JPH0818346B2 - Fiber-reinforced resin product and manufacturing method thereof - Google Patents

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 product having a fiber formed by a filament winding method (hereinafter abbreviated as FW method) as a reinforcing fiber and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a continuous fiber is used as a fiber reinforcing material, and a continuous fiber-reinforced resin obtained by molding a matrix resin by a reaction injection molding method uses a blade (braid), cloth or tape as the fiber reinforcing material. There is. When an attempt is made to obtain a fiber reinforced material in which a plurality of types of fibers are mixed with this type of fiber reinforced resin, a method is employed in which blades of each fiber type are separately prepared and laminated. That is, as shown in FIG. 4, the mandrel 1 has a fiber type A
After wrapping the blade 2 of No. 1, the blade 3 of another fiber type B is wound, and the fiber reinforcing material formed by laminating the different blades 2 and 3 is placed in the cavity of the mold, and the RIM nylon is placed in the cavity. Alternatively, cyclopentadiene is injected to mold the fiber reinforced resin by the reaction injection molding method.

[0003]

When the above-mentioned blades are laminated to form a fiber reinforced material, the rigidity, elastic modulus, impact resistance, weight, wall thickness, vibration absorption and other functions of the product can be obtained. If you try to design,
There is a problem in that the degree of freedom in design is reduced because it can be controlled only by the basis weight of the blade layer (fiber amount per unit length) or the number of laminated fibers of each type.

When different kinds of blades are laminated from the inner layer to the outer layer and a plurality of kinds of fibers are mixed, as shown in FIG. 5, for example, the fibers arranged on the outer layer side are emphasized in terms of smoothness and strength. When the small fibers 3 are arranged, the strength on the outer layer side becomes weak. That is, uniform strength cannot be given to the entire wall thickness from the inner layer to the outer layer, and a difference in strength occurs in the thickness direction. Therefore, for example, when it is desired to impart both smoothness and high strength to the surface side of the outer layer, it becomes difficult to satisfy the demand.

The present invention is intended to solve the problem that occurs when a plurality of types of fibers are laminated by laminating blades as described above, and the mixing ratio of different types of fibers can be arbitrarily controlled, and the wall thickness from the inner layer to the outer layer can be controlled. When a uniform function is required for the whole, the purpose is to be able to meet the demand.

[0006]

In order to achieve the above object, the present invention is characterized in that a fiber preform is provided by the FW method, and a continuous fiber reinforcement is wound around a core attached to a mandrel by the FW method. By sequentially stacking from the inner layer to the outer layer, it is possible to evenly distribute any fiber in any amount in any position, and arrange multiple types of fibers evenly throughout the wall thickness from the inner layer to the outer layer. It is characterized by doing.

That is, according to the present invention, in claim 1, a matrix comprising a fiber preform formed by winding a plurality of kinds of fibers by a filament winding method, and a resin impregnated into the fiber preform by a reaction injection molding method. The fiber preform is made of a resin, and the plurality of types of fibers are evenly distributed in the same layer, and a layer formed of the plurality of types of fibers is provided from the inner layer side to the outer layer side to distribute the entire thickness. We provide fiber-reinforced resin products that are characterized by

Further, according to the present invention, in claim 2, a plurality of kinds of fibers are mixed around the outer peripheral surface of the core by a filament winding method to uniformly wind a plurality of kinds of fibers in the same layer, and further, From the inner layer side to the outer layer side, a plurality of types of fibers are evenly wound to form a fiber preform, and the fiber preform is set in the cavity of the mold, and the resin is reactively injected. The present invention provides a method for producing a fiber-reinforced resin product, characterized in that the fiber preform is impregnated by molding to obtain a molded product having a desired shape.

The FW of a plurality of types of fibers may be fed from a roving of a plurality of fibers at the same time, fed through one eye and twisted to be supplied and wound around a core. Alternatively, the fibers of one roving may be wound instead of the roving of another fiber after being wound at the same time. At that time, a winding angle may be selected, and a fiber wound later between the fibers wound before is wound. It is also possible to wind a plurality of kinds of fibers in the same layer.
Further, a commingle yarn in which a plurality of types of fibers are mixed and woven in one roving and a plurality of types of the commingle yarns are used can easily mix various types of fibers having various functions.

The fibers wound around the core by the FW method are preferably dipped in water-soluble nylon, alcohol-soluble nylon, or water or an alcohol solution of water and alcohol-soluble nylon, and then wound around the core. By immersing in this soluble nylon solution,
When the fibers are wound around the core, they can function as a sizing agent and can be prevented from becoming disjointed.

As described above, the fiber preform obtained by winding the fiber around the core by the FW method is set in the cavity of the mold and impregnated with the matrix resin, and the resin is injected. Since the RIM method of polymerizing in a mold with a low-viscosity monomer is used, it is possible to improve the permeability of the resin into the fiber.

The continuous fibers used as reinforcing fibers by the FW method are carbon fibers, glass fibers, aramid fibers,
Silicon carbide fibers, steel fibers, amorphous metal fibers, organic fibers and / or mixtures thereof are preferably used.

As the resin used in the above reaction injection molding method or resin transfer molding, RIM nylon, cyclopentadiene, epoxy, urethane or polyester is used. For example, in the case of RIM nylon, it is molded by a monomer casting method in which molten lactams containing a polymerization catalyst and a polymerization initiator are injected into a mold, and the polyamide is polymerized by heating.

The ω-lactams which are the above-mentioned monomers include α-pyrrolidone, α-piperidone, ω-enanthlactam, ε-caprolactam, ω-caprylolactam,
ω-pelargonolactam, ω-decanolactam, ω-undecanolactam, ω-laurolactam, c-alkyl-substituted-ω-lactams thereof, and mixtures of two or more kinds of these ω-lactams. Also,
The ω-lactam can optionally contain an improving component (soft component). The soft component is a compound having a functional group that reacts with the initiator used in the molecule and has a low Tg, and a polyether having a normal functional group, liquid polybutadiene, or the like is used.

Commercially available raw materials used as the above-mentioned ω-lactams include UBE nylon (U manufactured by Ube Industries, Ltd.).
X-21) etc. It is composed of an A component consisting of an alkali catalyst and caprolactam, a prepolymer containing a soft component and a B component consisting of caprolactam.

As the above polymerization catalyst, sodium hydride is preferable, but other known ω-lactam polymerization catalysts such as sodium, potassium and lithium hydride can be used. The amount added is 0 for ω-lactam.
The range of 1-0.5 mol% is preferable.

As the polymerization initiator (activator), N-
Acetyl-ε-caprolactam is used, but other triallyl isocyanurates, N-substituted ethyleneimine derivatives, 1.1′-carbonylbisaziridine, oxazoline derivatives, 2- (N-phenylbenzimidoyl) acetanilide, 2- Compounds such as (N-phenylbenzimidoyl) acetanilide, 2-N-morpholino-cyclohexene-1.3-dicarboxanilide, and known isocyanates and carbodiimides can be used. The amount of the polymerization initiator added is preferably within the range of 0.05 to 1.0 mol% with respect to the amount of ω-lactam.

When a cyclopentadiene resin is used as the matrix resin, dicyclopentadiene may be used as the polymerizable monomer for the cyclopentadiene resin.
Dihydrodicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, cyclopentadiene-
A methylcyclopentadiene co-duplex or the like is used.

As the polymerization catalyst for the cyclopentadiene resin, halides such as tungsten, molybdenum and tantalum, oxyhalides, oxides and organic ammonium salts are preferably used. As the polymerization initiator, organometallic compounds centered on alkylated metals of metals of groups I to III of the periodic table, oxygen-containing compounds such as alcohols and phenols are preferably used.

Furthermore, since the polymerization reaction of the solution containing the above-mentioned polymerization catalyst and activator (polymerization initiator) is initiated very quickly, curing may occur before the solution sufficiently flows into the molding die. The monoether and / or monoester of a glycol compound selected from alkylene glycol or polyalkylene glycol is preferably used as the activity modifier. When injecting into the mold, the mold temperature is usually set in the range of 40 to 130 ° C.
It is preferable to carry out the polymerization reaction for 5 minutes.

In injection molding into the above mold, the mold temperature is usually in the range of 40 to 130 ° C. and the polymerization reaction is usually carried out for 1 to 5 minutes.

The above-mentioned core may be in any form capable of winding fibers, and may be a solid body made of plate material, metal material, rubber, sponge, plastic or the like, or a flexible tube for covering a mandrel. The tube is preferably made of nylon, cellophane, rubber, polyester, polyetherketone or the like.

[0023]

When the fiber preform is formed by the FW method as described above, it becomes possible to easily control the mixing ratio of fibers, the distribution of fibers, etc., and the rigidity, elastic modulus, impact resistance and vibration of the molded product can be controlled. Absorption and other functions can be freely designed by mixing different kinds of fibers.

Furthermore, the entire thickness of the molded product from the inner layer to the outer layer can be uniformly reinforced with fibers, and the occurrence of partial strength variations can be prevented. Further, the outermost fiber layer, which cannot be achieved by the conventional lamination of blades, can be composed of fibers for imparting smoothness and fibers for imparting strength.

[0025]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows a continuous fiber reinforced resin product 1 according to the present invention.
0, the fiber reinforcement of the product 10 is composed of carbon fibers 11 and glass fibers 12, and the matrix resin is composed of nylon molded by reaction injection molding. The carbon fiber 11 and the glass fiber 12 are composed of a fiber preform molded in advance by the FW method, and are uniformly mixed over the entire wall thickness from the inner layer side X to the outer layer side Y. Therefore, the product 10 is It has the same strength throughout its thickness.

The manufacturing method of the product 10 will be described in detail below. First, a fiber preform is formed by the FW method. That is, as shown in FIG. 2, a flexible tube 16 (a nylon tube having a width of 24 mm in this embodiment) as a core is passed through a mandrel 15 (a mandrel made of SUS having a diameter of 1.5 mm in this embodiment), and The carbon fiber 11 and the glass fiber 12 are sent out from the carbon fiber roving 17 (HTA-7-12000 manufactured by Toho Rayon Co., Ltd.) and the glass fiber roving 18 (T-30 manufactured by Nitto Boseki Co., Ltd.) to perform FW.

The FW method is the same as the well-known FW method, in which the mandrel 15 is rotated and linearly reciprocated in the axial direction by a driving means (not shown). The fiber winding side may be rotated and linearly reciprocally operated without forcibly driving the mandrel side. The carbon fiber 11 and the glass fiber 12 pulled out from the carbon fiber roving 17 and the glass fiber roving 18 are dipped in a container (not shown) that stores an alcohol solution of alcohol-soluble nylon, and then one eye 20. The two fibers into one, and while twisting the fibers, wind the fibers through the tension roll 21 around the outer peripheral surface of the flexible tube 16 from one end to the other end, and further reciprocate to wind only the required layers. Go.

By performing FW as described above, the carbon fiber 11 and the glass fiber are uniformly mixed over the entire axial direction of the mandrel and over the entire thickness direction from the inner layer side to the outer layer side. Becomes

After the predetermined winding of the carbon fiber 11 and the glass fiber 12 is completed to produce a fiber preform (layup), the layup together with the flexible tube 2 is pulled out from the mandrel 1. Then, as shown in FIG. 3, along the shape (U shape) of the cavity 26 of the mold 25,
The fiber preform is set in the cavity 26.

Then, the die 25 is clamped. The mold temperature is 150 ℃ while depressurizing the inside of the cavity with a vacuum pump.
While raising the temperature to 1, and applying internal pressure to the inside of the flexible tube 16, RIM nylon UX-21 manufactured by Ube Industries, Ltd. is injected under pressure and molded by reaction injection molding. Specifically, the required amount of RIM nylon was divided into two containers, a polymerization catalyst was added to one of them, and a polymerization initiator and an activity modifier were added to the other to prepare two stable reaction solutions. ing. The two types of reaction solutions are instantaneously mixed by the kneading head of the two-component reaction injection molding apparatus, and the mixed solution is immediately injected into the cavity of the mold. The injected mixed liquid causes a reaction while impregnating the lay-up placed in the cavity, and a polymerization reaction is performed for 1 to 5 minutes to cure the mixed liquid. After curing, the mold is opened and the molded product is taken out.

By the steps described above, a U-shaped pipe made of fiber reinforced resin, which is reinforced by FW of carbon fiber and glass fiber shown in FIG. 1 and whose matrix resin is nylon, can be obtained.

In the above embodiment, the carbon fiber and the glass fiber are drawn out from the carbon fiber roving and the glass fiber roving, respectively. At this time, the carbon fiber roving is further spun and two carbon fibers 1 and 1 are used. It is also possible to make the winding amount of the carbon fiber twice as much as that of the glass fiber by collectively combining the glass fibers of the book with the eye 20 and performing FW. Further, it is possible to mix three or more kinds of fibers by simultaneously drawing out by using other fiber roving other than carbon fiber roving and glass fiber roving. Further, as the fiber roving, a fiber roving in which a congruent yarn in which a plurality of fibers are mixed and woven is wound may be used, and a plurality of types of fibers may be extracted from one fiber roving for FW.

In the above embodiment, a plurality of types of fibers are simultaneously drawn out from the roving for FW. However, after one fiber is drawn out from one roving and subjected to FW,
Different types of fibers may be pulled out from other rovings for FW. At that time, when it is desired to distribute a plurality of types of fibers in the same layer, the fibers may be wound so that the fibers to be FW later are positioned between the fibers to FW before.

[0034]

As is apparent from the above description, according to the present invention, since the fiber reinforced material is molded by the FW method, the product has functions such as rigidity, elastic modulus, impact resistance and vibration absorption, and When designing weight, wall thickness, etc., the mixing ratio of different types of fibers can be controlled by the basis weight of each type of fiber at the roving level or the number of rovings of each fiber. Become.

Further, fibers of all kinds can be uniformly distributed over the entire thickness of the product, and a product can be obtained in which a weak portion in strength does not occur. On the contrary, it is possible to easily meet the requirement when the strength needs to be partially increased.

Furthermore, since the fiber reinforcement laid by FW is previously placed in the cavity of the mold and resin-molded, it is possible to select the type of matrix resin. On the other hand, RIM nylon, cyclopentadiene, epoxy, urethane, polyester, or the like, which has good penetrability and excellent properties such as impact resistance, vibration damping property, and heat resistance, can be used as the matrix resin.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a fiber reinforced resin product according to the present invention.

FIG. 2 is a schematic view showing an FW method according to the present invention.

FIG. 3 is a schematic diagram showing a state in which the fiber reinforcement molded by the FW method is placed in a mold.

FIG. 4 is a schematic view showing a state in which a fiber reinforcing material including a conventional blade is wound around a mandrel.

FIG. 5 is a cross-sectional view of a fiber-reinforced resin product showing conventional problems.

[Explanation of symbols]

 10 Fiber Reinforced Resin Product 11 Carbon Fiber 12 Glass Fiber 15 Mandrel 16 Core (Tube) 17 Carbon Fiber Roving 18 Glass Fiber Roving 20 Eyes

Claims (2)

[Claims] 1. A fiber preform comprising a plurality of kinds of fibers wound by a filament winding method and a matrix resin made of a resin impregnated in the fiber preform by a reaction injection molding method. The body is characterized in that the plurality of types of fibers are evenly distributed in the same layer, and that a layer composed of the plurality of types of fibers is provided from the inner layer side to the outer layer side and distributed over the entire wall thickness. Resin products. 2. The core is wound around the outer peripheral surface by a filament winding method while mixing a plurality of types of fibers to uniformly wind the plurality of types of fibers in the same layer, and further, from the inner layer side to the outer layer side. A plurality of types of fibers are evenly wound over the entire thickness to form a fiber preform, the fiber preform is set in a cavity of a mold, and a resin is impregnated into the fiber preform by reaction injection molding. A method for producing a fiber-reinforced resin product, characterized in that a molded product having a desired shape is obtained.