtaining the bathtub-shaped laminated molded body is about 1 hour.
9 minutes.

In the obtained laminated molded product (bath), a dicyclopentadiene polymer is integrated and reinforced on the back surface of the acrylic resin deformed shape 10, and the thickness of the dicyclopentadiene polymer is such that the side surface and the bottom surface are different. Both are about 5mm,
It was excellent in rigidity. In addition, no bubbles were observed in the dicyclopentadiene polymer layer, and the resin was filled to the end.

The polymerizable composition prepared by the above treatment was applied to a thickness of 5
mm, and heat-cured at 60 ° C. for 10 minutes to obtain the same composition as the dicyclopentadiene polymer.
A flat plate under curing conditions was prepared. 15m width from the obtained flat plate
A sample having a length of 80 mm and a length of 80 mm was cut out, and the sample was subjected to a three-point bending test at a distance between spans of 60 mm according to JIS K 7055, and the displacement in the load direction at a load of 100 N was measured. 7m
m (shown in Table 1 below).

The same bending test as in Example 1 was performed on a PMMA flat plate (thickness: 1 mm) made of the same material as the acrylic resin deformed body used in Example 1 to measure the amount of displacement in the load direction at a load of 100 N. However, since the rigidity was not high, it was greatly deformed before the load reached 100 N, and was removed from the test jig.

As can be seen from the above results, even a thin PMMA flat plate having low rigidity can be imparted with rigidity by being laminated and integrated with a dicyclopentadiene polymer.

<Example 2> Acrylic resin deformed form Polymethyl methacrylate (PMMA) vacuum formed body Shape: bath tub Wall thickness: about 1 mm Back-up material Resin: crosslinked norbornene resin Monomer: dicyclopentadiene monomer Metathesis polymerization catalyst : (3,3-dimethylbutynylidene) bis (tricyclohexylphosphine) ruthenium dichloride Filler: Calcium carbonate Average particle size 3.2 μm Dicyclopentadiene is used as a monomer, and 200 parts of toluene is represented by the following structural formula [IV]. (3,3-dimethylbutynylidene) bis (tricyclohexylphosphine)
A solution in which 10 parts of ruthenium dichloride is dissolved is
(3,3-dimethylbutynylidene) bis (tricyclohexylphosphine) ruthenium dichloride is mixed and stirred at 40 ° C. so that the molar ratio to dicyclopentadiene becomes 1/10000, and calcium carbonate of the same weight as the dicyclopentadiene monomer is added. Was blended to obtain a polymerizable composition.

[0101]

Embedded image

As shown in FIG. 5, a state in which a bathtub-shaped acrylic resin deformed shape 10 is used as a convex shape, and a concave mold 22 made of vinyl chloride resin is spaced from the acrylic resin deformed shape 10 by a predetermined gap 23. Arranged. The gap 23 between the concave mold 22 and the acrylic resin deformed body 10 was set to about 5 mm on both the side surface and the bottom surface.

Next, the above-mentioned polymerizable composition was poured into the gap 23 between the concave mold 22 and the acrylic resin shaped body 10 from the injection hole 22a of the concave mold 22. The polymerizable composition had a very low viscosity, and the resin could be easily poured into the gap even at normal pressure. Thereafter, heat curing was performed at 60 ° C. for 10 minutes to be integrated, and the laminated molded body was obtained by removing from the concave mold 22. The total molding time from setting the concave mold 22 to the acrylic resin deformed body 10 to removing the mold and obtaining a bathtub-shaped laminated molded body was about 19 minutes.

In the obtained laminated molded product (bath), a calcium carbonate-filled dicyclopentadiene polymer was integrated and reinforced on the back surface of the acrylic resin deformed shape 10. The bathtub had a thickness of about 5 mm on both the side and bottom surfaces, and was excellent in rigidity. In addition, no bubbles were observed in the dicyclopentadiene polymer layer, and the resin was filled to the end.

The polymerizable composition produced by the above treatment was applied to a thickness of 5
It was poured into a flat mold having a thickness of 10 mm, and was heated and cured at 60 ° C. for 10 minutes to produce a flat plate having the same composition and curing conditions as the above-mentioned calcium carbonate-filled dicyclopentadiene polymer. A sample having a width of 15 mm and a length of 80 mm was cut out from the obtained flat plate, and the sample was subjected to a three-point bending test at a span distance of 60 mm according to JIS K 7055, and the displacement in the load direction at a load of 100 N was measured. And the amount of displacement was 1.3 mm (shown in Table 1 below).

The same bending test as in Example 2 was performed on a PMMA flat plate (thickness: 1 mm) made of the same material as the acrylic resin deformed shape used in Example 2 to measure the amount of displacement in the load direction at a load of 100 N. However, since the rigidity was not high, it was greatly deformed before the load reached 100 N, and was removed from the test jig.

As can be seen from the above results, even a thin PMMA flat plate having low rigidity can be provided with rigidity by laminating and integrating with a calcium carbonate-filled dicyclopentadiene polymer.

<Example 3> Acrylic resin deformed form radical-curing acrylic resin Backup material Resin: crosslinked norbornene resin Monomer: dicyclopentadiene monomer Metathesis polymerization catalyst: bis (tricyclohexylphosphine) benzylidene ruthenium dichloride Filler: Unused A solution prepared by dissolving 10 parts of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride in 200 parts of toluene using dicyclopentadiene as a monomer was prepared by mixing a solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride with a molar ratio of 1 to dicyclopentadiene of 1 part. The mixture was mixed and stirred at 40 ° C. to give a polymerizable composition. Casting mold (bathtub shape)
Acrylic resin mixed with a catalyst and a promoter is sprayed on a mold surface of the convex mold (see FIG. 2) using a spray gun to reach 60 ° C.
For about 5 minutes to form an acrylic resin layer having a thickness of about 1 mm. The concave mold made of a vinyl chloride resin was arranged with a predetermined gap left from the acrylic resin layer. The gap between the concave mold and the acrylic resin layer was set to about 5 mm on both the side and bottom surfaces.

Next, after pouring the polymerizable composition into the gap between the concave mold and the acrylic resin layer, the composition is heated and cured at 60 ° C. for 10 minutes to be integrated, and removed from the casting mold to form a laminate. I got a body. The total molding time from forming the acrylic resin layer in the convex shape to removing the mold and obtaining the bathtub-shaped laminated molded body was about 20 minutes.

The obtained laminated molded article (bath) has a dicyclopentadiene polymer integrated on the back surface of the acrylic resin layer and is reinforced. The thickness of the bath tub is about 5 mm on both sides and bottom, and the rigidity is high. It was excellent.

The polymerizable composition produced by the above treatment was applied to a thickness of 5
mm, and heat-cured at 60 ° C. for 10 minutes to obtain the same composition as the dicyclopentadiene polymer.
A flat plate under curing conditions was prepared. 15m width from the obtained flat plate
A sample having a length of 80 mm and a length of 80 mm was cut out, and the sample was subjected to a three-point bending test at a distance between spans of 60 mm according to JIS K 7055, and the displacement in the load direction at a load of 100 N was measured. 7m
m (shown in Table 1 below) The same bending test as in Example 3 was performed on an acrylic resin plate (thickness 1 mm) of the same material as that used in Example 3, and a load direction of 100 N was applied. An attempt was made to measure the amount of displacement, but because the rigidity was not high, the deformation was large before the load reached 100 N, and it was out of the test jig.

As can be seen from the above results, even a thin acrylic resin flat plate having low rigidity can be provided with rigidity by being laminated and integrated with a dicyclopentadiene polymer.

<Comparative Example 1> Acrylic resin heteromorphic polymethyl methacrylate (PMMA) Shape: bathtub thickness: about 1 mm Backup material Resin: bis-type unsaturated polyester resin Primer: vinyl ester resin Reinforcement fiber: glass fiber Roving A vinyl ester resin mixed with a curing agent was sprayed with a spray gun in a state where the acrylic resin deformed body in the shape of a bathtub was set upside down in a convex shape, and heat-treated at 40 ° C. for 30 minutes to form a primer layer. Next, a chopped strand obtained by cutting the glass fiber roving with a spray gun and a bis-type unsaturated polyester resin mixed with a curing agent were simultaneously sprayed to form a resin and glass fiber layer.
Thereafter, impregnation and defoaming were performed with a defoaming roll, and the mixture was cured by heating at 40 ° C. for 30 minutes to be integrated. By removing from the mold, an acrylic resin deformed body reinforced with a glass fiber reinforced screw type unsaturated polyester fiber was obtained.

[0114] The total molding time from setting the acrylic resin irregularly shaped body to the convex shape to removing the mold to obtain a bathtub-shaped molded body was about 120 minutes.

The resulting bathtub was integrally reinforced with an unsaturated polyester resin reinforced by glass fibers on the back surface of the acrylic resin deformed shape. The bathtub had a thickness of about 3 mm on both sides and bottom, and was excellent in rigidity. However, because of the reinforcement by manual work, the reinforcing layer was thin in some places, and in particular, in the concave portions of the corners, there were also found portions where the glass fiber was not completely impregnated with the resin.

A glass fiber reinforced screw type unsaturated polyester resin flat plate having a thickness of 3 mm was prepared with the same composition as described above.
The composition was cured by heating at 0 ° C. for 30 minutes. Width 15 from the obtained flat plate
A sample having a length of 80 mm and a length of 80 mm was cut out, and the sample was subjected to a three-point bending test at a distance between spans of 60 mm according to JIS K 7055, and the displacement in the load direction at a load of 100 N was measured. 8
mm (shown in Table 1 below).

<Comparative Example 2> Acrylic resin deformed form Polymethyl methacrylate (PMMA) vacuum formed body Shape: bath tub Wall thickness: about 1 mm Back-up material Resin: bis-type unsaturated polyester resin Filler: calcium carbonate average particle Diameter 7.4 μm 100 parts by weight of calcium carbonate was previously mixed with 100 parts by weight of the bis-type unsaturated polyester resin.

The bath-shaped acrylic resin deformed body was placed in contact with the convex mold of the casting mold, and the concave mold was arranged with a predetermined gap from the acrylic resin deformed body. The gap between the concave mold and the acrylic resin deformed body was set to about 5 mm on both the side and bottom surfaces. Note that the convex mold and the concave mold of the casting mold were both made of vinyl chloride resin.

Next, the above-mentioned bis-type unsaturated polyester resin mixed with a curing agent was poured into the gap between the concave mold and the acrylic resin deformed body. Because of the high viscosity of the blended liquid, the resin was injected little by little. Then, it was heat-cured at 40 ° C. for 30 minutes to be integrated, and was removed from the casting mold to obtain a laminated molded body. The total molding time from setting the acrylic resin deformed body on the convex mold to removing the mold and obtaining the bathtub-shaped laminated body was about 50 minutes.

In the obtained laminated molded product (bath), a bis-type unsaturated polyester resin filled with calcium carbonate was integrally reinforced on the back surface of the deformed acrylic resin, and was reinforced. The thickness of the bathtub was about 5 mm on both sides and bottom. However, bubbles were observed in some places in the unsaturated polyester resin layer, and because of the high viscosity of the liquid mixture, the resin did not flow to the ends, and there were portions where the acrylic resin deformed shape could not be reinforced. .

A mixed solution having the same composition as above was poured into a 5 mm-thick plate-shaped mold, and was heated and cured at 40 ° C. for 30 minutes. A plate having the same composition and curing conditions as the calcium carbonate-filled bis-type unsaturated polyester resin was used. Was prepared. A sample having a width of 15 mm and a length of 80 mm was cut out from the obtained flat plate, and the sample was subjected to a three-point bending test at a span distance of 60 mm according to JIS K 7055, and a load of 1
When the amount of displacement in the load direction at 00N was measured, the amount of displacement was 4.2 mm (shown in Table 1 below).

[0122]

[Table 1]

As can be seen from the results in Table 1 above, according to the present invention, rigidity can be imparted by back-up reinforcing the acrylic resin deformed body with a crosslinked norbornene-based resin polymer. In terms of productivity, production can be performed in an extremely short time as compared with the conventional hand lay-up method.

[0124]

As described above, according to the present invention,
Since the crosslinked norbornene-based resin polymer having high mechanical strength and elastic modulus is laminated and integrated on the surface layer made of the acrylic resin molded product, sufficient rigidity can be imparted to the laminated molded product. Moreover, because the surface is made of acrylic resin, weather resistance,
A laminate molded article having excellent design properties such as water resistance and surface gloss can be obtained.

Further, the crosslinked norbornene-based resin used for reinforcement has a very low viscosity, so that even in the case of a laminated molded article having a complicated shape, backup reinforcement by casting is possible. Completes in a very short time. Therefore, it is superior in quality and productivity as compared with the conventional manual lay-up or reinforcement by spray-up.

As described above, according to the present invention, since the front surface is made of an acrylic resin, it has excellent design properties such as weather resistance, water resistance and surface gloss, and the back surface is backed up with a crosslinked norbornene resin polymer. Therefore, a laminated molded article having excellent rigidity can be obtained. Therefore, the laminated molded article of the present invention can be used for designing a bathtub, a waterproof pan, a kitchen counter, a washbasin, a toilet bowl, an exterior material, a deck material, a wall material, and the like.
It can be suitably used for members requiring rigidity.

[Brief description of the drawings]

FIG. 1 is a view showing one example of a method for producing a laminated molded article of the present invention.

FIG. 2 is a view showing another example of the method for producing a laminated molded article of the present invention.

FIG. 3 is a view showing another example of the method for producing a laminated molded article of the present invention.

FIG. 4 is an explanatory diagram of a manufacturing method used in Example 1 of the present invention.

FIG. 5 is an explanatory diagram of a manufacturing method used in Example 2 of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Acrylic resin variant 2 Norbornene-based resin polymer 11 Casting mold (convex) 12 Casting mold (concave) 12a Injection hole 13 Gap 10 Acrylic resin variant (vacuum molded) 21 Convex 22 Concave 22a injection hole 23 gap

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // B29K 45:00 B29K 45:00 105: 16 105: 16 B29L 9:00 B29L 9:00 31:00 31:00 F-term (reference) 2D032 AA00 AB03 2D061 CA02 CC05 CC11 4F100 AA01A AA08 AK02A AK25A AK44 BA01 BA02 CA23A GB07 GB09 GB71 JB07 JK01 JL09 JN21 YY00A 4F204 AA12C AB11 AB16 AD05 AG03 AH48 EB49 EB49 EB49 EB49

Claims (6)

[Claims] 1. A laminated molded article in which a crosslinked norbornene-based resin layer is integrally laminated on an acrylic resin molded article. 2. The laminated molded article according to claim 1, wherein the crosslinked norbornene resin is a dicyclopentadiene resin. 3. The laminated molded article according to claim 1, wherein the crosslinked norbornene-based resin layer is formed by adding an inorganic filler to the crosslinked norbornene-based resin. 4. An acrylic resin molded body is disposed with a predetermined gap provided with respect to a mold surface of a casting mold, and a norbornene-based monomer and metathesis polymerization are provided in a gap between the acrylic resin molded body and the mold surface. A composition containing a catalyst and having a viscosity of 1
A method for producing a laminated molded article, characterized by obtaining a laminated molded article in which a crosslinked norbornene-based resin layer is integrally laminated on an acrylic resin molded article by filling and curing a polymerizable composition of 0000 cps or less. 5. The method according to claim 4, wherein the norbornene-based monomer is dicyclopentadiene. 6. The method according to claim 4, wherein the polymerizable composition comprises a norbornene-based monomer and an inorganic filler.