JPH0811867B2 - Glass fiber for unsaturated polyester resin reinforcement - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass fiber for reinforcing an unsaturated polyester resin, which is preferably used for producing FRP.

[0002]

2. Description of the Related Art FRP is manufactured by impregnating a reinforcing fiber such as glass fiber, carbon fiber or organic fiber with a liquid thermosetting resin and curing the resin. FR
As P, unsaturated polyester resin is supplemented with glass fiber.
What was mightier are most commonly used, also non liquid
The saturated polyester resin, curing agent, curing initiator, those obtained by mixing materials caused Ru cause curing catalyst and the like, or, in this
Further, a substance mixed with a substance that accelerates curing (curing accelerator) is used. In recent years, there has been a demand for shortening the curing time for the purpose of improving productivity. For this purpose, the mixing amount of the hardening accelerator to be large occur.

[0003]

The prior art has the following problems. Liquid unsaturated polyester resin (hereinafter
When a large amount of curing accelerator is added to and mixed with this resin)
The curing speed of the resin is increased. For this reason, the viscosity of the present resin increases rapidly during use, which causes variations in working conditions, shortens the pot life of the present resin in a liquid state, and requires a small amount of mixing. Increase.

In addition, reinforcing glass fiber (hereinafter referred to as the present fiber)
U) and occurred minute cracks in the interface between the resin easily, Therefore resulting water resistance of the FRP is deteriorated, whitening occurs easily.

The curing rate can be increased by increasing the amount of the curing accelerator added, but the productivity is improved.
Therefore, if the addition amount is large, the cost increases. or,
Although the curing time can be shortened by performing the curing in a heating furnace, this method consumes extra energy, increases the equipment cost, and increases the cost.
It is easy to cause deterioration of quality.

The present invention solves the above-mentioned problems of the prior art, accelerates curing of the liquid unsaturated polyester resin without lowering the pot life of the liquid unsaturated polyester resin, improves productivity, and provides uniform quality. The purpose is to obtain an FRP having good water resistance.

[0007]

SUMMARY OF THE INVENTION In order to achieve the above object, the present invention is for reinforcing an unsaturated polyester resin.
As the glass fiber, a glass fiber coated with a curing accelerator that accelerates the curing of the present resin is used. Next, the present invention will be described more specifically.

[0008] As the reinforcing fiber used in the present invention, Ru with glass fibers.

The present fiber is formed by adding a sizing agent to a large number of monofilaments (monofilaments) to form a bundle of fibers, for example, strands or chopped strands (C).
S), chopped strand mat (CM), continuous strand mat (CSM), or monofilament, for example, surfacing mat, glass paper,
There is no particular limitation on the mode of use.

A liquid unsaturated polyester resin is used as the thermosetting resin . Liquid unsaturated polyester resins are glycols such as ethylene glycol and anhydrous phthalates,
Condensate with maleic anhydride, etc. is used as a monomer such as styrene
Although it is dissolved , it does not substantially cure by itself, and a crosslinking reaction (curing) occurs when a curing agent such as peroxide such as methyl ethyl ketone peroxide is added. Cobalt naphthenate or the like can be preferably used as the curing accelerator.

[0011] No particular limitation on the method of the curing accelerator to the fiber depositing, but the solution of the curing accelerator (or emulsion, suspension) was sprayed on the fiber as described above, or the present fibers above By immersing in a solution etc.,
The curing accelerator can be uniformly applied to the fibers.
The coating amount of the curing accelerator is determined according to the types of the resin and the curing accelerator, and the desired curing rate, but is 0.01% of the present fiber.
It is suitable to be about 2 wt%, preferably 0.05 to 1 wt%, and the amount of the curing accelerator used can be greatly reduced as compared with the case of mixing with a liquid resin. By using a sizing agent containing a curing accelerator, the curing accelerator is
It can also be applied simultaneously with focusing .

[0012] insufficient effect and is much smaller amount of the curing accelerator, also when this amount is too large, curing in the vicinity of the interface between the fibers and the resin proceeds rapidly, and lead to FRP of quality degradation easy.

The present fiber is impregnated with the present liquid resin, and the resin is heated if necessary to cure the resin to obtain FRP. F
The method for producing RP is not particularly limited, and a hand layup method, a spray up method, a pressing method, a resin injection molding method, a pultrusion molding method, a filament winding method or the like can be appropriately selected. Pultrusion method, in the filament winding method, is given whenever an excess of resin in the fibers, an excess of the resin is squeezed by the dies or the like, the curing accelerator from the fibers into the resin removed by the squeeze The transfer is slight and the squeezed resin can be reused as a raw material.

[0014] The fiber impregnation brought was present resin (this tree
As described above, the curing agent is contained in the fat.
It ) Is quickly hardening under the action of curing accelerator. In the present invention, since the curing accelerator is applied to the fiber surface, curing of the resin is initiated from the interface of the fiber and the resin gradually because the outer resin is cured to shrink, the cured resin of the fiber It becomes easy to adhere to the surface, the generation of minute cracks on the fiber surface is prevented, and the water resistance of FRP is improved.

Further, the curing accelerating action of the curing accelerator is comparable to the case where the curing accelerator is mixed in the present resin, and a small amount is sufficient, without lowering pot life and productivity. Can be improved and a homogeneous FRP can be obtained. Incidentally, the present resin as the resin pigment, it is also possible to use a filler, a resin composition containing an internal mold release agent. In addition, it is suitable that the resin contains a small amount of a curing accelerator (so that the pot life is not significantly reduced).

[0016]

[Function] By applying the curing accelerator of the present resin to the present fiber, the pot life of the present resin is not reduced,
Promotes resin curing, increases FRP productivity, and ensures uniform F
Get RP. Further, curing of the resin is started from an interface of the resin and the fibers, to prevent the occurrence of fine cracks in the vicinity of the interface, F
Improves the water resistance of RP.

[0017]

EXAMPLE A naphthenic acid was applied on the surface of a roving made of a glass fiber bundle having a weight of 2,300 g per 1,000 m, which was obtained by concentrating 1 wt% of polypinyl acetate binder as a solid content on E-glass fiber having a diameter of 11 μm. Cobalt (acceleration of hardening
Agent) emulsion was sprayed to deposit 0.1 wt% cobalt naphthenate as a solid content. An unsaturated polyester resin blend [resin 1 in the blend was added to this roving.
00 parts by weight , pigment 3 parts by weight , methyl ethyl ketone peroxide (curing agent) 1 part by weight , cobalt naphthenate (curing accelerator) 1 part by weight ) by a spray-up method
C30 wt% FRP was manufactured. The curing time is about 5 times as compared with the case of using roving which does not apply the curing accelerator.
It was possible to shorten by 0%. The pot life was the same as that of about 0.5 hours, and it was possible to obtain a homogeneous FRP having good water resistance.

[0018]

To the same manner as in Example a curing time by adding a curing accelerator to the Comparative Examples] in the resin, methyl ethyl ketone peroxide, amount respectively 3 parts by weight of cobalt naphthenate in the resin, and 3 parts by weight The total amount of the curing accelerator used was about 3 times that of the example, and the pot life was also reduced to 15 minutes. Also, the amount of hardener used is tripled.
became. Further, the water resistance of the comparative example was poor.

[0019]

EFFECT OF THE INVENTION F without reducing pot life.
It is possible to improve the productivity of RP and obtain a uniform FRP having good water resistance.

Claims (1)

[Claims] 1. A unsaturated port, characterized in that the curing accelerator to accelerate were deposited the curing of unsaturated polyester resins
Glass fiber for polyester resin reinforcement