JP2001038797A - Production of composite molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To mold a composite molded article excellent in adhesion in an extremely simple and inexpensive manner. SOLUTION: By evacuating the recessed part of a base material 6 comprising a polynorbornene resin having the recessed part 62 corresponding to a cavity, a thermoplastic resin sheet or film-like layer forming material is stretched along the inner surface of the recessed part to be closely bonded to the recessed part. It is pref. to provide a process for coating at least the recessed part 62 of the base material 6 with an adhesive before evacuation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a composite molded product suitable for housing-related applications such as a bathtub, and more particularly, to a method for producing a ring-opened polymer of a norbornene-based monomer on a substrate surface. In addition, the present invention relates to a method for producing a composite molded product in which a layer forming material made of a thermoplastic resin is adhered.

[0002]

2. Description of the Related Art Conventionally, molded articles composed of a ring-opened polymer of a norbornene-based monomer have been known. This resin molded article can be used in various fields such as a bathtub, a waterproof pan for a unit bath or a wash basin. It is being considered for use. In recent years, a method for producing a composite molded article in which a design property is imparted to this type of resin molded article has been proposed.

[0003] For example, the production methods proposed in Japanese Patent Application Laid-Open Nos. 9-156689 and 10-16935 disclose a method in which a resin molded product made of polyolefin or the like is placed as a core in a mold, The norbornene-based unreacted solution is injected into the cavity of the mold and cured.

[0004] Further, the manufacturing method proposed in Japanese Patent Application Laid-Open Nos. 1-316262 and 3-65319 discloses a method in which a layer forming material is previously formed into at least one mold by vacuum forming or pressure forming. In addition, a norbornene-based undiluted reaction solution is supplied to the voids in the mold and cured.

Further, a method has been proposed in which a resin molded article and a coating layer are separately molded, and these are bonded together via an adhesive to produce a composite molded article.

[0006]

However, in the production method proposed in Japanese Patent Application Laid-Open No. 9-156689, the adhesiveness between a resin molded product and a polynorbornene resin obtained by curing a reaction stock solution is reduced. There was a problem.

Further, in the manufacturing method proposed in Japanese Patent Application Laid-Open No. 1-316262, the mold must be opened and closed, which is troublesome and has a problem in workability.

Further, in the method of separately molding a resin molded article and a coating layer, the dimensional accuracy of the molded articles may be different from each other. In this case, a gap is increased between the two and a large amount of adhesive is required. For example, there is a problem that the manufacturing cost is increased.

An object of the present invention is to solve the problems of the prior art and to provide a method of manufacturing a composite molded article capable of extremely easily and inexpensively molding a composite molded article having excellent adhesion. It is in.

[0010]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors focused on the vacuum forming method and studied simplification and time saving of the apparatus. Was completed.

That is, in the method for producing a composite molded product according to the present invention, the base material made of a polynorbornene resin having a concave portion corresponding to a cavity is evacuated from the inner surface of the concave portion to form a thermoplastic resin sheet or film. The layer forming material is spread along the inner surface of the concave portion and closely adhered thereto.

It is preferable that the method further comprises a step of applying an adhesive to the base material before the evacuation. It is more preferable that the adhesive is formed by applying the adhesive to the entire surface including the concave portion of the base material.

The layer forming material is not particularly limited.
Any resin can be used as long as it is a thermoplastic resin that can be vacuum formed, but an acrylic resin is preferable.

By the method for producing a composite molded article according to the present invention, for example, a bathtub in which the thickness of the substrate is 2 to 50 mm and the thickness of the layer forming material after molding is 0.1 to 10 mm can be obtained.

[0015] The polynorbornene-based resin constituting the base material used in the method of the present invention is usually produced by reaction injection molding (RIM) of a stock solution containing a metathesis catalyst and an activator in addition to a norbornene-based monomer. Can be.

As the norbornene-based monomer, any monomer having a norbornene ring may be used. Specific examples thereof include bicyclics such as norbornene and norbornadiene, dicyclopentadiene (cyclopentadiene dimer), and dihydrodicyclopentadiene. Tricyclic, tetracyclic such as tetracyclododecene, pentacyclic such as cyclopentadiene trimer, heptacyclic such as cyclopentadiene tetramer,
And substituted products of these bicyclic to heptacyclic products such as alkyl such as methyl, ethyl, propyl and butyl, alkenyl such as vinyl, alkylidene such as ethylidene, aryl such as phenyl, tolyl and naphthyl, and the like.
Examples of such a bicyclic to heptacyclic substituent having a polar group such as an ester group, an ether group, a cyano group, and a halogen atom are exemplified. Among them, tricyclic or higher polycyclic norbornene monomers are preferable because they are easily available and excellent in reactivity, and more preferable are tricyclic, tetracyclic or pentacyclic norbornene monomers. These norbornene-based monomers can be used alone or in combination of two or more.

It should be noted that, within a range not to impair the object of the present invention,
Monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene and cyclododecene, which can be ring-opening copolymerized with norbornene monomers, can also be used as comonomers.

The metathesis catalyst is not particularly limited as long as it is capable of ring-opening polymerization of a norbornene monomer by the RIM method, and may be a known one. For example, the metathesis catalyst is not particularly limited as long as it is a known metathesis catalyst as a catalyst for bulk polymerization of norbornene-based monomers such as tungsten hexachloride, or organic ammonium molybdate such as tridodecyl ammonium molybdate or tri (tridecyl) ammonium molybdate. However, an organic ammonium molybdate is preferred.

The amount of the metathesis catalyst to be used is generally 0.01 mmol or more, preferably 0.1 mmol or more, and 50 mmol or less, preferably 20 mmol or less, per 1 mol of the monomers used in the whole reaction solution. If the amount of the metathesis catalyst used is too small, the polymerization activity is too low and the reaction takes a long time, so the production efficiency is poor.If the amount is too large, the reaction is too vigorous and the resin hardens before being sufficiently filled in the mold. Or the catalyst is likely to precipitate, making it difficult to store homogeneously.

The metathesis catalyst is usually used by dissolving it in a monomer. However, as long as the properties of a molded article obtained by the RIM method are not essentially impaired, the catalyst is suspended and dissolved in a small amount of a solvent and then dissolved in a monomer. May be used to make precipitation difficult or increase solubility.

As the activator (co-catalyst), JP-A-58-1983
127728, JP-A-4-226124,
JP-A-58-129003, JP-A-4-1452
There is no particular limitation as long as it is a known activator as disclosed in JP-A-47-47, for example, alkylaluminum halides such as ethyl aluminum dichloride and diethyl aluminum chloride, organic aluminum compounds such as alkoxyalkyl aluminum halides, and organic tin. And the like.

The amount of the activator used is not particularly limited,
Usually, 0.1 mol or more, preferably 1 mol or more, and 1 mol per 1 mol of the metathesis catalyst used in the whole reaction solution.
It is at most 00 mol, preferably at most 10 mol. If no activator is used or the amount of activator used is too small,
Since the polymerization activity is too low and the reaction takes time, the production efficiency deteriorates. Conversely, if the amount is too large, the reaction may be too vigorous and may be cured before the mold is sufficiently filled.

The activator is used after being dissolved in a monomer.
As long as the properties of the molded article by the RIM method are not essentially impaired, the substance is suspended in a small amount of a solvent and then mixed with a monomer to make it difficult to precipitate or to increase the solubility. Good.

The above-mentioned undiluted reaction solution may contain, if desired,
Various additives such as a reinforcing material, an antioxidant, a filler, an elastomer, a pigment, a coloring agent, a foaming agent, a flame retardant, a sliding agent, a dicyclopentadiene-based thermopolymerized resin and a hydrogenated product thereof can be compounded. The properties of the resulting RIM molded article (substrate) can be modified. Usually, it is preferable that such an additive is previously mixed with one or both of the reaction stock solutions.

As preparations for the reaction injection molding, a molding material mainly composed of a norbornene-based monomer, a metathesis catalyst and an activator was mixed with a liquid B composed of a norbornene-based monomer and a metathesis catalyst, It is preferable to divide the liquid into two stable liquids, the liquid and the liquid A, and put them in separate tanks.

At the time of reaction injection molding, these two liquids are mixed in a mixing head.
It is injected into the cavity of the mold and is subjected to bulk polymerization to obtain a RIM molded product (substrate).

At the time of reaction injection molding, the mold temperature is preferably 10 to 150 ° C., more preferably 30 to 12 ° C.
The temperature is 0 ° C, more preferably 50 to 100 ° C. The mold clamping pressure of the mold is usually 0.1 to 100 kgf / cm ^2.
Range. The polymerization time may be appropriately selected,
Usually, it is 30 seconds to 20 minutes, preferably 5 minutes or less after the completion of the injection of the reaction stock solution.

[0028]

According to the present invention, a preformed base made of a polynorbornene-based resin is used as a female mold, and a thermoplastic resin is vacuum-formed thereon to obtain an integrally molded product. Can have excellent adhesion.

Further, since a thermoplastic resin is vacuum-formed in accordance with the shape using a base made of a polynorbornene resin having relatively high dimensional accuracy, the gap between the resins can be reduced. . Therefore, when an adhesive is interposed between the resins, the amount of the adhesive can be reduced as compared with the conventional case.

Further, since the composite molded article is manufactured by vacuum molding, there is no need to open and close the mold, and the production of the molded article does not take much time and the workability can be improved. it can.

The composite molded article obtained by the method of the present invention is not particularly limited, but includes water tanks, kitchen fixtures (sinks and the like), toilets, bathrooms and toilet parts (laundry tubs, tubs,
Examples include sinks, bathtubs, walls, roofs, toilets, etc., and building components (floor materials, wall materials, pillars, window frames, etc.).

[0032]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method for producing a composite molded product according to the present invention will be described in detail based on an embodiment shown in the drawings. 1A to 1E are schematic views showing a method for manufacturing a composite molded product according to one embodiment of the present invention, and FIG. 2 is a schematic perspective view showing an example of a base material used as a female mold in this embodiment. is there.

First, a molding apparatus used in the method for producing a composite molded article according to the present invention will be described. As shown in FIG. 1A, a molding apparatus 2 according to the present embodiment includes a vacuum jig 4
And a base material 6 as a female mold.

The vacuum evacuation jig 4 is configured such that a space portion 42 is formed when a base material 6 described later is set, and a vacuum pump (not shown) Are connected. Jig 4
It is preferable to have a sealing structure on the contact surface 44 with the base material 6 so that there is no air leakage even when vacuuming is performed. The jig 4 may be provided in advance with a support (not shown) for preventing deformation as required. Such a jig 4 can be made of, for example, metal.

The substrate 6 has a concave portion 62 corresponding to a cavity.
Having. A vent hole 622 for evacuating is formed on the inner surface of the concave portion 62. The formation position of the ventilation hole 622 is not particularly limited, but it is preferable to provide the bottom hole and the side surface of the recess 62. Vent 6
The number of 22 is not particularly limited, and is appropriately selected depending on the shape of the substrate 6. The diameter of the vent 622 is preferably 0.5
About 5 mm, preferably at intervals of 5 to 20 cm. Such a vent 622 can be formed by using an automatic device such as a hole drilling MC / robot or by hand after forming the base material 6. It may be formed by providing a part.

The shape and size of the substrate 6 are not particularly limited, but in the present embodiment, as shown in FIG.
Is about 1.2 to 1.8 m, width W is about 0.6 to 1.2 m, depth D is about 0.4 to 0.8 m, and thickness is 3 to 20 m.
m, and illustrates a bathtub as an example of the base material.
When strength is required, a rib can be provided on the back surface.

The substrate 6 in this embodiment is made of a polynorbornene resin obtained by reaction injection molding. Specifically, dicyclopentadiene (DCP) 9
A norbornene-based monomer mixture comprising 0% by weight and 10% by weight of an asymmetric cyclopentadiene trimer is placed in two tanks, and one of the tanks is provided with 40 mmol of diethyl aluminum chloride (DEAC) based on the monomer mixture. It is added to a concentration of 1,3-dichloro-2-propanol (dcPrOH) 40 mmol (Solution A). In the other tank, tri (tridecyl) ammonium molybdate is added to the monomer mixture so as to have a concentration of 10 mmol (Solution B). The solution A and the solution B prepared as described above are respectively sent into a mixing head by a gear pump so as to have a volume ratio of 1 to 1, and then into a reaction injection molding die.
The injection is performed at a mold temperature of 70 ° C. and an injection pressure of 2 kgf / cm ² or less. Perform a reaction for 2 to 4 minutes in the mold,
These series of operations are performed under a nitrogen atmosphere. afterwards,
The substrate 6 can be obtained by removing the molded product from the mold.

It is to be noted that, in a mold at the time of reaction injection molding,
Metal fittings for reinforcement, insert nuts or bolts, drainage, etc. may be installed and integrally molded. It is preferable to perform post-processing such as deburring after molding.

Next, a method for producing a composite molded product will be described.
In vacuum forming using the forming apparatus 2, as shown in FIG. 1A, first, the sheet 14 clamped by the clamp frame 12 is heated using, for example, a heater (not shown).

The sheet 14 is made of, for example, polyethylene,
Polypropylene, propylene-ethylene copolymer (ethylene content is 1 to 50% by weight), high density polyethylene,
Polystyrene, vinyl chloride resin, acrylic resin, acrylonitrile-butadiene-styrene copolymer, AP
It can be composed of various synthetic resins such as ET (amorphous polyethylene terephthalate). Above all, it is preferable to be made of an acrylic resin. Such acrylic resin is not particularly limited, but may be polyacrylate,
Polymethacrylate or the like is used. Heat deformation temperature is 1
Those having a temperature of 00 ° C. or higher are preferable, and examples thereof include Paralinks (manufactured by Kuraray) and Chemax (manufactured by Sumika Haas). In addition, the sheet 14 may contain additives such as an inorganic filler, an antistatic agent, an ultraviolet absorber, and a pigment. The content of such additives is preferably 0.1 to 5 parts by weight in total with respect to 100 parts by weight of the resin. The sheet 14 may be formed of a single layer, a composite layer of a synthetic resin sheet and a foamed resin, or another resin, rubber, or the like, or may be a printed sheet. The thickness of the sheet 14 is not particularly limited, but is usually 0.1 to 12 mm, preferably 0.5 to 8 m.
m. If the thickness of the sheet is less than 0.1 mm, the rigidity tends to be insufficient, and if it exceeds 12 mm, the shapeability at the time of molding tends to be poor. The heating temperature of the sheet 14 is a temperature at which the synthetic resin constituting the sheet 14 is softened,
It is appropriately determined according to the type of the synthetic resin used, but is usually in the range of 60 to 320 ° C. When using an acrylic resin, it is preferable to heat to about 200 ° C.

Next, in the present embodiment, although not shown, an adhesive is applied to the entire surface including the surface of the concave portion 62 of the base material 6 before a lowering step of the sheet 14 described later.

The adhesive is not particularly limited, but is preferably, for example, a one-component curable urethane polymer, a two-component curable urethane polymer, an epoxy polymer, a modified silicone synthetic rubber, or the like. Before applying the adhesive,
It is preferable that the portion to be coated is cleaned and degreased (using a solvent such as acetone). After that, it is preferable to apply an adhesive after applying a primer. The primer is not particularly limited,
Urethane primers and polyisocyanate primers are preferred. How to apply the adhesive and primer
There is no particular limitation, for example, spray method, brush coating,
Known methods such as roll coating can be used. The application of the adhesive and the pramer may be performed after setting the substrate 6 on the jig 4 for evacuation, or may be applied before setting.

Next, as shown in FIG. 1B, the sheet 14 clamped by the clamp frame 12 is lowered and brought into close contact with the molding apparatus 2. Alternatively, the forming device 2 is raised toward the sheet 14.

Next, as shown in FIGS. 1C and 1D, the sheet 14 is evacuated by a vacuum pump (not shown) through the vent hole 622 and the pipe 10. At this time, using a shaping aid plug (not shown),
From the outside of the sheet 14, the sheet 14 is
The evacuation may be performed while pushing the inside.

In the evacuation, the sheet 14 is placed in the concave portion 6 of the substrate 6.
2 is performed at a degree of vacuum enough to adhere to the inner peripheral surface.

As a result, the sheet 14 is
2 is formed into a shape along the inner peripheral surface.

In vacuum forming the sheet 14, the temperature of the base material 6 as a female mold may be controlled together with the jig 4 by a jacket or a heater. The control temperature in that case can be appropriately selected according to the type of the synthetic resin constituting the sheet to be formed.

Next, as shown in FIG.
After cutting the sheet 14, the composite molded product 20 is taken out. The cooling temperature varies depending on the type of the synthetic resin constituting the sheet 14 or the shape of the substrate 6, but when the sheet 14 is made of an acrylic resin, it is preferable to cool the sheet 14 to about 50 to 60 ° C. The obtained composite molded article 20
The processing of the outer peripheral shape and the processing of drainage holes, hot water supply holes, etc. may be performed after molding.

In the present embodiment, when the composite molded product 20 is manufactured, the preformed substrate 6 is used as a female mold, and the sheet 14 is vacuum-formed thereon. The molded product 20 can be obtained. In particular, since the sheet 14 is vacuum formed according to the base 6 made of a polynorbornene-based resin having high dimensional accuracy, the gap between the resins can be reduced, and the amount of the adhesive used can be reduced.

Although the embodiments of the present invention have been described above, the present invention is not limited to these embodiments at all, and it is needless to say that the present invention can be carried out in various modes without departing from the gist of the present invention. It is.

For example, after the molding device 2 and the sheet 14 are brought into close contact with each other, for example, air or the like may be supplied from the air holes 622 to expand the sheet 14 to the outside, expand it to some extent, and then perform vacuuming. .

[0052]

As described above, according to the present invention, it is possible to provide a method of manufacturing a composite molded article which can form a composite molded article having excellent adhesion very simply and inexpensively.

[Brief description of the drawings]

FIGS. 1A to 1E are schematic views showing a method for manufacturing a composite molded product according to an embodiment of the present invention.

FIG. 2 is a schematic perspective view showing an example of a base material used as a female mold in the present embodiment.

[Explanation of symbols]

 Reference Signs List 2 Molding device 4 Vacuuming jig 42 Spatial part 44 Contact surface 6 Substrate 62 Recess 622 Vent 10 Piping 12 Clamp frame 14 Sheet 20 Bath tub (composite molded product)

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) // B29K 55:00 B29L 9:00 31:10 F term (Reference) 4D075 AC43 AE03 BB07Y BB56X BB92Z CA47 DA23 DB55 DC38 EA17 EA35 EB22 4F100 AK01B AK02A AK25B AT00B BA02 CB00 EC182 EH012 EH36 EJ592 GB08 JA20A JA20B JB16B JK06 JL02 YY00A YY00B 4F206 AA12 AA21 AC03 AG07 AG24 AH49 AR12 MG07 AA12 MG12 A0712

Claims (4)

[Claims] 1. A thermoplastic resin sheet or a film-like layer forming material is drawn along the inner surface of the concave portion by evacuating the inner surface of the concave portion of a substrate made of a polynorbornene resin having a concave portion corresponding to a cavity. A method for producing a composite molded product, which is spread and adhered. 2. The method according to claim 1, further comprising a step of applying an adhesive to the substrate before the evacuation. 3. The method according to claim 1, wherein an acrylic resin is used as the layer forming material. 4. A bathtub produced by the method according to claim 3, wherein the thickness of the substrate is 2 to 50 mm, and the thickness of the layer forming material after molding is 0.1 to 10 mm.