JPH03253308A - Glass fiber reinforced resin prepreg - Google Patents

Abstract

PURPOSE:To realize composite resin formed body having excellent surface appearance, coating properties and workability in addition to preferable physical properties in response to use application by a structure wherein the prepreg concerned is made of unidirectionally arranged glass fibers, reinforcing fibers, which are different from said unidirectionally arranged glass fibers, and matrix resin. CONSTITUTION:The prepreg concerned is made of unidirectionally arranged glass fibers 18, reinforcing fibers 19, which are different from the fibers 18, and matrix resin 13. The preferable monofilament diameter of useful glass fiber 18 is 10-20mum. Said glass fiber is normally obtained in the form of glass roving, which is produced by binding 2000 or less of monofilaments. Further, as the useful reinforcing fiber 19, which is different from the fiber 18, inorganic fiber such as PAN-based or pitch-based carbon fiber, graphite fiber or the like is exampled. As the matrix resin 13, thermosetting resin such as epoxy resin or the like can be used. The fiber reinforced resin prepreg is formed into laminated composite resin formed body by conventional procedure.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a glass fiber reinforced resin prepreg. More specifically, the present invention relates to a fiber-reinforced resin prepreg including a reinforcing layer made of glass fiber and a reinforcing layer made of reinforcing fibers different from the above, a method for producing the same, and a molded article obtained using the same.

[Prior Art] Fiber-reinforced resin prepregs, which are made by impregnating reinforcing fibers arranged in a thin layer in one direction with a matrix resin, are widely used in various technical fields. In particular, it is widely used in the manufacture of golf club shafts, fishing rods, tennis racket frames, etc. because it is lightweight and has high mechanical strength, and has achieved good results.

Conventionally, such fiber-reinforced resin prepregs have usually been formed using one type of reinforcing fiber, but when attempting to obtain a molded product that combines the characteristics of two or more types of reinforcing fibers, each A method has been used in which prepregs containing reinforcing fibers are combined and laminated, or such prepregs are laminated with other reinforcing fibers arranged between them.

[Problem to be solved by the invention]

The present invention aims to provide a fiber-reinforced resin prepreg that includes two reinforcing fiber layers made of two types of reinforcing fibers. Thereby, the present invention makes it possible to easily provide a composite resin molded article that utilizes the composite characteristics of two types of reinforcing fibers. Therefore, according to the fiber-reinforced resin prepreg of the present invention, the resin molded article obtained using the same has not only favorable physical properties corresponding to the intended use, but also
By utilizing the transparency of the surface and the desired colorability, it is possible to impart desirable fashion properties, and it is also possible to obtain a molded article with excellent paintability and processability.

The present invention also provides a method for manufacturing such m-fiber-reinforced resin prepregs, and a composite resin molded article obtained by laminating and molding such fiber-reinforced resin prepregs.

C Means for Solving the Problem 2 The present invention provides the following means to solve the above problem.

1. A fiber-reinforced resin prepreg consisting of glass fibers arranged in one direction, reinforcing fibers of a different type than glass fibers arranged in one direction, and a matrix resin.

2. A fiber-reinforced resin prepreg made of glass fibers arranged in one direction and IJ Fuchs resin, and a fiber-reinforced resin made of reinforcing m-fibers of a different type than glass fibers arranged in one direction and a matrix resin. A method for manufacturing fiber-reinforced resin prepreg, which is characterized by stacking prepreg and heat-pressing to integrate.

3. A large number of glass fiber rows arranged in one direction and a large number of reinforcing fiber rows of a different type than glass fibers arranged in one direction are superimposed, and then a matrix is added from both sides of the superimposed fiber rows. A method for producing fiber-reinforced resin prepreg, which is characterized by stacking resin-coated papers and heat-pressing them to integrate them.

4. Glass fibers arranged in one direction, reinforcing fibers of a different type than glass fibers arranged in one direction, and
A composite resin molded body made by laminating multiple sheets of fiber-reinforced resin prepreg made of IJ Fuchs resin.

Glass fibers useful in the present invention have a monofilament diameter of 1
Preferably it is between 0 and 20 rivers. Such glass strands are generally obtained as a glass roving in which 2,000 or less monofilaments, preferably 1,600 or less monofilaments are bundled.

In addition, as different types of reinforcing fibers useful in the present invention, PAN
and pitch-based carbon fibers and graphite fibers, inorganic fibers such as alumina fibers, silicon carbide fibers, silicon nitride fibers, and boron fibers, metals such as titanium fibers, amorphous fibers, stainless steel fibers, high-strength steel fibers, and aluminum fibers. and organic fibers such as polyarylate fibers, aramid fibers, polyethylene wt fibers.

Metal fibers generally have a strength of 50 to 150 J! m, preferably has a diameter of 70 to 1201 M, and the boron fiber has a diameter of 50 to 1201 M.
It has a diameter of 150□□□. Other inorganic fibers and organic fibers
The fiber usually has a monofilament diameter of 5 to 50-
These fibers are generally used in the form of a strand (fiber bundle), which is a bundle of many fibers.

As the matrix resin, thermosetting resins such as epoxy resins, unsaturated polyester resins, polyurethane resins, diallyl phthalate resins, and phenol resins can be used. If desired, a curing agent may be added to the matrix resin so that the curing temperature is 50 to 200°C, and various functional agents such as a flexibility imparting agent may be added.

Among the above resins, epoxy resins are preferred, and specific examples include glycidyl ether-based epoxy resins, such as bisphenol A1 bisphenol F or bisphenol S-based epoxy resins, novolac-based epoxy resins, and brominated bisphenol A-based epoxy resins; cyclic aliphatic Group epoxy resins; glycidyl ester-based epoxy resins; glycidylamine-based epoxy resins, such as tetraglycidyldiaminodiphenylmethane, triglycidyl-P-
Aminophenols; and heterocyclic epoxy resins may be mentioned, with bisphenol A-based, bisphenol F-based and bisphenol S-based glycidylamine epoxy resins being particularly preferred. These can be used alone or in a mixture of two or more. These epoxy resins also contain amine curing agents such as dicyandiamide (DICY) and diaminodiphenylsulfone (DO5).
and diaminodiphenylmethane (DDM); and acid anhydride systems, such as hexahydrophthalic anhydride (HHPA).
), methylhexahydrophthalic anhydride (MHHPA) and the like can be used, and it is particularly preferable to use an amine type curing agent.

In the present invention, the blending ratio of glass wA fibers, different types of reinforcing fibers, and matrix resin can be adjusted arbitrarily, but generally the weight ratio of glass fibers: different types of reinforcing fibers: matrix resin is (10 to 50):
(10-50): (30-60) is preferred. The thickness of the fiber-reinforced resin prepreg can be adjusted variously depending on the diameter of the glass fibers and different types of reinforcing fibers used;
Preferably it is 50μ.

Next, a specific example of the method for producing a fiber-reinforced resin prepreg of the present invention will be described with reference to the accompanying drawings.

In the first example, pre-prepared prepregs containing glass fibers and prepregs containing reinforcing fibers of different types are stacked on top of each other and are heat-pressed to be integrated. in particular,
For example, as shown in FIG. 1, a glass fiber-reinforced prepreg 1A containing glass fibers and a different kind of fiber-reinforced prepreg IB containing different kinds of reinforcing fibers are held in a release paper 2, and each is placed in an unwinder (unwinding section) 3A. and 3B. The release paper prepregs LA and IB pulled out from the unwinders 3A and 3B are press rolls 4A and 4.
B, where they are overlapped with each other, and then sent from the hot plate 5 to between the second press rolls 6A and 6B. In this way, these prepreg LA,
The IB is integrated and then cooled by a cooling means (not shown), and then wound up on a winder 8 together with the release paper 2 on one side as the prepreg 7 of the present invention. Also, the other release paper 2 is peeled off from the prepreg 7 and wound up on another winder 9, while the side of the prepreg 7 from which this release paper 2 has been peeled off is placed on the unwinder lO before winding. The supplied cover film 11 is attached.

In such a method, press rolls 4A, 4B and/or
Alternatively, the interval between 6A and 6B is set to 0.7 to 0.8 times the total thickness of the glass fiber reinforced prepreg 1 with release paper and the different fiber reinforced prepreg 2 with release paper, and the hot plate 5 is made of prepreg IA .

Preferably, the IB matrix resin is heated to a temperature such that it has a viscosity of 1,000 to 50,000 cp.

According to the above method, a long fiber-reinforced resin prepreg can be continuously and efficiently manufactured.

Naturally, the above-described operation can also be performed using other heat pressing means.

The glass fiber paper-reinforced prepreg and the heterogeneous fiber paper-reinforced prepreg used in the above-mentioned method can be manufactured using a normal prepreg machine comprising a hot roll press device having the same configuration as above. Thus, the construction and operation of such prepreg machines will be well understood by those skilled in the art.

If desired, glass fiber reinforced prepregs and dissimilar fiber reinforced prepregs can also be prepared using a drum winder. For example, as shown in FIG. 2, a resin-coated paper 14 having a release paper coated with a matrix resin is wrapped around the circumferential surface of a drum 12 having a predetermined diameter. Next, the fibers 16 from the bobbin 15 are transferred to the drum 12 from the traverse device 1.
7 and is wound on the resin-coated paper 14 wound around the peripheral surface of the drum 12 at a desired pitch. Next, the resin-coated paper 14 is wrapped again on top of the resin-coated paper 14, and a prepreg is obtained by heat-pressing this using an appropriate heat-pressing means (not shown). This method can be particularly advantageously used to produce prepregs containing reinforcing fibers with large diameters such as ordinary metal fibers and boron fibers.

In the second example of the manufacturing method of the present invention, a thin layer consisting of a large number of glass fiber rows and a thin layer consisting of a large number of different types of reinforcing fiber rows are superimposed, and the layer of the superimposed fiber rows is Layer matrix resin coated paper on both sides and heat press to integrate. Specifically, for example, the third
As shown in the figure, glass fibers 18 and reinforcing fibers 19 of different types are fed between press rolls 4A and 4B while being opened by opening means each consisting of a series of opening bars 20. On the other hand, first and second resin-coated papers 14 made by coating release paper 2 with IJ Lux resin 13 are wound around unwinders 3A and 3B, respectively, and the fibers 18 and 19 are coated on both sides thereof. These fiber layers are then fed between press rolls 4A and 4B with the layers sandwiched between them. Here, they are superimposed and then sent from the hot plate 5 to between the second press rolls 6A, 6B. In this process, the fibers 18 and 19 are embedded and impregnated into the matrix 13 of the first and second resin-coated papers 14,
be integrated. Then, after cooling with a cooling means (not shown), as in the case of FIG. It is also wound onto the winder 8.

In this case as well, press rolls 4A, 4B and/or
Alternatively, the interval between 6A and 6B is set to 0.7 to 0.8 times the total thickness of the resin-coated paper and the fiber layer, and the hot plate 5 has a matrix resin of 1000
Preferably, it is heated to a temperature that results in a viscosity of ˜50,000 cp.

The fiber-reinforced resin prepreg of the present invention obtained as described above is molded into a laminated composite resin molded article according to a conventional method. For example, a molded article can be obtained by winding a plurality of layers on a mandrel so as to overlap or by stacking a plurality of layers in a desired shape, and heat-treating the matrix resin to completely cure the matrix resin. As shown in FIG.
It has a cross section in which the layers and layers are alternately and orderly laminated in the IJ Fuchs resin 13. Therefore, such a molded article has desirable characteristics that are a combination of the characteristics of each fiber. In addition, by having a glass fiber layer as the outermost layer, a transparent surface appearance can be given.
If desired, colored glass fibers can also be used to provide a desirable colored appearance.

Furthermore, by combining such reinforcing fibers, a molded article with excellent paintability and processability can be obtained.

〔Example〕

The present invention will be further explained below with reference to Examples.

Using the method shown in FIG. 1 or the method shown in FIG. 3, prepregs as shown in Table 1 below were manufactured. The raw materials used, manufacturing conditions, and product properties are summarized in Table 1.

Table 1 1 Technora Cured Epoxy Figure 3 110℃
2 Pectran Same as above Figure 1 110℃3
Titanium 1 Same as above 110℃ 5 sUs” Same as above 6 Boron” Same as above 7 CF 70 Ton Same as above Figure 3 8
CF 24 Ton Same as above Note: Cured epoxy resin is Epicoat 828:Ecoat 1
001:DJCY:DCMU=30 Near 0:
4.2: A composition of 4.2 (weight ratio) cured at 130°C.

110℃ 110℃ 110℃ 110℃ Table 1 (continued) Weight ratio (%) Prepreg thickness (al) 1 3
2 32 36 63 852
32 32 36 63 853
23 38 39 63 1(](
1416453963145 516453963145 626363863100 73232366369 83236366375 In the above, the glass roving is monofila 1:/
) A diameter of 13 m and a convergence number of 800 pieces (manufactured by Central Glass, 290Tex) were used. Further, details of the reinforcing fibers are as follows.

Technora made by Music University, T241J, 1500de Pectran made by Kuraray, HD type, 1500de titanium 0
Kobe Steel, KS40.100 mark SUS" Boron 0 CF 70 Ton CF 24 Ton Nippon Seiren, NAS304.100 mark AVCO, 100 square Tonen, FORCA FT700 (3K) 450Te
x Made by Mitsubishi Rayon, TR30 (12K) 830Tex
In addition, the fibers marked with an asterisk (*) are made of titanium, high-strength steel, and SUS using the method shown in Figure 2.
0.33mm for , 0.20m for boron
m is a prepreg.

〔Effect of the invention〕

As explained above, the fiber-reinforced prepreg of the present invention can provide a composite resin molded article that has favorable physical properties corresponding to the intended use, as well as a surface appearance with excellent fashionability and excellent paintability and processability. .

[Brief explanation of drawings]

FIG. 1 is a schematic diagram illustrating an embodiment of the prepreg manufacturing method of the present invention. FIG. 2 is a schematic diagram illustrating an example of a method for producing a starting prepreg used in the method of FIG. 1. FIG. 3 is a schematic diagram illustrating another example of the prepreg manufacturing method of the present invention. FIG. 4 is a diagram schematically showing an example of a cross section of a composite resin molded article of the present invention. IA, IB...Prepreg, 4A, 4B, 6A, 6B...Press roller, 5...
hot plate, 13...matrix resin, 14
...Resin coated paper, 18...Glass fiber, 19
...Different types of reinforcing fibers. jl:5 Figure

Claims (1)

[Claims] 1. A fiber-reinforced resin prepreg comprising glass fibers arranged in one direction, reinforcing fibers of a different type than glass fibers arranged in one direction, and a matrix resin. 2. Layering a fiber-reinforced resin prepreg made of glass fibers and matrix resin arranged in one direction and a fiber-reinforced resin prepreg made of reinforcing fibers different from glass fibers and matrix resin arranged in one direction. Combine,
A method for producing fiber-reinforced resin prepreg characterized by heat-pressing and integrating. 3. A large number of glass fiber rows arranged in one direction and a large number of reinforcing fiber rows of a different type than glass fibers arranged in one direction are superimposed, and then a matrix is added from both sides of the superimposed fiber rows. A method for producing fiber-reinforced resin prepreg, which is characterized by stacking resin-coated papers and heat-pressing them to integrate them. 4. Composite resin molding made by laminating multiple fiber-reinforced resin prepregs made of glass fibers arranged in one direction, reinforcing fibers of a different type than glass fibers arranged in one direction, and matrix resin. body.