JPH1017676A - Fiber-reinforced norbornene resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a norbornene resin molding having high strengths and a low coefficient of linear expansion by bulk-polymerizing a norbornene monomer in the presence of a fibrous reinforcement and a particulate filler both surface-treated with a silane coupling agent. SOLUTION: This molding is formed by bulk-polymerizing a norbornene monomer in the presence of a fibrous reinforcement surface-treated with a silane coupling agent and a particulate filler surface-treated with a silane coupling agent and having a mean particle diameter of 100μm or below. The norbornene monomer is not particularly limited so far as it has a norbornene ring. An at least tricyclic norbornene monomer is desirable because it can give a molding excellent in heat resistance and shape stability. The silane coupling agent is especially desirably an amino-free one having an oxygen-free organic chain. A particularly desirable example is vinyl-tris(2-methoxyethoxy) silane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber-reinforced norbornene-based resin molded product, and more particularly, to a molded product made of a fiber-reinforced norbornene-based resin having high strength and a small linear expansion coefficient.

[0002]

2. Description of the Related Art A method for obtaining a molded product by reaction injection molding (RIM) of a norbornene-based monomer such as dicyclopentadiene or methyltetracyclododecene, that is, by ring-opening bulk polymerization in a mold is known. is there. At that time, it is also known to incorporate a filler, glass fiber, or other reinforcing material.

[0003] When bulk polymerizing norbornene-based monomers in a mold, an insert such as a metal may be included therein. However, while the norbornene resin has a linear expansion coefficient of about 7 to 8 × 10 ⁻⁵ / ° C., many metals and the like have a linear expansion coefficient of 3 × 10 ⁻⁵ / ° C. or less. As described above, since the linear expansion coefficients of the resin and the insert differ greatly,
In the molding step, the temperature of the molded article becomes high due to the heat of reaction, and the molded article is exposed to high temperatures during use, which may cause problems such as distortion of the shape of the molded article and generation of cracks.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a norbornene which is heated to a high temperature by reaction heat during molding, and which does not deform or crack even when a high temperature is encountered when using a molded article. An object of the present invention is to provide a base resin molded product. The present inventors have conducted intensive studies to achieve the above object, and as a result, combined a fiber reinforcing material surface-treated with a silane coupling agent and a particulate filler having a small particle diameter surface-treated with a silane coupling agent. It has been found that by using the same, a norbornene-based resin having high strength and a small linear expansion coefficient can be obtained, and the present invention has been completed.

[0005]

Thus, according to the present invention, there is provided a fiber reinforcing material surface-treated with a silane coupling agent and a particulate filler having an average particle size of 100 μm or less, surface-treated with a silane coupling agent. The present invention provides a fiber-reinforced norbornene-based resin molded product obtained by bulk-polymerizing a norbornene-based monomer in the presence.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION (Norbornene-Based Monomer) The norbornene-based monomer used in the present invention is not particularly limited as long as it has a norbornene ring, but a molded article excellent in heat resistance and shape stability. Thus, it is preferable to use a tricyclic or higher polycyclic norbornene-based monomer.

Specific examples of the norbornene monomer include:
Bicyclics such as norbornene and norbornadiene; tricyclics such as dicyclopentadiene and dihydrodicyclopentadiene; tetracyclics such as tetracyclododecene; pentacyclics such as cyclopentadiene trimer; Ring; alkyl such as methyl, ethyl, propyl, butyl, alkenyl such as vinyl;
Substituents such as alkylidene such as ethylidene, aryl such as phenyl, tolyl, and naphthyl; further having a group containing an element other than carbon and hydrogen such as an ester group, an ether group, a cyano group, and a halogen atom, a so-called polar group Substitutes are exemplified. These monomers are used alone or in combination of two or more. Tricyclic, tetracyclic, and pentacyclic monomers are preferred from the viewpoint of easy availability, excellent reactivity, and excellent heat resistance of the obtained resin molded product.

The norbornene-based resin molded product is preferably of a thermosetting type. For this purpose, a crosslinkable monomer of 10% by weight or more, preferably 30% by weight or more of the monomer used is used. Good. The crosslinkable monomer is a polycyclic norbornene monomer having two or more reactive double bonds, and specific examples thereof include dicyclopentadiene, tricyclopentadiene, and tetracyclopentadiene. In addition, as long as the object of the present invention is not impaired, cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, and cyclooctene that can be ring-opened copolymerized with a norbornene-based monomer,
A monocyclic cycloolefin such as cyclododecene may be used as a comonomer.

(Metathesis catalyst) In the production of the norbornene-based resin molded article of the present invention, the catalyst used for polymerizing the norbornene-based monomer is a metathesis catalyst. The metathesis catalyst is not particularly limited as long as the ring-opening polymerization of the norbornene monomer can be performed by bulk polymerization.
Known ones may be used. For example, halides such as tungsten, molybdenum, and tantalum, oxyhalides, oxides, organic ammonium salts, and the like can be given.

The amount of the metathesis catalyst used is usually at least 0.01 mmol, preferably at least 0.1 mmol and at most 50 mmol, preferably at most 20 mmol, per 1 mol of the monomer used in the whole reaction solution. is there. 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 the bulk polymerized resin molded product are not substantially impaired, the catalyst is suspended and dissolved in a small amount of a solvent, and then simply dissolved. By mixing with the monomer, it is possible to make precipitation difficult or to increase the solubility.

(Activator) In the production of norbornene-based resin molded articles, bulk polymerization is carried out using an activator, also called a metathesis cocatalyst, together with a metathesis catalyst. The activator is not particularly limited as long as it can activate a metathesis catalyst capable of ring-opening polymerization of a norbornene-based monomer by bulk polymerization, and may be a known one. For example, alkyl aluminum, alkyl aluminum halide, alkoxyalkyl aluminum halide, aryloxyalkyl aluminum halide, organic tin compound and the like can be mentioned.

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 used in an amount of at most 00 mol, preferably at most 10 mol. If the used amount of the activator is too small, the polymerization activity is too low and the reaction takes a long time, resulting in poor production efficiency. Sometimes. The activator is also used by dissolving it in the monomer.However, as long as the properties of the molded article by the bulk polymerization are not substantially impaired, the activator is suspended or dissolved in a small amount of a solvent and then mixed with the monomer. By doing so, it is difficult to precipitate,
You may use it, raising solubility. Further, by using an activity modifier in combination, the reaction rate, the time from the mixing of the reaction solution to the start of the reaction, the reaction activity, and the like can be changed. As the activity regulator, a compound having an action of reducing a metathesis catalyst is used.

As the activity regulator, a compound having an action of reducing a metathesis catalyst is used, and examples thereof include alcohols and halo alcohols. Specific examples of alcohols include n-propanol, n-butanol, n-hexanol, 2-butanol, isobutyl alcohol, isopropyl alcohol, t-butyl alcohol, and the like. Specific examples of halo alcohols include 1, 3-Dichloro-2-propanol, 2-chloroethanol, 1-chlorobutanol and the like. The amount of the activity modifier added is 1.0 or more, preferably 1.1 or more, and 1.5 or less, preferably 1.4 or less in terms of the molar ratio of the activity modifier / activator. If the amount of the activity modifier is too small, the reaction is too fast, and the undiluted reaction solution is less likely to flow between the fibers or into a narrow portion. Conversely, if the amount is too large, the reaction is too slow even when heated, resulting in poor molding efficiency.

(Reaction stock solution) As a reaction stock solution used for producing a norbornene-based resin molded product, a norbornene-based monomer, a metathesis catalyst, an activator, an activity regulator and optional components were prepared by dividing into two or more solutions. Things are used.
These reaction stock solutions do not undergo bulk polymerization with only one solution,
When all the liquids are mixed, each component has a predetermined ratio, and the norbornene-based monomer undergoes bulk polymerization.

For example, a reaction stock solution comprising a norbornene monomer, a metathesis catalyst and an optional component and a reaction stock solution comprising a norbornene monomer, an activator, an activity regulator and an optional component do not polymerize as they are. If the total amount of each component contained in the two solutions is the amount of each component used in the present invention, each of the two solutions is a reaction stock solution used in the present invention, and when both are mixed, bulk polymerization is started.

In general, bulk polymerization is carried out using two reaction stock solutions for good workability, but three or more reaction stock solutions may be used. In order to allow other components to be sufficiently diffused into the norbornene-based monomer after mixing of the reaction stock solution, all the reaction stock solutions usually contain a norbornene-based monomer, and the other components are composed of a norbornene-based monomer. It is preferable that the reaction solution is dissolved or dispersed in the monomer, but there may be a reaction stock solution containing no norbornene-based monomer.
Also, when the three components of norbornene-based monomer, metathesis catalyst, and activator are contained in one reaction stock solution, bulk polymerization starts, and therefore, a metathesis catalyst and an activator such as tri-lower alkyl aluminum are usually used in one reaction stock solution. Is not contained. The reaction stock solution is usually preferably prepared, stored, and transferred under an atmosphere of an inert gas such as nitrogen gas for the purpose of preventing deactivation of the metathesis catalyst and the like.

(Fiber Reinforcing Material) The molded article of the present invention can be obtained by using a fiber surface-treated with a silane coupling agent as a reinforcing material. Specific examples of fibers used include inorganic fibers such as glass fibers, carbon fibers, silicon carbide fibers, steel fibers and amorphous fibers, and organic fibers such as aramid fibers and ultrahigh molecular weight polyethylene. The form of the fiber reinforcement is not particularly limited,
Any of woven fabric, knitted fabric, continuous strand mat, filament winding and the like may be used. The fiber reinforcement is not limited to a single type or a single type, and two or more types or two or more types can be used in combination.

Among the fibers, glass long fibers are preferred. Specific forms of the long glass fiber include a glass strand, a roving in which glass strands are bundled, a roving cloth woven by roving, a glass yarn in which strands are twisted, a glass cloth, and the like. Particularly, a continuous strand mat is preferable. Fiber reinforcement is
It is cut into a desired length according to the shape of the mold and used.

In the present invention, a silane coupling agent is used as a surface treatment agent for the fiber reinforcing material. Among them, a silane coupling agent having no amino group and containing no oxygen atom in the organic chain is particularly preferred. It is preferable to use The silane coupling agent used in the present invention is, for example, vinyl-tris (2-methoxyethoxy) silane, vinyl-trimethoxysilane or 5- (bicycloheptenyl) triethoxysilane, a hydrochloride, a nitrate, an acetate or a salt thereof. Salts such as propionate are exemplified.
Among them, those having an ethylenic double bond typified by vinyl-tris (2-methoxyethoxy) silane or a salt thereof in the molecule are particularly preferable.

The surface treating agent is used by adhering it to the fiber at a ratio of 0.1 to 5% by weight, preferably 0.5 to 3% by weight. If the amount of adhesion is too small, the effect of reinforcement by the fiber reinforcing material and the effect of reducing the coefficient of linear expansion are small. Conversely, if the amount is too large, it is not economical and improvement in physical properties cannot be expected. The method of attaching the surface treatment agent to the fiber may be in accordance with a conventional method.For example, the coupling agent is dissolved or dispersed in water or a mixed solution of water and a hydrophilic solvent, and the fiber is immersed in the solution. Alternatively, the solution may be applied directly to a long fiber drawn from a furnace at the time of manufacturing a long glass fiber by a roller. By adjusting the concentration of this solution, the amount of the surface treatment agent attached to the fibers can be adjusted.

The filling amount of the fiber reinforcing material can be appropriately selected from a small amount to a high filling amount as desired. In the present invention, even if the filling amount is as high as about 70% by weight, the physical properties are not inhibited without causing polymerization inhibition. An improved molded product can be obtained. Generally, the filling amount of the fiber reinforcing material is 20 to 80% by weight based on the weight of the resin molded product excluding the insert.

(Filler) In the production of the molded article of the present invention, a particulate filler surface-treated with a silane coupling agent is used in addition to a fiber reinforcing material surface-treated with a silane coupling agent. By using a particulate filler surface-treated with a silane coupling agent in combination, the linear expansion coefficient is much lower and higher in strength than when only a fiber reinforcing material surface-treated with a silane coupling agent is used. A resin molded product can be obtained. The particulate filler used has an average particle diameter of 100 μm or less. The average particle size is preferably 0.01 to 50 μm, more preferably 0.1 to 50 μm.
The range is 1 to 30 μm, most preferably 1 to 20 μm.

The filler to be used is not particularly limited except for the particle size, and is appropriately selected. Specific examples include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, and pumice. Powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, calcium sulfite, talc, clay, mica, glass flakes, glass beads, calcium silicate , Montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, antimony oxide, red phosphorus and the like. These particulate fillers may be microencapsulated with a phenol resin or the like. Among these, a red phosphorus powder filler is particularly preferred because it has a high balance between strength properties and linear expansion coefficient and has good flame retardancy.

The type and amount of the surface treatment agent used for the surface treatment of the filler and the surface treatment method may be the same as in the case of the fiber reinforcing material. These fillers may be used alone or in combination of two or more. The amount of the filler is 1 to 20 parts by weight based on 100 parts by weight of the reaction stock solution,
Preferably it is 3 to 10 parts by weight.

(Optional components) If desired, various additives such as an antioxidant, a foaming agent, a sliding agent, a combustible, an elastomer, a dicyclopentadiene-based thermopolymerized resin and a hydrogenated product thereof may be added to the stock solution for molding. Can be formulated, thereby modifying the properties of the resulting RIM product.
As the antioxidant, various antioxidants for plastics / rubbers such as phenol type, phosphorus type and amine type are used.

Further, an elastomer may be added to the reaction solution for the purpose of adjusting the viscosity of the reaction solution. Examples of the elastomer used include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene copolymer, and ethylene-propylene-diene copolymer. Diene-based elastomers, ethylene-vinyl acetate copolymers, and hydrides thereof. Preferably a diene-based elastomer, more preferably a butadiene-based elastomer, particularly preferably a block copolymer of styrene and butadiene or cis-1,
Use 4-polybutadiene. By adding these elastomers to the reaction stock solution, the impact resistance of the resulting molded article is improved. The amount of elastomer added is 2
The viscosity at 5 ° C. is usually 3 cps or more, preferably 5 cps
ps or more, more preferably 10 cps or more, and 10
00 cps or less, preferably 500 cps or less, more preferably 100 cps or less.

(Bulk polymerization) In the production of a norbornene-based resin molded product, particles having an average particle diameter of not more than 100 μm and having been subjected to a surface treatment with a silane coupling agent in the presence of a fiber reinforcing material surface-treated with a silane coupling agent. The reaction mixture obtained by mixing the reaction mixture containing the filler is cured. In general, a mold is pre-filled with a surface-treated fiber reinforcing material, and then two or more undiluted reaction solutions are instantaneously mixed using a mixing head or the like. A method of injecting into a mold to initiate bulk polymerization and curing is used. The mold used here is not limited to a metal mold, and may be a glass mold, a wooden mold, or a resin mold. The surface-treated fiber reinforcing material is preferably used after removing the adsorbed water by means such as drying in advance so as not to contain the adsorbed water.

When the insert is fixed in the mold and the bulk polymerization is carried out, the fiber reinforcing material is filled as uniformly as possible between the surface of the insert and the inner surface of the mold, and then the undiluted solution is poured and cured. Let me know. In the bulk polymerization step, in order to avoid problems such as deactivation of the catalyst, the inside of the mold is preferably set to an inert atmosphere by purging an inert gas such as a nitrogen gas.

(Fiber-reinforced norbornene-based resin molded article) The fiber-reinforced norbornene-based resin molded article of the present invention generally has
It has a small coefficient of linear expansion of less than × 10 ^-5 / ° C.
A composite molded article with a metal or the like does not deform its shape and does not crack on its surface even when it is exposed to high temperatures during or after molding. Further, not only mechanical properties such as flexural strength and flexural modulus are sufficient, but also excellent in long-term reliability. Further, those containing red phosphorus particles as a filler have sufficient flame retardancy and good mechanical properties.

[0030]

EXAMPLES Hereinafter, examples of the long fiber reinforced norbornene resin molded article of the present invention will be described in detail.

Example 1 A norbornene-based monomer composed of 90% of dicyclopentadiene and 10% of a cyclopentadiene trimer (asymmetric trimer) is placed in two containers, and one of them is provided with diethylaluminum chloride relative to the monomer. 40 mM, 1, 3
-Dichloro-2-propanol was added to a concentration of 48 mmol (Solution A). On the other hand, tri- (tridodecyl) ammonium molybdate was added to the monomer at a concentration of 10 mmol, and vinyl-tris (2-methoxyethoxy) silane (A-172, manufactured by Nippon Unicar) was added to 100 parts by weight of the monomer. Phenol resin-coated red phosphorus particles (Rinno Kabushiki Kaisha: Nova Excel F-5, average particle size 2.1 μm, 80% or more of the total amount having a size not more than twice the average particle size) adhered to the surface. 10 parts by weight were added (Solution B). The amount of vinyl-tris (2-methoxyethoxy) silane attached to the phenolic resin-coated red phosphorus particles was 1 part by weight based on 100 parts by weight of the particles before the attachment.

In a 200 mm × 200 mm × 5 mm plate-forming mold iron cavity, vinyl-tris (2-
A continuous glass fiber continuous mat (M9600, manufactured by Asahi Fiberglass Co., Ltd.) surface-treated with (methoxyethoxy) silane (A-172) is 200 mm × 200 mm.
And 5 plies were installed. This glass mat is 1
A drying treatment was performed in advance at 10 ° C. for 1 hour, and the amount of vinyl-tris (2-methoxyethoxy) silane adhered to the glass mat was 1 to 100 parts by weight of the glass mat before adhesion.
Parts by weight. Note that a glass mold was used for the core.

The same volume of the solution A and the solution B was mixed and injected into the mold by a low-pressure mixing and injection machine. Immediately after the completion of the filling of the reaction solution, each mold is placed in a 150 ° C inert oven for 1 hour.
Cured for 0 minutes. After that, remove the molded product from the mold,
A flat plate as a long glass fiber reinforced resin molded product was obtained. This flat plate was cut into a size of 15 mm × 120 mm to obtain a sample piece. Flexural strength of the above sample (measurement condition: 80 m between spans)
m, bending speed 2.5 mm / min), oxygen index (measurement conditions: JIS-K 7201) and bending fatigue strength were measured.

(Evaluation of physical properties) The bending strength is about 210MP.
a, the oxygen index was 27, and the bending fatigue strength was not broken even at 10 ⁸ times with a stress of 3 kgf / mm ² . Further, the coefficient of linear expansion is 3.2 × 10 ⁻⁵ / ° C.
Met.

Reference Example 1 A flat plate was formed in the same manner as in Example 1 except that nothing was attached to the surface of the phenol resin-coated red phosphorus particles, and the bending strength, oxygen index, and bending fatigue strength were measured. (Evaluation of physical properties) The flexural strength was about 190 MPa, the oxygen index was 27, and the flexural fatigue strength was 3 kgf / mm ² , and it did not break even at 10 ⁸ times until breaking. But,
The coefficient of linear expansion was 4.5 × 10 ⁻⁵ / ° C.

Comparative Example 1 A flat plate was formed and the flexural strength, oxygen index, and flexural fatigue strength were measured in the same manner as in Example 1 except that the glass mat and the phenol resin-coated red phosphorus particles were not used. (Evaluation of physical properties) Flexural strength is about 70 MPa, oxygen index is 2
2. Regarding the bending fatigue strength, it was broken 68 times with a stress of 3 kgf / mm ² . The coefficient of linear expansion was 7.6 × 10 ⁻⁵ / ° C.

[0037]

The fiber-reinforced norbornene-based resin molded article of the present invention has a very small coefficient of linear expansion. Therefore, the molded article may be heated to a high temperature due to reaction heat or may be exposed to a high temperature when the molded article is used. Also, no cracking or distortion in shape occurs. In addition, those having high and uniform bending strength and other mechanical strengths, and those containing red phosphorus particles exhibit good flame retardancy.

(Preferred Embodiment) The fiber-reinforced norbornene resin molded article of the present invention, ie, a fiber reinforcing material surface-treated with a silane coupling agent and particles having an average particle diameter of 100 μm or less, surface-treated with a silane coupling agent Preferred embodiments of a fiber-reinforced norbornene-based resin molded product obtained by bulk-polymerizing a norbornene-based monomer in the presence of a fibrous filler are as follows.

(1) The fiber reinforcing material is a long glass fiber, more preferably a continuous glass strand mat. (2) The amount of the fiber reinforcing material is 20 to 80% by weight based on the weight of the resin molded article excluding the insert. (3) The particulate filler has an average particle size of 0.01 to 50 μm, more preferably 0.1 to 30 μm. (4) The particulate filler is resin-coated red phosphorus particles.

(5) The amount of the particulate filler is 1 to 20 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the reaction solution used for molding the resin molded article. (6) The silane coupling agent is a silane compound having an ethylenic double bond in the molecule. (7) The silane coupling agent is selected from vinyl-tris (2-methoxyethoxy) silane, vinyl-trimethoxysilane, 5- (bicycloheptenyl) triethoxysilane and salts thereof.

(8) The amount of the silane coupling agent applied to the fiber reinforcing material and the particulate filler is 0.1 to 5% by weight, more preferably 0.1 to 5% by weight, based on the fiber reinforcing material and the particulate filler, respectively. 0.5 to 3% by weight. (9) The linear expansion coefficient of the norbornene-based resin molded product is 4 × 1
0 ⁻⁵ / ° C. or less. (10) The norbornene-based monomer is a tricyclic or higher polycyclic norbornene-based monomer. (11) The norbornene-based monomer is a cross-linkable polycyclic norbornene-based monomer having two or more reactive double bonds.
It is a monomer mixture containing at least 30% by weight, more preferably at least 30% by weight.

Claims (1)

[Claims] 1. A norbornene-based monomer is subjected to bulk polymerization in the presence of a fiber reinforcing material surface-treated with a silane coupling agent and a particulate filler having an average particle size of 100 μm or less surface-treated with a silane coupling agent. Fiber-reinforced norbornene resin molded product.