JPH0780182B2 - Glass / Continuous Strand Mat - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a fiber reinforced plastic.
The present invention relates to a glass continuous strand mat used as a reinforcing material for (FRP), and the glass continuous strand mat is preferably used as a fiber reinforcing material for reaction injection molding.

[0002]

2. Description of the Related Art A glass / continuous strand mat is made of continuous glass fibers which are mainly spirally or non-directionally stacked and formed into a mat with a binder. By using press molding, the above glass / continuous strand mat is capable of deep drawing without preform (preforming), and is placed in a mold after preforming, It is also possible to inject a resin into and use it as a FRP fiber reinforcing material.

As the above-mentioned preformable glass continuous strand mat, there is provided one using a thermoplastic polyester as a binder (hereinafter referred to as a binder). In the glass / continuous strand mat, continuous glass fibers are laid on a flat plate in a mat shape, and then thermoplastic polyester is attached as a binder. When preforming using the glass / continuous strand mat, the temperature is raised to above the melting point of the polyester, the shape is formed using a required mold, and then the mold is cooled to below the melting point of the polyester and released from the mold. After that, the shape shaped as above is maintained.

As described above, as a method of obtaining a FRP molded product by injecting a resin with the fiber reinforcement placed in the mold, an unreacted raw material liquid such as nylon, cyclopentadiene, epoxy, urethane is injected. There is provided a reaction injection molding method in which a fiber reinforcement is impregnated with the above raw material liquid in a mold to cause a reaction and solidify.

Further, the following methods (a) to (c) are provided as methods for producing FRP molded articles other than the above reaction injection molding method. (a) A method in which a thermoplastic resin reinforced by mixing short fiber reinforcement is injected into a mold to obtain a molded article; (b) a prepreg obtained by impregnating continuous fibers with a thermosetting resin is heated and pressed. A method for obtaining a molded article; (c) A method for obtaining a molded article by mixing and weaving a fiber reinforced material and a thermoplastic resin composed of a matrix resin, and heating and pressing.

[0006]

When the method for producing an FRP molded article by the above reaction injection molding method is used, the above (a) to
The other production methods listed in (c) have a problem that polymerization failure is likely to occur during the reaction, which is not a problem. That is, in the above other manufacturing method, when the thermoplastic resin of (a) and (c) is used, the molding of the resin has already been completed, so that the polymerization failure that occurs during the reaction that is a problem in reaction injection molding is a problem. I won't. Further, even when the thermosetting resin (b) is used, there is no concern that the fiber reinforced material may cause curing failure of the resin.

On the other hand, in the case of using the reaction injection molding method, when a polymerization inhibitor compound is produced during the reaction, the polymerization inhibitor compound deprives the activity of the polymerization catalyst mixed in the unreacted raw material liquid, resulting in poor polymerization. cause. For example, in the case of reaction injection molding of RIM nylon or cyclopentadiene, one of the above-mentioned polymerization inhibiting compounds is a compound having poor alkali resistance. These compounds are decomposed to generate active hydrogen, and the active hydrogen is a polymerization catalyst. Will be a factor to deprive the activity of.

When the preformed glass / continuous strand mat is placed in a mold to produce an FRP molded product by a reaction injection molding method, the heat used as a binder for the glass / continuous strand mat is used. The plastic polyester corresponds to the above-mentioned compound having poor alkali resistance, and is decomposed during reaction to generate active hydrogen, which causes a problem of poor polymerization as described above. Therefore, there has been a drawback that the FRP molded article cannot be manufactured by reaction injection molding using the conventionally provided preformed glass continuous strand mat as a fiber reinforced material.

The present invention is based on the above-mentioned preformed glass.
It aims to solve the problem of producing FRP molded products by reaction injection molding using continuous strand mat as a fiber reinforced material, and is used for reaction injection molding, especially when using RIM nylon or cyclopentadiene as matrix resin. It is intended to provide a preformable glass continuous strand mat that is possible.

[0010]

SUMMARY OF THE INVENTION The present invention uses soluble nylon that does not interfere with polymerization as the binder, instead of using thermoplastic polyester that causes polymerization inhibition to RIM nylon, and thus the glass continuous It is possible to manufacture an FRP molded product by a reaction injection molding method using a fiber reinforced material in which asstrand mat is preformed.

More specifically, the present invention relates to a glass continuous strand mat in which continuous glass fibers are mainly spirally or non-directionally stacked to form a mat with a binder, and the binder is soluble in water or alcohol. As a nylon (hereinafter referred to as soluble nylon),
The present invention provides a glass / continuous strand mat, characterized in that the glass / continuous strand mat is preformed into a required shape to obtain a fiber reinforced material used for reaction injection molding. Nylon or cyclopentadiene is preferably used as the resin obtained by the reaction injection molding. Further, the soluble nylon is preferably alcohol-soluble nylon, and
The amount of the soluble nylon attached is preferably 0.5 to 10.0%.

The glass continuous strand mat using the above-mentioned soluble nylon as a binder is a state in which alcohol-soluble nylon is dissolved in alcohol such as methanol, and glass fibers continuous in the solution are spirally or non-directionally stacked. It is also possible to manufacture by dipping the glass mat of No. 1 or spreading the solution in the form of a mist on a glass mat spread in a flat plate and then drying.
It is also possible to lay the continuous glass fibers in a mat shape on a flat plate, sprinkle with soluble nylon in the form of powder, then heat and melt to adhere to the glass fibers, and cool to manufacture.

The amount of the soluble nylon deposited is optimally 0.5 to 10% of the weight of the mat. If it is less than 0.5%, the preformability may be insufficient, and if it is more than 10%, the strength of the molded product may be reduced. As the soluble nylon, AQ nylon manufactured by Toray, Resin, manufactured by Teikoku Chemical Industry Co., Ltd. and the like are preferably used. These are polyamides modified by a method such as introducing a methoxymethyl group into the nitrogen of an amide group existing in nylon and having a function of dissolving in water or alcohol. These are supplied in the form of pellets, powders, solutions and the like, and a suitable form can be selected depending on the method of adhering to the continuous strado mat. The melting point of these soluble nylons is 8
It is possible to select in the range of 0 to 185 ° C., and it is possible to select the optimum melting point grade according to the preforming method.

When the matrix resin molded by the above reaction injection molding method is nylon, that is, when RIM nylon is used, molten lactams containing a polymerization catalyst and a polymerization initiator are injected into a mold, and this is used. It is molded by a monomer casting method in which polyamide is polymerized by heating.

The ω-lactams which are the above-mentioned monomers include α-pyrrolidone, α-piperidone, ω-enanthlactam, ε-caprolactam, ω-caprylactam,
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 are 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-mentioned polymerization catalyst, sodium hydride is preferable, but other known .omega.-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 isocyanurate, N-substituted ethyleneimine derivative, 1.1′-carbonylbisaziridine, oxazoline derivative, 2- (N-phenylbenzimidoyl) acetanilide, 2- N-morpholino-cyclohexene-
A compound such as 1.3-dicarboxanilide or a known isocyanate or carbodiimide 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, as well as dicyclopentadiene, can 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, organic ammonium salts and the like 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.

[0022]

As described above, since the glass continuous strand mat according to the present invention uses soluble nylon as a binder, a preformed glass continuous strand mat is placed in the mold. Then
When RIM nylon, cyclopentadiene, and the like are injected into the mold to react and solidify while impregnating the preform of the glass continuous strand mat, the binder made of soluble nylon does not hinder the polymerization. Therefore, it is possible to manufacture an FRP molded product having a matrix of nylon or cyclopentadiene, which could not be molded by using the glass / continuous strand mat in the related art.

[0023]

EXAMPLES Examples of the present invention will be described below. Glass continuous strand mat 1 according to the present invention
As shown in FIG. 1, glass continuous fibers 2 are spirally or non-directionally stacked to form a mat shape, and soluble nylon 3 is used as a binder and held in the mat shape.

In the method for producing the above-mentioned glass / continuous strand mat 1, a continuous glass fiber is piled up in a spiral shape to form a mat, but a binder is not attached (a prototype manufactured by Asahi Fiber Glass Co., Ltd.). , Sandwiching this in a wire mesh, for example, soluble nylon (manufactured by Toray)
It is immersed in a solution of AQ nylon K-80: melting point 142 ° C.), vibration is applied using ultrasonic waves in the immersed state, and then pulled out of the solution and dried.

In the above embodiment, the soluble nylon is
% Methanol solution, soak in this solution,
In the immersed state, ultrasonic vibration is applied for 5 minutes. Further, after pulling out from the solution, it is left overnight to dry the solvent methanol. Further, the amount of the alcohol-soluble nylon attached is set to 2.4% in this embodiment. (Measured by thermogravimetric analysis)

The continuous strado mat according to the present invention is not limited to the above-mentioned manufacturing method, and a continuous nylon stroma with no binder is spread on a Teflon sheet and powder of soluble nylon K80 (particle size 180
(~ 350 μm) evenly, then cover this continuous strado mat with another layer of Teflon sheet,
It can also be prepared by heating to 190 ° C. to melt the powder, attaching it to glass, and then cooling. In the modification, the amount of soluble nylon powder is 3% of the glass weight.

Next, a method for producing an FRP molded article by a reaction injection molding method using a glass continuous strand mat using soluble nylon as the binder according to the present invention will be described.

First, as shown in FIG. 2, a preformed glass continuous strand mat 1'which is held in a plate shape is placed in the cavity 15 of the molds 12,13. The mold surface of the cavity 15 is the same as the mold surface of the upper and lower molds for the preform. Then, the molds 12 and 13 are heated to 150 ° C. while the pressure inside the cavity 15 is reduced by a vacuum pump (not shown).

In the cavity 15 of the molds 12 and 13,
RIM nylon melted at 90 ° C (UX-2 made by Ube Industries)
1) Inject 20. Specifically, the required amount of RIM nylon is divided into two containers and the polymerization catalyst is placed in one of them.
On the other hand, a polymerization initiator and an activity modifier are added to prepare two kinds of stable reaction solutions. The two types of reaction solutions are instantaneously mixed by a mixing head of a two-liquid reaction injection molding apparatus, and the mixed solution is immediately injected into the cavity of the mold heated to 150 ° C.

The mixed solution injected into the mold is the cavity 1
In 5 the reaction occurs while impregnating the preformed glass continuous strand mat. 1
After the polymerization reaction is performed for 5 minutes to complete the solidification of the mixed liquid, the mold is opened and the molded FRP is taken out.

At the time of the above reaction injection molding, since soluble nylon is used as the binder of the glass continuous strand mat 1, R is used as the matrix resin.
Polymerization inhibition does not occur when using IM nylon.

[0032]

Comparative Example A glass continuous strand mat (M8608-X5J manufactured by Asahi Fiber Glass Co., Ltd.) containing a thermoplastic polyester as a binder was molded by reaction injection molding using RIM nylon in the same manner as in the example. When the above glass / continuous strand mat was used, RIM nylon was not polymerized, a polymerized molded product was not obtained, and the molded product was in a non-polymerized state.

The performances of the non-polymerized molded article of the above comparative example and the molded article according to the present example were compared using the three-point bending test method shown in JIS K7055. That is, the plate-shaped test piece molded by the method described in the above-mentioned example and the plate-shaped test piece formed by the non-polymerized molding of the above-mentioned comparative example were provided. These plate-shaped test pieces are 10 mm wide x 150 mm long x
It has a thickness of 4 mm. A three-point bending test was performed on the test piece with a sample support length of 80 mm to measure the bending elastic modulus and bending strength.

The results are shown in Table 1 below.
The test pieces according to the examples of the present invention were superior to the comparative examples in flexural modulus and flexural strength.

[0035]

[Table 1]Flexural modulus kgf / mm ² Bending strength kgf / mm ²   Example 730 21.2 Comparative example 220 6.5

Although the above-described embodiment of the present invention has a plate shape, the present invention is not limited to the plate shape, and other curved surface shapes, box shapes, and other shapes are the same as those of the known preformable CSM. By using the preformability of the glass / continuous strand mat according to the present invention, a preform can be formed and set in a mold to obtain a molded product.

[0037]

As is apparent from the above description, according to the present invention, a soluble nylon that does not cause polymerization inhibition when used in reaction injection molding is used as a binder for glass continuous strand mats. Therefore, there is an advantage that an FRP molded product can be molded using RIM nylon or cyclopentadiene as a matrix resin by using a preformed glass continuous strand mat.

When RIM nylon or cyclopentadiene is used as the matrix resin, an FRP product excellent in vibration absorption and impact resistance can be obtained.

[Brief description of drawings]

1 is a cross-sectional view of a glass continuous strand mat according to the present invention.

FIG. 2 is a cross-sectional view showing a state of reaction injection molding using a preformed glass continuous strand mat.

[Explanation of symbols]

 1 Glass / Continuous Strand Mat 2 Glass Fiber 3 Binder 12,13 Mold 15 Cavity

Claims (3)

[Claims] 1. A glass continuous strand mat in which continuous glass fibers are stacked and formed into a mat with a binder, wherein the binder is soluble nylon and the glass continuous strand mat is preformed into a required shape. A glass continuous strand mat characterized by being used as a fiber reinforced material for reaction injection molding. 2. The glass continuous strand mat according to claim 1, wherein the resin obtained by the reaction injection molding is nylon or cyclopentadiene. 3. The glass according to claim 1, wherein the soluble nylon comprises nylon soluble in water or alcohol, and the amount of the alcohol-soluble nylon deposited is 0.5% to 10.0%.・ Continuous Strand Mat.