JP3298166B2 - Composite molded article and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite molded article using a polynorbornene resin as a substrate, and more particularly, to a composite molded article made of a member having excellent fusion property with a polynorbornene resin.

[0002]

2. Description of the Related Art A substrate made of a polynorbornene resin such as polydicyclopentadiene or polymethyltetracyclododecene and a member made of an olefin resin such as polyethylene (PE) or polypropylene (PP) are extremely well bonded. It is known that a composite molded body in which both are integrated can be obtained (JP-A-1-316262).
issue). These produce a composite adhered to each other by fusion. However, depending on the type of the member, there are some which have insufficient adhesive strength, and some whose adhesive strength is partially insufficient at an end face or the like.

[0003] However, due to problems such as appearance, weather resistance and surface hardness, there is a case where a material having insufficient bonding strength must be used. Further, depending on the member, the adhesive strength may be reduced by mixing a pigment, a flame retardant, a conductivity imparting agent, and the like. When such a material having insufficient adhesiveness is used as a member, there is a problem that the adhesive strength of the member is reduced due to a thermal shock test, a water resistance test, or the like, and the member is peeled off. Further, in a pipe joint in which a heating element layer containing a large amount of carbon is covered with a norbornene-based polymer, the fusion between the heating layer containing a large amount of carbon provided as a heating element of the pipe joint and the norbornene-based resin becomes insufficient.
May cause leakage.

[0004]

SUMMARY OF THE INVENTION The present inventors have studied a method for improving the adhesive strength between a polyolefin-based member and a polynorbornene-based resin base material. It has been found that when a member formed of a mixture containing a polyolefin is used, good adhesion strength is exhibited when integrated with a polynorbornene-based resin, and the present invention has been completed.

[0005]

Thus, according to the present invention, in a composite body in which a base made of a polynorbornene-based resin and a member made of a thermoplastic polyolefin-based resin are integrally formed, at least Is a thermoplastic polyolefin-based resin and 2
30 wt% of the density of 0.9 g / cm ³ or less of amorphous ethylene -α- olefin copolymer and / or density 0.9
A composite molded article characterized by being formed of a mixture with an amorphous propylene-α-olefin copolymer having a g / cm ³ or less . Further, according to the present invention, the heat
Plastic polyolefin resin is used for low or medium density
There is provided the above-mentioned composite molded article, which is polyethylene. Change
In accordance with the present invention, a thermoplastic polyolefin resin,
2 to 30 wt% of the density of 0.9 g / cm ³ or more contrast
Ethylene-α-olefin copolymer and / or
Propylene-α-olefin having a degree of 0.9 g / cm ³ or less
A member formed of a mixture with a copolymer is placed in a mold.
And a norbornene-based monomer and
Supplying an undiluted solution containing a thasis catalyst to cure it
Heat and the substrate made of polynorbornene resin
Parts made of plastic polyolefin resin are integrally formed
A method for producing a composite article is provided.

(Substrate) In the composite molded article of the present invention, the polymer serving as the substrate is a polynorbornene-based resin.
A reaction injection molding method in which a molded article made of a polynorbornene resin is mixed with two or more low-viscosity raw materials which react with each other to quickly produce a polymer, and is then supplied into a mold and cured in the mold ( RIM), a resin transfer molding method (RTM), a casting method, or the like.

[0007] For example, a reaction solution containing an activator and a norbornene-based monomer and a reaction solution containing a metathesis catalyst and a norbornene-based monomer are used as a reaction solution. When the ring polymerization is carried out, a polynorbornene-based resin molded product is obtained. The molding pressure of polynorbornene-based resin by RIM is significantly lower than that of injection molding of ordinary thermoplastic resin, so that an inexpensive and lightweight mold can be used, and the flowability of the raw material in the mold is reduced. Because of its good quality, it is suitable for producing large-sized molded products and molded products having complicated shapes.

In the present invention, the polynorbornene resin serving as a base material may be any resin having a norbornene ring, but is preferably a resin produced using a tricyclic or higher polycyclic norbornene monomer. . By having three or more rings, a polymer having a high glass transition temperature and a high heat distortion temperature can be obtained, and the heat resistance required as a composite material can be satisfied. Further, by using at least 10% by weight, preferably 30% by weight or more of the crosslinkable monomer in all the monomers, the resulting polymer can be made thermosetting.

Examples of the norbornene-based monomer include bicyclic compounds such as 2-norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene and dihydrodicyclopentadiene, tetracyclic compounds such as tetracyclododecene, and pentacyclic compounds such as tricyclopentadiene. Ring, heptacyclic such as tetracyclopentadiene, alkyl-substituted thereof (eg, methyl, ethyl, propyl, butyl-substituted), alkenyl-substituted (eg, vinyl-substituted), alkylidene-substituted (eg, Examples include substituents having a polar group such as an ethylidene substituent, an aryl substituent (for example, a phenyl, tolyl, or naphthyl substituent), an ester group, an ether group, a cyano group, and a halogen atom. Among them, tricyclic or pentacyclic is awarded from the viewpoints of availability, reactivity, heat resistance and the like.

[0010] The crosslinkable monomer has two reactive double bonds.
It is a polycyclic norbornene-based monomer having at least one dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene and the like.
Therefore, when the norbornene-based monomer and the crosslinkable monomer are the same, it is not necessary to use any other crosslinkable monomer. These norbornene-based monomers may be used alone or in combination of two or more.

It should be noted that one of the above norbornene monomers is
Monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, cyclododecene and the like, which can be ring-opening polymerized together with at least one kind, can be used in combination as long as the object of the present invention is not impaired.

The catalyst used for the polymerization of the norbornene monomer may be any metathesis catalyst known as a catalyst for ring-opening polymerization of the norbornene monomer, and specific examples thereof include halides such as tungsten, molybdenum, and tantalum; Metathesis catalysts such as oxyhalides, oxides, and organic ammonium salts,
Specific examples of the activator (cocatalyst) include an alkylaluminum halide, an alkoxyalkylaluminum halide, an aryloxyalkylaluminum halide, and an organotin compound.

The metathesis catalyst is usually used in an amount of about 0.01 to 50 mmol per 1 mol of the norbornene monomer,
Preferably, it is used in the range of 0.1 to 10 mmol.
The activator is used in a molar ratio of 0.1 to the metathesis catalyst component.
It is used in the range of 1 to 200, preferably 2 to 10. It is preferable that both the metathesis catalyst and the activator are dissolved in a monomer before use. However, the metathesis catalyst and the activator may be suspended or dissolved in a small amount of a solvent as long as the properties of the product are not substantially impaired.

The polynorbornene-based resin may contain additives such as an antioxidant, a filler, a reinforcing material, a foaming agent, a pigment, a colorant, and an elastomer. These additives are usually dissolved or dispersed in a reaction stock solution. When the base material is a foam, a foaming agent is added to the reaction solution, and this is injected into a mold. Preferred blowing agents are typically liquid, readily volatile, low boiling organic compounds such as pentane, hydrocarbons such as hexane, methylene chloride, trichlorofluoromethane, halogenated hydrocarbons such as dichlorodifluoromethane, and the like. Examples include thermally expandable microcapsules containing an organic compound, or an inert gas such as nitrogen or argon.

(Thermoplastic Polyolefin Resin) The thermoplastic polyolefin resin used in the present invention may be any as long as it can be integrally molded with a polynorbornene resin as a base material.

Examples of such a thermoplastic polymer include high-density polyethylene (PE), medium-density PE, low-density PE, ultrahigh-molecular-weight PE, ethylene-propylene copolymer, ethylene-butene-1 copolymer, Polypropylene (PP), polybutene-1, polypentene-1, poly4
-Methylpentene-1, an ethylene-vinyl acetate copolymer, an olefin-based polymer containing an olefin-based monomer such as an ethylene-acrylate copolymer as a main component, and a mixture thereof. Among these polymers, polyolefins composed of only olefin monomers are preferable from the viewpoints of adhesion to the substrate and integral moldability, and low- or medium-density polyethylene is particularly excellent in adhesion to the substrate. ing.

These thermoplastic polymers include fillers such as titanium oxide, calcium carbonate, aluminum hydroxide, and talc; coloring agents such as various pigments and dyes; antioxidants; ultraviolet absorbers; By adding a modifier such as an antistatic agent and an adhesion improver such as a petroleum resin, coloring or improvement in weather resistance can be achieved. It is necessary that these fillers and additives do not substantially inhibit metathesis polymerization.

(Amorphous ethylene-α-olefin copolymer or propylenelen-α-olefin copolymer)
In the present invention, as the adhesion improving resin, amorphous ethylene-α
-An olefin copolymer resin and / or an amorphous propylene-α-olefin copolymer resin is used.

Here, the term "amorphous" includes low crystallinity, and more specifically, the density (ASTM-D1505) is 0.
9 g / cm ² or less. Such an amorphous copolymer resin is obtained by polymerization using ethylene or propylene as a main component and a different α-olefin having a larger number of carbon atoms as a subcomponent using a Ziegler catalyst, -Examples of olefins include those using propylene, butene-1, pentene-1, hexene-1, and the like. The content of ethylene or propylene used as a main component is usually at least 50% by weight, preferably at least 60% by weight.

[0020] Preferred specific examples is an ethylene-based copolymer resin TAFMER A or TAFMER P, a propylene-based copolymer resin TAFMER X R (trade name, manufactured by Mitsui Petrochemical) etc. Among them ethylene The -α-olefin copolymer resin is more preferable in terms of adhesiveness.

(Member) The member used in the present invention has at least a joint surface with the base material formed of a mixture of a thermoplastic polyolefin resin and the above-mentioned amorphous copolymer resin. Of course, the entire member may be formed of the mixture. The member is formed by blending a predetermined amount of the thermoplastic resin and the adhesion improving resin, and then molding the member into a desired shape by a conventional method such as injection molding or extrusion molding. The shape of the member is fiber, film,
Examples of the sheet include a three-dimensional shape such as a sheet, a column, a square, and a hollow body.

The addition amount of the adhesion improving resin is usually 2 to 30% by weight, preferably 5 to 25% by weight with respect to the thermoplastic resin.
%, More preferably 7 to 20% by weight. If the amount is large, the softening point of the mixture is low, and the member is likely to be deformed. If the amount is small, the intended purpose is not achieved.

The method of mixing the adhesion improving resin and the thermoplastic polyolefin resin differs depending on the properties of the two resins.
When both resins are pellets, the operation is simple and preferable since it is only necessary to stir and mix a predetermined amount in a blender.
Even when one of the resins is a block, both resins can be kneaded with a predetermined amount of rolls and then pelletized with a pelletizer for use.

Since the adhesion between the thermoplastic polyolefin-based resin and the polynorbornene-based resin is improved by blending the adhesion-improving resin, even if the thermoplastic resin is hard to obtain a sufficient adhesive strength, it can be strongly combined with the polynorbornene-based resin. Glue. For this reason, the types of selection of the thermoplastic resin used as the member can be widened, and the reliability of the adhesion between the polynorbornene-based resin and the member can be enhanced.

As described above, fillers and additives can be blended in the member. In general, by adding a filler or an additive, the adhesive force between the thermoplastic polyolefin resin and the polynorbornene resin is reduced, but in the present invention, it is possible to prevent the adhesive force from being reduced by the presence of the adhesiveness improving resin. it can.

Using the mixture as a material, a member is formed by a conventional thermoplastic resin molding method such as compression molding, extrusion molding, blow molding, vacuum molding, or injection molding. The mixture may be extruded into a film and wound around another polyolefin, or may be used as a member provided on another polyolefin. Alternatively, a mixture of the above mixture and another polyolefin, for example, a polyolefin containing no adhesion improving resin and extruded in two layers, may be used as the member.

(Composite Molded Product) In the composite molded product of the present invention, the above members are disposed in a mold, and
It can be manufactured by supplying and curing a reaction solution containing a norbornene-based monomer and a metathesis catalyst. When the member is a hollow body, the member itself can be used as a mold, and a base layer can be provided on the inner surface of the member by rotational molding.

In the case where the member is formed of two or more layers that do not include a layer containing the adhesion improving resin, the layer containing the adhesion improving resin may be in contact with the norbornene-based polymer. Arrange the members.

In a preferred method for producing a polynorbornene-based resin, a norbornene-based monomer is divided into two parts and placed in another container. One of them is provided with a metathesis catalyst, and the other is added with an activator. Prepare liquid. The two kinds of reaction liquids are mixed, and then injected into a mold or a mold having a predetermined shape (both are referred to as a mold), where ring-opening polymerization is performed in a lump.

The mold temperature is usually 30 ° C. or higher, preferably 40 to 200 ° C., particularly preferably 50 to 130 ° C. The components used for the polymerization reaction are preferably stored and operated under an atmosphere of an inert gas such as nitrogen gas.
The material of the mold may be any of metal, resin, wood, plaster and the like.

[0031]

According to the present invention, by using a member formed of a mixture of a polyolefin-based resin and a specific amorphous polyolefin, excellent adhesion to a substrate formed of a polynorbornene-based resin is obtained. Composite molded article is provided.

[0032]

The present invention will be described in more detail with reference to the following examples. Reference Example 1 A pellet-like thermoplastic polyolefin and a pellet-like amorphous ethylene-α-olefin copolymer resin were put in a polyethylene bag at a predetermined ratio shown in Table 1 and sufficiently blended. The mixture of the pellets was placed in a mold for forming a sheet having a thickness of 1 mm and compression-molded at 180 ° C. by a pressure press to form a sheet.

Example 1 25 sheets obtained in Reference Example 1
cm × 25 cm, placed on a flat surface in a flat mold (one of the split molds), placed a 3 mm thick iron spacer on top of the other split mold, The air inside was replaced by flowing nitrogen gas. The size of the mold is 2
With a size of 0 cm × 20 cm, the sheets were aligned at the bottom of the mold, and arranged so as to protrude 5 cm upward and 2.5 cm left and right respectively. The mold was heated to 60 ° C.

As the norbornene monomer, 75% of dicyclopentadiene (DCP) and 25% of cyclopentadiene trimer were used, and 5% of styrene-isoprene-styrene block copolymer (Clayton 1170, manufactured by Shell Co.) was used. And 2% of Irganox 1010 (manufactured by Ciba-Geigy), which is a phenolic antioxidant, was put into two containers. One of them was charged with diethyl aluminum chloride (DEAC) at a concentration of 40 mmol, n- Propanol was added to a concentration of 44 mmol and silicon tetrachloride to a concentration of 20 mmol. On the other hand, tri (tridecyl) ammonium molybdate was added to the monomer at a concentration of 10 mmol. Both reaction liquids were conveyed to a power mixer by a gear pump so as to have a volume ratio of 1: 1 and injected into a cavity in a mold.

About 3 minutes after the injection, the polymerization reaction was completed. The mold was opened to obtain a plate-shaped sample in which a member having the composition of each example shown in Table 1 and a substrate made of a thermosetting polynorbornene resin were integrally formed.

This plate was fixed in a vise, the portion of the protruding member was pulled, and the adhesive strength between the two was measured. Adhesion to the substrate was evaluated as ◎ for those that could not be peeled even when trying to peel, ○ for those that peeled off a little when pulled too hard, and Δ for those that could be peeled off without applying much force. . Table 1 shows the results. The glass transition temperature (Tg) of the polynorbornene resin in the outer layer
Was 170 ° C.

[0037]

[Table 1]

Example 2 Low-density polyethylene (melt index: 0.3, density: 0.92, melting point: 110 ° C.) and Tuffmer P-0480 (manufactured by Mitsui Petrochemical) were 80/20.
Was mixed with a Banbury mixer, formed into a sheet with a receiving roll, and then formed into pellets.

The pellets were extruded by an extruder to an outer diameter of 36.
mm, extruded into a pipe with an inner diameter of 33 mm, length 60 m
m to form a pipe-shaped member.

This member was used as a core for RIM molding, and an aluminum cylindrical mold having an inner diameter of 41 mm and an outer diameter of 80 mm was fixed around the core through upper and lower lids and sealed. An inlet for injecting the unreacted reaction solution into the gap between the cylinder and the core was provided on the upper lid.

The assembled cylinder as a whole was heated to 60 ° C., nitrogen gas was flowed from the injection port, and the gap between the core and the cylinder was replaced with nitrogen gas. Then, the same reaction solution as in Example 1 was injected. .

About 3 minutes after the injection, the polymerization reaction was completed. The upper and lower lids of the cylindrical mold were removed, the member was used as an inner peripheral layer, and a hollow body around which a base made of thermosetting polynorbornene resin was integrally molded was obtained. The outer peripheral layer and the inner peripheral layer of this hollow body were excellent in adhesiveness and could not be peeled off even if they were to be peeled off.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-185331 (JP, A) JP-A-3-69322 (JP, A) JP-A-3-69357 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) B32B 7/10 B32B 27/00 B32B 27/08 B32B 27/32 B32B 31/06 C08J 5/18

Claims (3)

(57) [Claims] 1. A composite in which a substrate made of a polynorbornene-based resin and a member made of a thermoplastic polyolefin-based resin are integrally formed, at least a joining surface of the base of the member is made of a thermoplastic polyolefin-based resin, 2 to 30 wt% of the density of 0.9 g / cm ³ or less of amorphous respect
Composite molded body characterized by being formed of a mixture of sex ethylene -α- olefin copolymer and / or density 0.9 g / cm ³ or less of amorphous propylene -α- olefin copolymer. 2. The method according to claim 1, wherein the thermoplastic polyolefin resin has a low content.
2. The method according to claim 1, wherein the polyethylene is high density or medium density polyethylene.
Composite moldings. 3. A thermoplastic polyolefin resin having a density of 0.9 g / cm ³ or less of 2 to ³⁰ wt% based on the thermoplastic polyolefin resin.
Disposed member formed of a mixture of amorphous ethylene -α- olefin copolymer and / or density 0.9 g / cm ³ or less of amorphous propylene -α- olefin copolymer into a mold Then, by supplying the unreacted solution containing the norbornene-based monomer and the metathesis catalyst to the cavity in the mold and curing the same, the base composed of the polynorbornene-based resin and the member composed of the thermoplastic polyolefin-based resin are integrally formed. A method for producing a formed composite article.