JPH05169541A - Manufacture of fiber-reinforced secondary molded product - Google Patents

Abstract

PURPOSE:To manufacture a fusible fiber-reinforced molded product consisting of reinforcing fiber impregnated adequately with matrix resin with outstanding heat resistance and mechanical strength. CONSTITUTION:A primary molded product of fusible norbornene polymer obtained by polymerizing a norbornene monomer in a metathesis lump in a die where a reinforcing fiber is arranged, is shaped with a predetermined part fused using a press, and then is cooled.

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 secondary molding using a fiber-reinforced polynorbornene-based molding material. More specifically, the present invention relates to a method for efficiently producing a secondary molded body having a predetermined shape by using a fusible molding material whose matrix is formed by bulk polymerization of norbornene-based monomers.

[0002]

2. Description of the Related Art In recent years, fiber-reinforced resin primary moldings have been widely used in the fields of civil engineering, construction, and transportation equipment as lightweight, highly rigid, and non-rusting materials. For example, primary moldings made of polypropylene as a matrix resin and reinforced with glass fibers are used in automobile fields for bumper beams, seat frames, floor panels, battery trays, steps, baffles, and the like. In the civil engineering field, it is used for concrete formwork, and in the distribution field, it is used for pallets and containers. The operation of forming a secondary molded body using such a primary molded body is performed in a very short time using, for example, a press molding machine used for plastic working of sheet metal.

Such a fiber-reinforced resin primary molded article is
Generally, a thermoplastic resin is used as a matrix resin, and as a manufacturing method thereof, a method of heating and melting the thermoplastic resin to impregnate the fiber mat and then cooling and curing, or a method of suspending the powdery thermoplastic resin and the fiber in suspension A method is known in which a sheet is formed, dried, and then heat-cured. In either method, the thermoplastic resin is melted by heating and impregnated into the fiber in a high-viscosity state, so impregnation between the fibers is poor, and physical properties such as mechanical strength cannot be sufficiently obtained. Since the matrix is used, there is a problem that the heat resistant temperature is low.

As a method for producing a molding material in which a polymer is uniformly impregnated between fibers, a method of impregnating a low-viscosity reaction liquid between the fibers and polymerizing is known. For example, a molded product of a fiber-reinforced norbornene-based polymer is obtained by carrying out reaction injection molding by combining a norbornene-based monomer represented by dicyclopentadiene (hereinafter referred to as DCP) with a metathesis catalyst system (for example, JP-A-1-31953).
No. 8). This molded product has excellent heat resistance, chemical resistance, etc.
It is known that it has a shape memory property and can be secondary-molded into a desired shape by applying a mechanical force under heating (JP-A-2-225518).

By the way, it is necessary to provide an uneven thickness portion such as a rib or a boss in the molded product, if necessary, for the purpose of reinforcement and assembly. However, when directly molding a molded product having such an uneven thickness portion, there is a problem that a sink mark is generated in the thick portion and the appearance is remarkably impaired, or a distortion is left inside the molded product, which causes a crack. Further, since the flow of the resin in the mold becomes complicated, there is a problem that the desired strength cannot be guaranteed due to the inclusion of air bubbles and the generation of a portion not filled with the resin.

Further, it is difficult to form a complicated shape such as a rib or a boss even if the primary molded body is simply secondary molded.

[Problems to be Solved by the Invention]

The inventors of the present invention have conducted extensive studies to improve the above-mentioned drawbacks of the prior art. As a result, the polynorbornene-based primary molded product obtained by bulk polymerization has good glass fiber matrix impregnation. When the reinforcing effect of the fiber is sufficiently obtained, and when a crosslinkable norbornene-based monomer and a non-crosslinkable norbornene-based monomer are copolymerized,
It was found that the primary molded product has a heat fusion property even though it is a cross-linked polymer, and by applying this property, a high-performance fiber-reinforced secondary molded product having a complicated shape can be efficiently obtained by a simple operation. The present invention has been completed and the present invention has been completed.

[0008]

Thus, according to the present invention, a fusible polynorbornene-based primary molding obtained by bulk polymerization of a norbornene-based monomer in the presence of a metathesis catalyst system in the presence of reinforcing fibers. By fusing the other fusion-bonded portion of the primary molded body or the fusion-bonded portion of another primary molded body formed of a material that can be fused with the primary molded body to the fusion-bonded portion of the body, and by fusing Provided is a method for producing a fiber-reinforced secondary molded body, which comprises melting the fusion-bonded parts together, shaping them into a predetermined shape, and then cooling.

The present invention will be described in detail below.

(Primary molded product) The primary molded product in the present invention means a norbornene-based polymer having a fusion property obtained by bulk polymerization of a norbornene-based monomer in the presence of a reinforcing fiber in the presence of a metathesis catalyst system. Is a molded body of
It has a fused portion in a part thereof. The norbornene-based monomer may be only a non-crosslinkable one, but usually, a non-crosslinkable norbornene-based monomer and a crosslinkable norbornene-based monomer are used in combination. Since the primary molded product uses a low-viscosity norbornene-based monomer as a raw material, it can well impregnate fibers and has a high fiber-reinforced effect. Further, since it is possible to use a crosslinkable norbornene-based monomer, it is possible to obtain a molded product having higher heat resistance than a fiber-reinforced primary molded product using a mere thermoplastic resin. Norbornene-based monomer The non-crosslinkable norbornene-based monomer (A) is a compound having one norbornene ring in the molecule. Specific examples include norbornene, methylnorbornene, dimethylnorbornene, ethylnorbornene, chlorinated norbornene, chloromethylnorbornene, trimethylsilylated norbornene, phenylnorbornene, cyanonorbornene, dicyanonorbornene, methoxycarbonylnorbornene, pyridylnorbornene, nadic acid anhydride, nadic Bicyclic compounds such as acid imides, tricyclic compounds such as dihydrocyclopentadiene and its alkyl and alkylene, alkylidene and aryl substitution products, tetracyclododecene, dimethanooctahydronaphthalene and its alkyl and alkylene, alkylidene and aryl substitution products. 4 ring bodies, 5 ring bodies, 6 ring bodies and the like.

On the other hand, the crosslinkable norbornene-based monomer (B) is a polycyclic norbornene-based monomer having two or more reactive double bonds. Specific examples thereof include norbornadiene, DCP, tricyclopentadiene, dimethanohexahydronaphthalene, dinorbornene, tetracyclopentadiene, compounds in which two norbornene rings are linked by a hydrocarbon chain or an ester group, alkyls and aryls thereof. Substitutes and the like can be mentioned.

The composition of the non-crosslinkable norbornene-based monomer (A) and the crosslinkable norbornene-based monomer (B) is usually
(A) 100 to 30 wt%, (B) 0 to 70 wt%
%, Preferably 100 to 60 wt% for (A), 0 to 40 wt% for (B), and more preferably 90 to 60 w for (A).
t% and (B) are selected from the range of 10 to 40 wt%. When the amount of the monomer (A) used is small, the heat resistance of the obtained polymer is improved, but the behavior of thermoplasticity is reduced, and the resin does not easily flow when heated and press-molded. Fusing is less likely to occur.

When the amount of the monomer (B) used is large, it has a characteristic as a thermosetting resin, but nevertheless, it is possible to perform press molding by heating and to fuse the same type of molded bodies to each other. This is a characteristic of the norbornene-based crosslinked polymer that is not found in thermosetting resins. The cause is not clear, but it is considered to be due to the large elongation property.

The metathesis polymerization of norbornene-based monomers generally has a very high molecular weight, but the addition of a small amount of a molecular weight modifier to the monomer can reduce the molecular weight and improve moldability. As such a compound,
Examples include α-olefins. Further, since vinyl norbornene also functions as a molecular weight regulator at the same time as the metathesis polymerization, a low molecular weight compound does not remain and a primary molded product having good mechanical strength can be obtained.

Further, monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, and cyclododecene, which are capable of ring-opening polymerization with one or more of the above norbornene-based monomers, are used in combination within a range not impairing the object of the present invention. can do.

The metathesis polymerization catalyst type ring - opening polymerization catalyst may be any metathesis catalyst known as a bulk polymerization catalyst of norbornene type monomers (for example, JP-A-58-127728 and JP-A-58-58).
No. 129013), but there is no particular limitation.

As the metathesis catalyst, tungsten,
Examples thereof include halides such as molybdenum, tantalum, ruthenium, oxyhalides, oxides, organic ammonium salts, oxyacid salts, and heteropolyoxygen acid salts.

The cocatalyst is a compound that acts to reduce the metathesis catalyst. Specific examples include alkylaluminum, alkylaluminum halides, alkoxyalkylaluminum halides, aryloxyalkylaluminum halides, organotin compounds, organozinc compounds, and organomagnesium compounds.

An activator is used to accelerate the polymerization rate and increase the reaction rate of the norbornene-based monomer. Examples of the activator include halogenated alcohol, halogenated ketone, halogenated ester, oxygen, a small amount of water, metal alkoxide, metal halide, halogenated hydrocarbon and the like. When the reaction is too fast and only local polymerization proceeds, the amount of the catalyst can be reduced, the ratio of the metathesis catalyst to the cocatalyst can be changed, and an activity modifier can be used.
As the activity regulator, a compound composed of alcohol, ether, acid, ester, nitrile, amine and the like is used.

The metathesis catalyst is used in an amount of usually 0.01 to 50 mmol, preferably 0.2 to 20 mmol, based on 1 mol of the norbornene-based monomer. The cocatalyst is generally used in the range of 0.1 to 200 (molar ratio), preferably 1 to 10 (molar ratio) with respect to the catalyst component. The activator is usually 0.1 to 10 relative to the catalyst component.
It is used in the range of 0 (molar ratio), preferably 0.2 to 5 (molar ratio). The activity modifier is generally used in the range of 0.1 to 200 (molar ratio), preferably 1 to 10 (molar ratio) with respect to the catalyst component.

The metathesis catalyst, the cocatalyst, the activator and the activity modifier are preferably dissolved in norbornene-based monomers and used, but a small amount of a solvent is used as long as the properties of the polymer are not essentially impaired. It may be used after being suspended or dissolved. Fiber In producing the primary molded product used in the present invention, the reinforcing fiber (C) is placed in a mold and used.
Any of (C) can be used as long as it does not substantially inhibit metathesis polymerization. For example, carbon fiber, glass fiber, polyvinyl fiber, metal fiber, ultra high molecular weight polyethylene fiber, etc. may be mentioned. Among them, glass fiber is economical and preferable. Surface treatment of the surface of (C) with a silane coupling agent or the like is preferable because the adhesiveness with the matrix resin is improved and the physical properties are improved.
The length of (C) is preferably 3 mm or more, more preferably 5 mm.
mm or more. When the length of (C) is short, the effect of improving the strength is small. The thickness of (C) is not particularly limited, but a bundle of fibers having a thickness of several microns is generally used.

(C) can be used in the form of mat or cloth using a sizing agent. As the sizing agent, one that does not inhibit metathesis polymerization is used. Examples include thermoplastics such as polystyrene, petroleum resins, polyolefins and the like. The orientation of (C) may be random or a sequence having orientation, and a composite of these may be used.

(C) is used in the form of a mat, a cylinder, a thick plate, a rod or the like. Further, in order to make the appearance of the molded product smooth, a surfacing mat in which continuous fibers are crossed in the surface layer to form a thin paper can be used. In either case (C), it is necessary to dry it sufficiently before use to remove water and other substances that inhibit metathesis polymerization.

The content of (C) is 5 to 65 wt%, preferably 10 to 50 wt%, and more preferably 15 with respect to the total amount of the filler and other additives such as fibers and elastomers and the resin. Is about 40 wt%. If the amount of the fibers is small, a sufficient reinforcing effect cannot be obtained, and if the amount of the fibers is large, the reaction heat is absorbed by the fibers, and the resin is not sufficiently cured. In this case, the molding temperature may be raised to promote the effect.

Thermoplastic Polymer In the present invention, a thermoplastic polymer (D) can be used in addition to (A), (B) and (C). The thermoplastic polymer (D) referred to here is polyethylene, polypropylene, polystyrene, ethylene-vinyl acetate copolymer,
In addition to resinous polymers such as petroleum resin and hydrogenated petroleum resin,
Natural rubber, polybutadiene, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer, 1,2-polybutadiene, polyisoprene, styrene-isoprene-styrene block copolymer, ethylene-propylene-diene terpolymer, butyl rubber Although such elastomers are included, it is preferable to use a resinous polymer from the viewpoint that the reaction stock solution has good operability and the heat resistance of the primary molded product is improved. The amount of (D) used is usually (A)
0 to 40 wt with respect to 100 wt parts of the total amount of (B)
Parts, preferably in the range of 5 to 30 wt parts.
When (D) is used, the fluidity of the molten resin is improved during secondary shaping, and fusion tends to occur, but when used in a large amount, the viscosity when added to the norbornene-based monomer is It becomes high, which causes deterioration of impregnation in (C). Additives, antioxidants and the like formulation stock solution fillers, ultraviolet absorbers, crosslinking agents, coloring agents and flame retardants, oxalic whether agent, incorporating the various additives and fillers such as fillers for weight reduction The properties of the molded body can be modified thereby.

Examples of the antioxidant include various antioxidants for phenol, phosphorus, amine, and other plastics and rubber. These antioxidants may be used alone or in combination. The compounding ratio is usually 0.5 part by weight or more, preferably 1 to 3 parts by weight, based on 100 parts by weight of the total amount of the norbornene-based monomer and the thermoplastic resin. Further, the antioxidant may be copolymerizable with a monomer, and specific examples thereof include norbornenylphenol compounds such as 5- (3,5-di-t-butyl) -4-hydroxybenzyl-2-norbornene. And the like (see JP-A-57-83522).

As the cross-linking agent, sulfur, selenium, tellurium,
Examples thereof include oximes, dinitroso compounds, organic peroxides such as dicumyl peroxide and benzoyl peroxide, divinyl compounds such as divinylbenzene and hexatriene, diallyl compounds such as allyl phthalate and diallyl carbinol, and dicarboxylic acids.

Examples of the colorant include carbon black, titanium white, quinacridone pigment, polyazo pigment, phthalocyanine pigment, oil dye, acid dye and basic dye.

As the filler, inorganic fillers such as glass powder, carbon black, talc, calcium carbonate, mica, aluminum hydroxide, antimony trioxide, graphite, molybdenum disulfide, metal powder, fine powder polyethylene, Examples of organic fillers include high molecular weight polyethylene, polyvinyl chloride, fluororesins, silicone resins, polyamide resins, polyester resins, polyphenylene oxide, and phenolic thermosetting resins.

The additives and cross-linking agents are often used by dissolving or dispersing them in the norbornene-based monomer in advance.

(Molding of Primary Molded Body) A norbornene-based monomer is mixed with a thermoplastic resin and various additives, a metathesis catalyst is added, and then the fiber is impregnated and cured. The fibers are mats, cloths, sheets, etc. laid in a mold (form) in a batch system, or while the fibers impregnated with the compound liquid are continuously sandwiched between rotating belts such as a double belt laminator. Pull out and perform ring-opening bulk polymerization.

Further, a norbornene-based monomer is blended with a thermoplastic resin and various additives, divided into two liquids and placed in another container, a metathesis catalyst is added to one, and a cocatalyst is added to the other. Prepare a stable stock solution of. It is also possible to mix these two types of reaction stock solutions and then inject the reaction solution into a mold in which fibers are set or into the gap of the laminator in which the fibers are set, impregnate the fibers with the reaction solution, and polymerize. ..

Further, an inert solvent in which a metathesis catalyst and a cocatalyst are dissolved (for example, a solvent which does not undergo a metathesis reaction such as toluene) is added to a liquid prepared by mixing a norbornene-based monomer with a thermoplastic resin and various additives, and well. After mixing, the fibers may be poured into a set mold, and the fibers may be impregnated with a reaction solution to polymerize.

For the polymerization, a molding machine used in ordinary RIM molding or extrusion molding, such as a gear pump, a plunger pump, a lance pump, and a screw type extruder can be used. For example, in an RIM machine, the mixing pressure of the two liquids is preferably about 100 Kg / cm ^2, but the injection pressure into the fiber is not particularly limited, and 10 kg / cm ² or less is usually sufficient. The temperature of the mold or laminator is usually 30 ° C or higher,
Preferably 50 to 200 ° C., particularly preferably 60 to 13
It is 0 ° C. The polymerization time may be appropriately selected, but is usually 1 minute to 15 minutes.

Monomers and other compounding components used in the polymerization reaction are preferably stored and operated in an atmosphere of an inert gas such as nitrogen gas. The mold and laminator to be molded do not need to be sealed with an inert gas, but sealing is more preferable because metathesis polymerization is less likely to be hindered.

Further, when curing, a polyolefin sheet is preliminarily laid in a mold, or bulk ring-opening polymerization is performed while continuously flowing it through a laminator, whereby a sheet-shaped molded article having a polyolefin surface layer can be manufactured.

The sheet-shaped molded product has a plate-like shape and a thickness of 1
It is at least mm, preferably at least 2 mm.

(Fusable Material) The material that can be fused with the molded body of the norbornene-based polymer having a fusion property, which is the primary molded body, includes the same type of norbornene polymer as the primary molded body, DCP and tetra Ring-opening polymers of norbornene-based monomers such as cyclododecene, hydrogenated products thereof, addition copolymers of the norbornene-based monomers and ethylene, polyethylene, polypropylene, polystyrene, polyvinyl chloride, ethylene vinyl acetate copolymer, styrene-isoprene-
Examples thereof include styrene copolymers, styrene-butadiene copolymers, styrene-butadiene-styrene copolymers, and the like. These are used by determining the heat fusion temperature according to the material used, the molecular weight and the like. Among them, it is prized for the fact that the polymer of the same kind as that of the primary molded body is firmly fused.

(Manufacturing Method of Secondary Molded Body) The above-mentioned primary molded body has a glass transition temperature of resin or higher, preferably glass transition temperature to 300 ° C., more preferably glass transition temperature + 20 ° C.
Secondary heating is performed by heating in the range of up to 250 ° C. That is,
After heating the fusion part or the whole of the primary molded body to a temperature within a predetermined range, the predetermined parts are overlapped and set in a mold, and the predetermined part is simultaneously fused by applying an external force by a mechanical pressing force to a predetermined shape. It is shaped and then solidified by cooling to obtain a secondary molded body. A step of cutting an extra portion is provided if necessary.

When two or more types of molded products are used as the primary molded product, each of them is heated to a glass transition temperature or higher, a predetermined part is overlapped and set in a mold, and an external force is applied by a mechanical pressing force. As a result, the predetermined portion is fused.

As means for heating the primary molded body, either internal heating or external heating can be used, and it may be selected appropriately. Specifically, for example, any of heating with a heating line such as an oven, a hot plate, a heat gun, a far-infrared heater, or heating with high frequency or ultrasonic waves may be used, but external heating with a heating line that can be applied to a large or thick molded product is also possible. preferable.

Since the primary molded body according to the present invention has a fusion-bonding property, any portion of the primary molded body can be a fusion-bonded portion. The fused portion refers to the portion of the unfused primary molded body which is desired to be fused. As the fusing method, a fusing part of the primary molding and another fusing part of the primary molding or a fusing part of another primary molding formed of a material that can be fused with the primary molding. Examples of the method include a method of directly superposing the materials at a glass transition temperature or higher and pressing with a pressing machine directly or through a jig, and a method of pressing a fused portion by an operator while heating the fused portion with an electric iron.

As an example of fusing two or more fusion-bonded portions of one primary molded body, for example, a plate-shaped primary molded body is wound and both ends thereof are fused to form a columnar shape. .. As an example of fusing a plurality of primary molded bodies, for example, those in which plate-shaped primary molded bodies are stacked to increase the thickness,
Ribbed pieces (example: molded article shown in FIG. 2), primary molded articles having convex portions stacked and hollow ends fused (example: molded article shown in FIG. 4), rod-shaped An example is one in which the end portions of the molded body are fused and joined together.

In this heating step during secondary molding, the double bond of the ring-opening polymer of the norbornene-based monomer may react. In particular, when a crosslinking agent is blended, the double bond reacts, and thermal properties such as heat distortion temperature, bending and tensile modulus and mechanical properties are improved.

For cooling, the mold may be cooled by air, or cooling equipment such as water cooling installed in the mold may be used. When the secondary molded product is solidified, the secondary molded body is taken out from the mold.

[0046]

【The invention's effect】

According to such an invention, it is possible to manufacture a molded product having an uneven thickness portion without impairing the appearance and mechanical strength due to sink marks or bubbles. Further, it is possible to manufacture a molded product having a complicated or peculiar shape which cannot be obtained by simply press-molding the primary molded product.

EXAMPLES Examples will be described below. Unless stated otherwise, the description in the text is in weight unit.

Example 1 A glass ampoule kept under a nitrogen atmosphere was treated with a glass fiber having a length of 6 mm, which was surface-treated with styrylsilane, to prepare a non-crosslinkable monomer, a crosslinkable monomer, a thermoplastic resin and a glass fiber. 20% was added to the total amount, and the non-crosslinkable monomer and the crosslinkable monomer shown in Table 1 and the thermoplastic resin were mixed in predetermined amounts, dispersed and dissolved. Thereafter, ethyl norbornene (hereinafter referred to as E
1 mol / liter concentration of diethylaluminum chloride dissolved in tNB (abbreviated as tNB) to 20 mmol / liter concentration (the same applies to the norbornene-based monomer).
1 mol / liter concentration of n-propanol dissolved in EtNB was added to a concentration of 20 mmol / liter, and 1 mol / liter concentration of silicon tetrachloride dissolved in EtNB was added to a concentration of 7 mmol / liter. 3 ampoules
After the temperature was kept at 5 ° C., tri (tridecyl) ammonium molybdate having a concentration of 0.5 mol / liter was added with sufficient stirring so as to obtain a concentration of 5 mmol / liter, and reacted.

In the reaction, after the components were uniformly mixed, the viscosity increased a while later, a rapid heat generation was observed, and a cured primary molded body was obtained. The molded body was taken out by breaking the glass ampoule, and the glass transition temperature (Tg)
And conversion was measured.

Further, the obtained primary molded body was divided into two pieces, and in a space of the spacer of a metal frame in which two metal plates were stacked with a 5 cm × 6 cm frame through a spacer having a thickness of 3 mm. The primary compact was sandwiched, heated at 180 ° C. for 10 minutes, and then pressed at a pressure of 50 kg / cm ² . Then, after cooling to room temperature, the secondary molded body was taken out from the frame, and the fluidized state and the fused state were observed. Then, the glass transition temperature (Tg) and the conversion rate were measured.

Measurement composition of charge composition, glass transition temperature (Tg) of primary molded article and conversion rate, observation state during molding of secondary molded article, measurement result of glass transition temperature (Tg) of secondary molded article and conversion rate Is shown in Table 1.

The Tg is measured by a differential scanning calorimeter. The conversion rate was based on the residual rate of weight obtained by heating a polymer sample from room temperature to 400 ° C. with a thermobalance. The notes in the table are described below. 1) Distinction between Examples and Comparative Examples 2) NB: Norbornene EtNB: Ethylnorbornene VNB: Vinylnorbornene 3) DCP: Dicyclopentadiene TCP: Tricyclopentadiene 4) PS: Polystyrene (Asahi Kasei, trade name Styron,
Vicat softening point 87 ° C.) SIS: styrene-isoprene-styrene block polymer (manufactured by Nippon Zeon Co., Ltd., trade name Quintac 3421) HDCP: hydrogenated DCP resin (manufactured by Exxon Co., trade name Escalets) Number of copies relative to the total amount of crosslinkable monomer 5) A: The surface is smooth and flows to every corner. B: The surface is slightly uneven but flows to every corner. C: Surface is uneven and does not flow to every corner. 6) A: Interface Good fusion without B: There is no interface, but there is opacity. C: There is an interface and peeling occurs.

[0053]

[Table 1]

The primary moldings shown in Experiment No. 1-1 and Experiment No. 1-4 were each divided into two pieces, and their cross sections were cut with a knife. The fibers did not come off, and the resin was sufficiently impregnated in the fibers. On the other hand, when a commercially available fiber reinforced sheet having polypropylene as a matrix (made by Idemitsu NSG, trade name: X sheet) was cut and the cross section was cut with a knife, the fibers peeled off and the resin was not sufficiently impregnated into the fibers.

As shown in Experiment No. 1-1, Experiment No. 1-3 and Experiment No. 1-4, the Tg increased as the amount of crosslinkable monomer increased.
Rose.

As shown in Experiment Nos. 1-1 to 1-5,
Based on the total amount of non-crosslinkable monomer and crosslinkable monomer,
Even if the crosslinkable monomer was mixed by about 46%, the resin flowed to every corner in the mold for secondary molding and was fused well, but the crosslinkable monomer was 77% of the total norbornene-based monomer.
When it exceeded, the fluidity was lost and fusion did not occur.

Experiment number 1-3 and experiment numbers 1-6 to 1-
As shown in Fig. 8, when the type of the monomer or the thermoplastic resin is changed, the glass transition temperature (T
It was found that g) can be adjusted and a primary molded product having excellent heat resistance can be obtained.

Example 2 Ethyl norbornene 30% and ethyl tetracyclododecene 3 as non-crosslinkable monomers
0%, dicyclopentadiene 40 as a crosslinkable monomer
The experiments were carried out using a monomer mixture consisting of%.

The above S was added to 100 parts of the monomer mixture.
In a rubber solution in which 10 parts of IS and 2 parts of a phenolic antioxidant (Ciba Geigy, trade name Irganox 1010) were dissolved, under a nitrogen atmosphere, diethylaluminum chloride concentration of 40 mmol / liter, n-propanol 4 was used.
A concentration of 4 mmol / liter and a concentration of silicon tetrachloride of 12 mmol / liter were respectively added to prepare a liquid B.

SIS was added to 100 parts of the monomer mixture.
A solution of 10 parts of dissolved rubber was added with a concentration of 10 mmol / liter of tri (tridecyl) ammonium molybdate under a nitrogen atmosphere to prepare a solution A.

Liquid A and liquid B were sent to a power mixer so that the volume ratio of each was 1: 1, and then 1300 g
/ M ² chopped mat and surfacer glass (area weight 30 g / m ² ) laid at a thickness of about 3 mm at 70 ° C
Immediately poured into a flat plate mold heated to. The injection time was about 20 seconds, and the reaction was performed for 3 minutes in the mold.

In the above chopped mat, styrylsilane-treated E glass fiber was cut into a length of 50 mm, and polystyrene was used as a sizing agent at 1300 g / m ^2.
The mat of the weight of 1 was formed, and it was previously shaped by the mold. The same chopped mat was used in the following experiments.

The glass transition temperature (T
g) was 137 ° C., the heat distortion temperature was 133 ° C., and the Izod impact strength was 125 Kgf · cm / cm ² (23 ° C., notched). The glass content was 34%.

The heat distortion temperature is JIS-K-691.
It is the value measured according to No. 1 with a load of 18.5 Kg / cm ² . The glass fiber content is a value measured according to JIS-K-70525.

The primary molded body was heated to 200 by an electric warmer.
After heating to ℃, it was bent into an L shape. The primary molded body and another primary molded body are heated to 200 ° C. by an electric warmer and then overlapped with each other, and the overlapped portion has a mold clamping pressure of 50.
Press molding was performed at Kg / cm ² and a mold temperature of 180 ° C. for 10 minutes. (FIG. 2) After that, the mold temperature was cooled to room temperature, and the secondary molded body was taken out. A secondary compact having only ribs was obtained. (Fig. 1)

Example 3 A primary molded body was molded in the same manner as in Example 2 except that a trough-shaped mold was used.
The plate-shaped primary molded body molded in Example 2 and the box-shaped primary molded body were stacked so as to have a hollow portion, and the stacked portion was clamped with a ring-shaped jig at a mold clamping pressure of 50 Kg.
/ Cm ² and mold temperature 180 ° C. for 10 minutes for fusion.
Then, the mold temperature was cooled to room temperature, and the secondary molded body was taken out. The inside of the molded product was hollow (Fig. 4), and a secondary molded product (Fig. 3) was obtained in which the ends of the molded product were fused. Tg of the obtained secondary compact was 140 ° C., heat distortion temperature was 138 ° C., Izod impact strength was 130 Kgf · cm / cm ² (23 ° C.),
Flexural strength 15 Kgf / mm ² , flexural modulus 490 Kgf
/ Mm ² .

[Brief description of drawings]

FIG. 1 is a perspective view of a secondary molded body of Example 2.

[Explanation of symbols]

 1; Primary molded body

FIG. 2 is a front view of Example 2 during pressing.

[Explanation of symbols]

 1; Primary molded body 2; Steel fusion-bonding part pressing jig 3; Press surface

FIG. 3 is a perspective view of a secondary molded body of Example 3.

[Explanation of symbols]

 1; trough-shaped primary molded body 2; plate-shaped primary molded body 3; fused portion

FIG. 4 is a sectional view of a secondary molded body of Example 3 (A- in FIG. 3).
It is A'sectional view).

[Explanation of symbols]

 1; trough-shaped primary molded body 2; plate-shaped primary molded body 3; fused portion 4; hollow portion

Claims (1)

[Claims] 1. A fusion-bondable polynorbornene-based primary molded article obtained by bulk polymerization of a norbornene-based monomer in the presence of a reinforcing fiber in the presence of a metathesis catalyst system. Along with fusing other fusion bonding parts or fusion bonding parts of other primary moldings formed of a material that can be fused with the primary molding, and fusing the fusion bonding parts by heating under fusion. A method for producing a fiber-reinforced secondary molded article, which comprises cooling into a predetermined shape and then cooling.