JP2717330B2 - Epoxy resin composition for high tension material made of FRP for pultrusion molding - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an FR as a structural member.
The present invention relates to an epoxy resin composition for a high tensile strength material made of FRP for pultrusion used for a high tensile strength material made of P.

[0002]

2. Description of the Related Art Pultruded glass fiber reinforced plastic rods, which have a high tensile strength in the longitudinal direction, are widely used as structural industrial materials for tension members of communication cables. I have.

In addition, application to concrete reinforcing bars is being developed by utilizing features such as corrosion resistance, high strength, light weight, and non-magnetism.

[0004] Among various reinforcing fibers, glass fibers are most often used because of their functions and economy.

However, when viewed as a composite material, despite the glass fiber having a tensile elongation at break of 4 to 4.8%, the tensile elongation at break of an epoxy resin cured material generally used widely as a matrix is 1.5 to 3%. %, When considering the use as a high-tensile material, when the material is stretched by applying a high tensile load, the matrix is first broken and stress concentration occurs in the glass fibers in the vicinity, There is a disadvantage that the high-strength function of the device itself cannot be sufficiently exhibited.

Some resins are of a so-called flexible type and have a breaking elongation of 4% or more, but are not practical because of low strength.

On the other hand, as another method for increasing the toughness of an epoxy resin, a method of adding a flexible rubber, an elastomeric polymer or a tough thermoplastic polymer is also known. In this case, since the viscosity of the resin is increased by the above-described addition, a combination with an acid anhydride-based curing agent is suitable for pultrusion molding. However, when considering the use of a high-tensile material in an alkaline environment such as concrete reinforcement, acid anhydride-based curing is unsuitable because of the presence of ester bonds and degradation due to hydrolysis.

The present inventors have intensively studied a tough epoxy resin treatment method which has excellent interfacial adhesion to glass fibers without deterioration of the resin even in an alkaline environment and follows the elongation of the fibers. Glass fiber reinforced plastic rods obtained by mixing dimer acid type epoxy resin with epoxy resin of epoxy type or bisphenol F type epoxy resin or mixed resin of both and hardening with amine type hardener exhibits unprecedented tensile strength as a high tension body After confirming this, the present invention was completed.

[0009]

The gist of the present invention will be described with reference to the accompanying drawings.

A glass fiber having a tensile strength of 45 gf / TEX or more is used, and the amount of the epoxy resin is set so that the glass fiber is 55 to 75% by volume. The epoxy resin is bisphenol A type, bisphenol F type or both. 2 to 35 parts by weight of an amine-based curing agent were added to 60 to 95 parts by weight of these epoxy resins and 40 to 5 parts by weight of a dimer acid type epoxy resin to obtain a tensile elongation at break after curing. The present invention relates to an epoxy resin composition for a high-tensile material made of FRP for pultrusion , wherein the epoxy resin composition is set to 3.5 to 5%.

[0011]

[Function] Since glass fiber is the main material for securing the product strength, if the glass fiber content is less than 55% by volume, the function as a high tension material is lost. On the other hand, if the content exceeds 75% by volume, the amount of resin is insufficient such that a portion where the resin does not adhere between the fibers is generated, so that the adhesive force is not obtained and the characteristics as FRP are not exhibited.

When the amount of the epoxy resin is less than 60 parts by weight, the cured resin is easily stretched, and the strength is lost. Conversely, if the amount is more than 95 parts by weight, the elongation becomes small and the cured resin breaks down first, so that the intended reinforcing action cannot be achieved.

The dimer acid type epoxy resin is mixed so as to be 100 parts in both cases in order to adjust the elongation of the epoxy resin.

Bisphenol A type epoxy resin has excellent adhesive properties and physical and chemical properties, and is the most widely used epoxy resin among the epoxy resins (more than 80% of the entire epoxy resin is of this type). is there.

The bisphenol F-type resin has properties similar to those of the bisphenol A-type resin and has a low viscosity, so that it is suitable for improving workability in pultrusion molding.

In the case of using both of them, usually, the viscosity of the bisphenol A type epoxy resin is higher, so that the bisphenol F type is mixed for the purpose of lowering the viscosity of the resin system. There is no mixing problem.

The tensile elongation at break of glass fibers used for FRP applications is 4 to 5.5% for monofilaments. Hundreds to tens of thousands of these monofilaments are bundled to form a so-called glass robin. In the glass robin state, it is practically impossible to align all the monofilaments in parallel.Therefore, as the number of monofilaments increases, the tensile strength of the glass robin is expressed by the magnification of the number of monofilaments. Can not be.

For example, even when glass fibers having an elongation rate of 4% of monofilaments are subjected to a tensile load in a state where hundreds or tens of thousands of fibers are bundled, the monofilaments which have reached elongation at break (4%) are sequentially broken. As a result, the fiber breaks as a whole with an elongation smaller than that of the monofilament. The same applies to the case of the tensile strength, and breakage occurs at a value lower than the value calculated from the strength of the monofilament. The reason for this is that monofilaments that are always loose or distorted are mixed, and they break first.

Accordingly, the tensile elongation at break after curing was 3.5.
Set to ~ 5%.

[0020]

The present invention has a tensile strength of 45 gf in a roving state.
A bisphenol A type epoxy resin, a bisphenol F type epoxy resin or a mixed resin of both is selected so that the E glass fiber bundle having a tensile strength of not less than / TEX is 55 to 75% by volume. A resin composition obtained by adding 45 to 25% by volume of a resin composition obtained by adding 2 to 35 parts by weight of an amine-based curing agent to 40 to 5 parts by weight of a dimer acid type epoxy resin and maintaining the shape after shaping into a rod by a shaping guide For this reason, the yarn was spirally wound around the rod-shaped body, pulled into a heating furnace and cured, and the tensile elongation at break was set at 3.5 to 5%. As a result, a high-tensile material excellent in toughness was obtained.

The epoxy resin used in the present invention is a bisphenol A type epoxy resin such as LY556 and GY250 manufactured by Ciba-Geigy, Epicoat 827 manufactured by Yuka Shell, and the like.
Epon 9302 and others. As bisphenol F type resin, XPY306 by Ciba-Geigy, Epicoat by Yuka Shell
807 etc. are raised.

As the dimer acid type epoxy resin, there are Epicoat 871 and Epicoat 872 manufactured by Yuka Shell Co., Ltd.

Examples of the amine-based curing agent include Epon 9350 manufactured by Yuka Shell Co. and HY932 manufactured by Ciba Geigy.

As the reinforcing fiber substrate used in the present invention, it is desirable to use roving-like E glass fibers. The reason is that E-glass fiber is lighter than steel, has improved handling properties, is easy to produce in factories, is easy to transport, has excellent corrosion resistance, and can reduce the thickness of concrete. In particular, E glass fiber is about 1/10 of the cost lower than aramid fiber and carbon fiber.

[0025]

[Table 1]

Using the above liquid epoxy resin composition having a viscosity of 46 poise (25 ° C.), an FRP rod was obtained by pultrusion molding. That is, 19 E glass rovings 4630 count (TEX) were introduced into the impregnation tank containing the above epoxy resin, and after sufficient impregnation, excess resin was squeezed with a squeeze roll, then bundled, and passed through an 8.1 mmφ shaping nozzle. At the very least, make it a rod-shaped body, and use 630 denier nylon thread with a tension of 120 to maintain its shape.
While being spirally wound at a gf pitch of 5 mm, it was passed through a 1000 mm heating furnace set at 130 ° C.
mm, and a heating furnace of 160 ° C. and 2000 mm sequentially at a speed of 0.3 m / m
After passing through in minutes, the rod was hardened and then taken out with a take-up machine to obtain an FRP rod having a nominal diameter of 8 mmφ.

[0027]

[Table 2]

The above liquid epoxy resin composition having a viscosity of 28 poise (25 ° C.) was subjected to a drawing hardening furnace at 110 ° C. (1000 mm length) and 130 ° C. (2000 mm) at a speed of 0.5 m / min in the same manner as in Example 1.
Length), set to 140 ° C (2000mm length), also with nominal diameter 8
A mmφ FRP rod was obtained.

Next, as a comparative example, an FRP rod without using a dimer acid type epoxy resin was molded from the epoxy resin compositions of Examples 1 and 2.

[0030]

[Table 3]

The liquid epoxy resin composition having a viscosity of 36 poise (25 ° C.) was molded in the same manner as in Example 1 to a nominal diameter of 8 m.
An mRP FRP rod was obtained.

[0032]

[Table 4]

The above liquid epoxy resin composition having a viscosity of 7.4 poise (25 ° C.) was molded in the same manner as in Example 1 to obtain an FRP rod having a nominal diameter of 8 mmφ.

The results of the comparative tests of the above Examples and Comparative Examples are shown in the following table. In the test of the casting plate in which the resin used was simply molded into a resin plate, and in the comparative test as the FRP rod of the present invention. It was also proved that the present invention was also excellent in tensile strength.

[0035]

[Table 5]

[0036]

[Table 6]

[0037]

The present invention exhibits, for pultrusion molding the FRP high tensile material for use in pultrusion for the FRP high tensile material which exhibits toughness were also Xiu in elongation at break even at a tensile strength as described above It becomes an epoxy resin composition.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08L 63/02 C08L 63/02 (73) Patent holder 000230010 Geostar Co., Ltd. 4-chome, Shiba, Minato-ku, Tokyo No. 2-3 (72) Inventor Toshiyuki Tachibada 2-1 Tsukudo-cho, Shinjuku-ku, Tokyo, Japan Kumagaya Gumi Tokyo Head Office (72) Inventor Tsutomu Honda 2-1 Tsukudo-cho, Shinjuku-ku, Tokyo Co., Ltd. Gumi Tokyo Head Office (72) Inventor Yuichi Tanaka 1-5-5 Minamihonmachi, Joetsu-shi, Niigata Inside Arisawa Manufacturing Co., Ltd. (56) References JP-A-2-142213 (JP, A) JP-A-1- 185351 (JP, A)

Claims (1)

(57) [Claims] 1. A glass fiber having a tensile strength of 45 gf / TEX or more is used, and an amount of an epoxy resin is set so that the glass fiber accounts for 55 to 75% by volume. This epoxy resin is bisphenol A type or bisphenol F type. Alternatively, select both mixed epoxy resins, add 2-35 parts by weight of an amine-based curing agent to 60 to 95 parts by weight of these epoxy resins and 40 to 5 parts by weight of a dimer acid-type epoxy resin, and obtain a tensile elongation at break after curing. The drawing is characterized by setting the rate at 3.5 to 5%.
Epoxy resin composition for high tension material made of FRP for molding.