JPH0881566A - Fiber-reinforced resin - Google Patents

Abstract

PURPOSE: To obtain a fiber-reinforced resin which has been reinforced with a fiber without causing undercure and based on polydicyclopentadiene by using a specified resin as a binder for the fibrous reinforcement. CONSTITUTION: This resin is made of a fiber bundle.formed by binding with a polyolefin having an introduced polar group and a dicyclopentadiene resin. By using a thermoplastic binder as the binder, a network filling material made of fiber bundles can be used as preformable one. By using at most 30 single fibers to form a fiber bundle, the formed bundle can reinforce polydicyclopentadiene without detriment to the surface properties of the resin component. An example of the binder used is an aqueous solution (emulsion) formed from a mixture of polypropylene with maleic acid. In addition to polypropylene, polyethylene or the like may be. Examples of the fibrous reinforcements used include glass fibers, carbon fibers, metal fibers and lowly polar organic fibers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber-reinforced resin which is a fiber-reinforced thermosetting resin, and more particularly to a fiber-reinforced resin containing dicyclopentadiene as a main component.

[0002]

2. Description of the Related Art Conventionally, thermosetting resins such as epoxy resins, unsaturated polyester resins, vinyl ester resins and urethane resins have been used for the purpose of molding as thinly as possible and increasing mechanical strength, or When used as an outer panel of a vehicle, it may be reinforced with fibers for the purpose of suppressing the linear expansion coefficient to be small and improving the dimensional accuracy. Here, the fiber reinforcing material as a filler used for the thermosetting resin includes glass fiber, carbon fiber, metal fiber and the like. When these fiber reinforcements are mixed with a thermosetting resin, when the number of single fibers converged is glass fiber, the fiber reinforcements are converged by a sizing agent into a state of 30 or more and then a reticulated filler. Often molded and used. As the sizing agent used here, resins such as urethane type and unsaturated polyester type have been used.

By the way, polydicyclopentadiene (P
DCPD) is adopted as a main forming raw material for resin parts, for example, outer plate parts such as air dam skirts of vehicles. This polydicyclopentadiene is formed by dimerizing cyclopentadiene (CH ₂ .CH = CH.CH = CH), which is a colorless liquid, and is a stable crystalline substance at room temperature. Such polydicyclopentadiene (PDCP
When the resin part D) is molded, a RIM (reaction injection molding) molding method, which is a type of conventional injection molding method, is used.

When a resin component of polydicyclopentadiene (PDCPD) is molded by this RIM molding method, a metathesis catalyst is mixed and used in two parts containing a dicyclopentadiene monomer as a main component. Here, one part of the metathesis catalyst contains a tungsten-containing catalyst such as WCl ₆ WOCL ₄ and the other part of the metathesis catalyst contains an activator such as diethylaluminium chloride Et ₂ AlCl. During this molding, two parts (A liquid and B
(Liquid) is set in a RIM molding machine, and both liquids are mixed at a ratio of 1: 1 and fed into the mold, metathesis polymerization occurs, rapid heat generation is observed after a short time, and an insoluble polymer is formed. . The obtained resin part is non-adhesive and can be taken out of the mold without a release agent. Moreover, the surface of this polydicyclopentadiene (PDCPD) has unsaturated groups, which are air-oxidized to introduce polar groups. Therefore, the adhesiveness with a paint or adhesive made of epoxy resin, polyurethane or the like is good.

[0005]

By the way, as the above-mentioned thermosetting resin, polydicyclopentadiene (PDCP) is used.
In the case of adopting D) and molding the fiber reinforced resin, at the time of molding, glass fibers are bundled in advance by using a sizing agent to form a mesh filler, and the mesh filler is set in a mold. Then, set the above two parts (liquid A and liquid B) in the RIM molding machine, mix both liquids in a ratio of 1: 1 and supply into the mold in which the reticulated filler is placed, A polymer will be produced. However, in this case, there are the following problems.

That is, polydicyclopentadiene (PDC
When PD) is to be fiber-reinforced, it is assumed that a urethane-based resin, an unsaturated polyester-based resin, or the like is used as a sizing agent for the fiber reinforcement. The urethane-based or unsaturated polyester-based sizing agent used here is a resin having a relatively high polar group. For this reason, when the two portions containing the dicyclopentadiene monomer as the main component undergo a curing reaction by metathesis polymerization, the polymerization is hindered, and a problem of curing failure occurs. For this reason, using a fiber reinforced material that has been converged by a sizing agent consisting of resins having a polar group,
It was difficult to obtain a fiber-reinforced resin of polydicyclopentadiene (PDCPD).

Furthermore, polydicyclopentadiene (PDC
There is a demand for molding a (PD) -based resin in a relatively thin manner and for reinforcing the fiber as much as possible in order to keep the linear expansion coefficient of the molded resin component low, but there are the following problems. That is, single fibers such as glass fibers, carbon fibers, and metal fibers are reinforced as the number of converged fibers increases, but in this case, the surface properties of resin parts made of polydicyclopentadiene (PDCPD) resin are significantly deteriorated. It was a problem. An object of each of the first to third aspects of the invention is to provide a fiber-reinforced resin containing fiber-reinforced polydicyclopentadiene as a main component without causing curing failure.

In particular, the second aspect of the present invention is intended to use the sizing agent adhered to the fiber reinforcing material as thermoplastic and the reticulated filler as preformable. In particular, claim 3
Aims at fiber-reinforced polydicyclopentadiene without the deterioration of the surface properties of resin parts.

[0009]

In order to achieve the above object, the invention of claim 1 is characterized in that it is formed of a fiber bundle bundled with a polar group-introduced polyolefin and a PDCPD resin. . The invention of claim 2 is the fiber reinforced resin according to claim 1, wherein the sizing agent is thermoplastic. The invention of claim 3 is characterized in that, in the fiber-reinforced resin of claim 1 or 2, the number of single fibers of the fiber bundle is 30 or less.

[0010]

According to the invention of claim 1, when the polyolefin into which the polar group is introduced converges the fiber, the polar group is attached so as to cover the fiber, and the outside thereof is bonded so as to be covered by the nonpolar polyolefin. As a whole, the bundled fiber bundles maintain nonpolarity or low polarity around the fiber bundles and do not hinder the metathesis polymerization of the PDCPD resin. According to the invention of claim 2, the sizing agent used in the fiber reinforced resin of claim 1 is made to be particularly thermoplastic so that the reticulated filler can be easily deformed by heating. According to the invention of claim 3, the fiber bundle used in the fiber reinforced resin according to claim 1 or 2,
In particular, the number of single fibers converged is 30 or less so that the fiber bundle does not affect the surface shape of the resin component.

[0011]

1 shows a drag wheeler which is a resin component made of fiber reinforced resin according to the present invention. The drag wheeler D is composed of an outer plate D-1 that receives traveling wind and a plurality of reinforcing rims D-2 inside thereof, which are fixed to a roof of a cab (not shown) by a fixing tool for use. The fiber-reinforced resin used here is mainly made of polydicyclopentadiene (PDCPD) resin, and the fiber-reinforced material is glass fiber. The glass fiber, which is a fiber reinforcing material, is prepared as a single fiber GF in advance. The single fibers are bundled into a thread shape by a primary binder that is a sizing agent, and are bundled into a net shape by a secondary binder that is a sizing agent.
Molded as 2.

Here, the primary binder and the second binder which are sizing agents.
As the next binder, a polyolefin resin, here, an aqueous solution (emulsion) PPE containing polypropylene (PP) as a main component is used. As shown in FIG. 2A, 1
In the converging step with the next binder, the polypropylene (PP) aqueous solution PPE as the primary binder is prepared in the container 1. Here, while the glass fiber monofilaments GF are immersed in the aqueous solution PPE, the monofilaments are bundled into a filamentous bundle GF1 by the operator so that the number of monofilaments converges to 30 or less. Next, as shown in FIG. 2B, in the converging step with the secondary binder, the polypropylene aqueous solution PPE as the secondary binder is prepared in the container 2. Here, the filamentous converging body GF1 is soaked in the polypropylene aqueous solution PPE and bundled into a net by an operator to form a net-like filler GF2.
Formed as.

As mentioned above, the aqueous solution (emulsion)
As PPE, a non-polar, low softening point thermoplastic polypropylene (PP) is used as a main component, and maleic acid M of a polar group is mixed. When this aqueous solution PPE is attached to the glass fiber monofilament GF, first, as shown in FIGS. 4A and 4B, the polar group maleic acid M is first added to the monofilament GF.
Are sequentially attached so as to cover the above, and hydrogen in the unsaturated carbon portion of each maleic acid M (see FIG. 5) is substitution-bonded to the end of the non-polar polypropylene PP. The polypropylene PP is sequentially connected in a long chain. In this case, the polar group maleic acid M is attached so as to cover the bundle of the monofilaments GF, and the polypropylene PP long-bonded to the outside in the chain of the nonpolar group.
Is linked via another maleic acid M to another, long chain polypropylene PP. As a result, monofilament GF
In contrast to the maleic acid M, which is a polar group that covers the bundle, the amount of polypropylene PP that is sequentially and longly connected to the outside of the bundle is extremely large. As a result, the outer peripheral portion of the bundle of the single fibers GF, that is, the periphery of the filamentous converging body GF1 and the net-like filler GF2 shows no polarity or low polarity.

The reticulated filler GF thus formed
In the pre-molding molding step 2, the pre-molded product 2 is pre-molded. Here, as shown in FIG. 2C, the reticulated filler GF2 is cut into a required size by a cutter C and then heated by a hot press machine 4 equipped with a heating means 3 to have a pre-molded shape. Press molded. In this case, since the primary and secondary binders as the sizing agent are thermoplastic polypropylene (PP), they exhibit plasticity at a low softening point and can be easily deformed into a desired shape. That is, the mesh filler GF2 can be used as a preformable material. Moreover, after this, the cooling means 5 of the hot press machine 4 operates, and the softened reticulated filler GF2 is hardened and formed into a desired shape, here, the shape as the core material of the drag wheeler 1.

The reticulated filler GF2 cured in the shape of a substantially drag wheeler D is the following polydicyclopentadiene (P
DCPD) resin is used in the molding process. Figure 2
As shown in FIG. 3D and FIG. 3, in the molding step, the hardened network filler GF2 is set in the mold 33. The RIM molding machine 6 is attached to the mold 33. Here, the RIM molding machine 6 includes a first raw material tank 7 and a second raw material tank 8, and
In the raw material tank 7, dicyclopentadiene monomer (DC
The liquid A described later containing PD) as a main component is stored, and the liquid B described later containing a dicyclopentadiene monomer as a main component is stored in the second raw material tank 8.

Both tanks are composed of first and second transfer pumps 9 and 10.
The first and second pipes 13 and 14 are extended through the service tank 16 with a pair of temperature adjusting means 15
17 and metering pumps 18 and 19 are provided, and the extending first and second pipes 13 and 14 are connected to the A liquid inlet 22 and the B liquid inlet 23 of the mixing head 21. The mixing head 21 has a hydraulic chamber 2 inside the main body 24.
5, a pressure chamber 27 in which the other end of the plunger 26 faces, and a pair of A liquid inlet 22 and B liquid inlet 23 that are provided opposite to the side wall of the plunger 26.
And a pair of A liquid outlet 28 and B liquid outlet 29. The A liquid outlet 28 and the B liquid outlet 29 are formed so as to extend the return path toward the service tanks 16 and 17.

A hydraulic pressure supply system 30 is connected to the hydraulic chamber 25, and a mold cavity 31 for molding the drag wheeler 1 communicates with the pressurizing chamber 27 via a high pressure pipe (not shown). The plunger 26 switches and slides according to the hydraulic pressure supplied from the hydraulic pressure supply system 30 to the hydraulic chamber 25.
That is, the plunger 26 is formed with a pair of communication grooves 261 on both sides thereof, and when the plunger 26 is at the circulation position P1 (see the chain double-dashed line in FIG. 3), both liquids A and B described later are separately provided. When the plunger 26 is circulated and is at the discharge position P2 (see the solid line in FIG. 3), both liquids A and B can be introduced into the pressure chamber 27, mixed, and supplied to the mold cavity 31. The mold cavity 31 is clamped and opened at appropriate times by a clamping device 32, and a molded product can be molded and discharged.

Drag wheeler D by RIM molding machine 6
In the case of molding, a metathesis catalyst is used in two parts (both liquids A and B) containing a dicyclopentadiene monomer as a main component. Dicyclopentadiene monomer containing a tungsten-containing catalyst of tungsten chloride (Wcl ₆ ) is supplied to the first raw material tank 7 for the liquid A which constitutes one part, and to the second raw material tank 8 for the liquid B which constitutes the other part. Is supplied with a dicyclopentadiene monomer containing an activator of diethylaluminium chloride (Et ₂ AlCl).
Here, a molding process using the RIM molding machine 6 of FIG. 3 will be described below. Here, first, the RIM molding machine 6 is set in a molding standby state. That is, dicyclopentadiene containing tungsten chloride in the first raw material tank 7 is supplied to the service tank 16 through the first pipe 13 together with the driving of the first transfer pump 9.

Tungsten chloride is supplied to the service tank 16 in a fixed amount ratio (here, the ratio of dicyclopentadiene: tungsten chloride is 100: 0.05 on a molar basis) to dicyclopentadiene (DCPD). The temperature is maintained at the set temperature (about 60 °) by the warming means 15 and then premixed. On the other hand, dicyclopentadiene mixed with diethylaluminum chloride in the second raw material tank 8 is supplied to the service tank 17 through the second pipe 14 while driving the second transfer pump 10. Diethylaluminum chloride is supplied to the service tank 17 at a constant quantitative ratio to dicyclopentadiene (DCPD) (here, the ratio of dicyclopentadiene to diethylaluminum chloride is 100: 0.33 on a molar ratio basis), and adjusted. The temperature is maintained at the set temperature (about 60 °) by the warming means 15 and then premixed.

Here, both metering pumps 18, 1
9 is driven, and at the same time, the hydraulic pressure is supplied from the hydraulic pressure supply system 30 to the hydraulic chamber 25 of the mixing head 21. The plunger 26 is held at the circulation position P1, whereby the A liquid circulates through the first pipe 13 and the B liquid circulates through the second pipe 14. Prior to this, the mold cavity 31 that has been prepared for the mold is clamped by the clamping device 32. In this molding standby state, the plunger 26 is held at the circulation position P1 according to the hydraulic pressure supplied from the hydraulic pressure supply system 30. Thereafter, in the molding process, the plunger 26 is switched and held at the discharge position P2 for a predetermined injection time in accordance with the hydraulic pressure supplied from the hydraulic pressure supply system 30, and is returned to the circulation position P1 again to wait for the next injection. To be kept

At the time of injecting this mixed liquid, the A liquid inlet 22 and the B liquid inlet 23 of the mixing head 21 are communicated with the pressurizing chamber 27, and both liquids are pressurized in the pressurizing chamber 27 at high speed at high speed. It is mixed and sent to the mold cavity 31. At this time, the metathesis catalyst A, tungsten chloride, and the metathesis catalyst B, diethylaluminum chloride, are highly chemically active, and when mixed in the mixing head 21 and the mold 4, a metathesis reaction occurs and heat of reaction is generated. ,
The dicyclopentadiene solution undergoes a curing reaction into a dicyclopentadiene polymer.

At this time, in particular, since the reticulated filler GF2 is covered with the polar group maleic acid M, and the polypropylene PP bonded to the nonpolar group in a chain form is covered therewith,
The polar group (maleic acid M) of the sizing agent causes the metathesis polymerization reaction of tungsten chloride (metathesis catalyst A) and diethylaluminum chloride (metathesis catalyst B) because it has no polarity or low polarity around the reticulated filler GF2. The curing reaction takes place without any hindrance, and polydicyclopentadiene (PDCP
A resin in which the D) -based resin is reinforced with glass fibers is molded. After that, the clamping device 32 is opened, and the drag wheeler D, which is a resin component molded in the mold cavity 31, is discharged. In this drag wheeler D, the number of converged single fibers was suppressed to 30 or less, so that the surface irregularities were reduced and the outer shape was relatively smooth. After that, the drag wheeler D is subjected to post-processing, and coating or plating is appropriately performed on the surface of the outer plate D-1 having a low linear expansion coefficient and high dimensional accuracy, and becomes a finished product.

In the above description, the fiber-reinforced resin uses the glass fiber reticulated filler GF2 as the fiber reinforcement, but instead of the glass fiber, carbon fiber, metal fiber, or polyolefin-based or polyester-based filler is used. It is also possible to use an organic fiber having a low polar group such as. Further, those obtained by treating these fiber reinforcements with a surface treatment agent such as a silane coupling material may be used. Furthermore, although polypropylene PP was used as the above-mentioned sizing agent as the non-polar, low-melting point polyolefin, high density polyethylene HDPE or low density polyethylene LDPE may be used instead.

[0024]

As described above, according to the first aspect of the present invention, the fibers into which the polar groups are introduced can be reliably bundled, and the fibers are bundled and kept around the fiber bundle in a nonpolar or low polarity. Thus, the metathesis polymerization of the PDCPD-based resin is not impeded, so that the fiber-reinforced resin containing fiber-reinforced polydicyclopentadiene as a main component can be obtained without causing curing failure. According to the invention of claim 2, since the sizing agent used in the fiber-reinforced resin according to claim 1 is made to be particularly thermoplastic so that the mesh filler can be easily deformed by heating, the mesh filler is preformed. , Can be used. According to a third aspect of the present invention, the fiber bundle used in the fiber-reinforced resin according to the first aspect has a number of single fibers converged to 30 or less, and the fiber bundle does not affect the surface shape of the resin component. Polydicyclopentadiene can be fiber reinforced.

[Brief description of drawings]

FIG. 1 is a side view of a drag wheeler that is a resin component molded from the fiber-reinforced resin of the present invention.

FIG. 2 is a process explanatory view of molding a drag wheeler D using the fiber reinforced resin of the present invention, (a) is a converging process with a primary binder, (b) is a converging process with a secondary binder, and (c) is Pre-forming forming step, (d) is a schematic view of each forming step.

FIG. 3 is an enlarged schematic view of a RIM molding machine used in a molding step of the drag wheeler D in FIG.

FIG. 4 is a diagram for explaining the function of a sizing agent used in the fiber-reinforced resin of the present invention, (a) is a schematic diagram of the binding of maleic acid and polypropylene adhering to glass single fibers, and (b) is a diagram of (a). It is a schematic diagram of a cross-sectional direction.

FIG. 5 is an explanatory diagram showing the structure of a sizing agent used in the fiber-reinforced resin of the present invention by using a chemical formula.

[Explanation of symbols]

 6 RIM Molding Machine 21 Mixing Head 31 Mold Cavity 32 Clamping Device 33 Type D Drag Wheeler PP Polypropylene PPE PP Aqueous Solution GF Glass Fiber Single Fiber GF1 Filamentary Convergent GF2 Net Filler M Maleic Acid PDCPD Polydicyclo Pentadiene

Claims (3)

[Claims] 1. A fiber reinforced resin comprising a fiber bundle bundled with a polar group-introduced polyolefin and a PDCPD resin. 2. The fiber reinforced resin according to claim 1, wherein the sizing agent is thermoplastic. 3. The fiber reinforced resin according to claim 1, wherein the fiber bundle has a number of single fibers converged to 30 or less.