JPH0559129B2 - - Google Patents

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to resin-reinforcing glass fiber bundles and fiber-reinforced resin bodies that are suitably used as reinforcing fibers in fiber-reinforced resin bodies such as FRP and FRTP, particularly FRTP. .

[Conventional technology]

Glass fiber bundles are fiber reinforced resin bodies (hereinafter referred to as FRTP).
It is widely used industrially as a reinforcing fiber for the production of

A glass fiber bundle is produced by applying a sizing agent to glass fibers pulled out from a bushing, converging the fibers, and winding the fibers around a mandrel rotating at high speed.

It is usually sold in a cylindrical state, but once it is bundled into a relatively small number of fiber bundles (strands)
This strand is wound on a rotating mandrel to form a "cake", and after drying the "cake", the strands are pulled out from the "cake", and multiple strands are pulled together to form "roving", and this roving is It can be manufactured by winding it into a cylindrical shape, or it can be manufactured by directly collecting a large number of glass fibers drawn from a bushing into a "roving", winding it into a cylindrical shape, and drying it. There are cases.

The "roving" obtained as described above is soaked with resin either as it is or in a cut state,
Widely used as reinforcing fiber when manufacturing FRTP etc.

[Problem to be solved by the invention]

Although the drawn roving has a high resin impregnation speed, the individual strands that make up the roving have length differences, which causes problems such as the roving getting caught on a guide or the like when being pulled out. Roving that is directly wound into a cylindrical shape (directly wound roving) does not have such problems, but since many glass fibers are bundled together, the impregnation speed of the resin is low, and the resin does not spread evenly to the inside. The problem is that it is difficult to seep in, and when drying the roving, the water contained in the sizing agent evaporates, causing "migration" in which the sizing agent migrates and concentrates on the cylindrical surface area along with the water. There is a problem in that the content of the sizing agent in the longitudinal direction of the roving is non-uniform, resulting in coloring of the roving in the surface area.

By reducing the amount of sizing agent applied, the resin and impregnation speed can be increased and the resin impregnation can be made uniform. A new problem arises in that fuzz tends to occur when the roving is pulled out from the roving, and the problem of migration remains unresolved.

Also, for both aligned roving and direct-wound roving, when pulling out the roving from the wound roving,
There is a problem that twist occurs in the roving, and the twist causes non-uniform resin impregnation.

It has also been proposed to solve the above-mentioned problems by converging a large number of glass fibers drawn from the bushing into rovings and depositing the rovings in a non-directional manner into the box body. If the rovings are pulled out after drying, the rovings adhere to each other with the sizing agent, which causes the rovings to become tangled, making it difficult to pull out the rovings smoothly.

The roving deposited in the box body is curved clockwise or counterclockwise, and has a shape in which these directions are reversed in some places.

When such rovings are pulled out, the rovings pulled out from the clockwise curved portion and the rovings pulled out from the counterclockwise curved portion are twisted in opposite directions. These twists in opposite directions are equal in magnitude, and since this twist is in the opposite direction and equal in magnitude to the twist imparted to the roving during deposition, in principle, the twist can be canceled out and untwisted roving can be obtained. It should be possible.

However, when this method was actually carried out, it was found that local twists remained.

The reason for this is not clear, but the sizing agent in the roving during deposition is not hardened and the roving is easily deformed plastically. Since some of the fibers are absorbed, the twist imparted at the time of drawing cannot be completely canceled, and the twists in opposite directions locally remain. Since the dried glass fiber bundle has high rigidity and is difficult to plastically deform, and is used within a short period of time, it is thought that the twists in the opposite directions along the longitudinal direction do not cancel each other out and remain.

It is an object of the present invention to solve the problems of the prior art described above and to provide a resin-reinforcing glass fiber bundle with less twist and a high resin impregnation rate, as well as homogeneous FRTP.

[Means to solve the problem]

In order to achieve the above object, the present invention
As reinforcing fibers for FRTP, etc., a sizing agent of 0.01 to 2 wt% is added as a solid content to the glass fibers pulled out from the bushing, and the bundles of glass fibers are allowed to fall in a non-directional manner into a box without being cut, and are allowed to dry. In a fiber-reinforced resin body mainly composed of resin-impregnated glass fiber bundles, 0.01 to 2 wt% of a sizing agent is added as a solid content to the glass fibers pulled out from the bushing as the glass fiber bundles. The bundled glass fiber bundle is dropped and deposited in a box without cutting, and after drying, the fiber bundle is pulled out from the box and the resin-impregnated glass fiber bundle is used to make a fiber-reinforced resin body. .

Next, the present invention will be explained in more detail.

In the present invention, the glass fiber has a diameter of 3
It is appropriate to use one with a diameter of ~23μ, preferably 10-16μ.

As the glass fiber bundling agent, 0.05 to 10 wt%, preferably 1 to 5 wt%, of a film forming agent such as epoxy resin or urethane resin, and 0.05 to 0.5 wt% of a lubricant such as fatty acid amide, preferably 0.1 to 0.3 wt%. Coupling agents such as wt% organosilicon compounds from 0.05 to
Those containing 0.8wt%, preferably 0.1 to 0.6wt% can be suitably used.

The amount of sizing agent added is 0.01-2wt% as solid content,
Preferably, it is determined to be 0.1 to 0.8 wt%.

If the amount added is too small, the efficiency of yarn collection will deteriorate and fuzzing will occur easily, and if the amount added is too large, it will be difficult to achieve the object of the present invention.

The number of focused lines is 400 to 10,000, preferably 800 to 10,000.
It is appropriate to set the number to 4000 pieces.

If the number of bundles is too small, productivity will decrease and costs will increase, and if the number of bundles is too large, resin impregnation tends to be uneven.

The above-mentioned glass fiber bundle can be manufactured according to conventional methods.

For example, glass fibers drawn from a bushing are coated with a liquid sizing agent using an applicator, passed through a sizing member to be concentrated, and excess sizing agent is removed, for example by a pair of rolls rotating in opposite directions. Pinch and pull it to let it fall and accumulate inside the box. At this time, it is desirable to cause the glass fiber bundle to fall through a guide and to give reciprocating motion to the guide or to give reciprocating motion to the box. The glass fiber bundle dropped into the box has a shape curved clockwise or counterclockwise, and these directions are reversed at some places.

The glass fiber bundles thus deposited are dried by blowing hot air or by circulating hot air.

Drying time is 10 min at 100-200℃
It is about 8 hours.

The glass fiber bundle of the present invention is used by being pulled out from inside the box. At this time, the twists in opposite directions that occur in the longitudinal direction are easily canceled out, and a continuous glass fiber bundle without twists can be obtained. .

This seems to be because the glass fiber bundle of the present invention has a small amount of sizing agent added, has low rigidity, and is easily plastically deformed.

As described above, the resin-reinforcing glass fiber bundle (main fiber bundle) is pulled out from the box and impregnated with liquid resin.

Liquid resins include nylon, polypropylene, polycarbonate, saturated polyester resin,
Examples include thermoplastic resin melts such as polyphenylene sulfide resins, thermosetting resins such as unsaturated polyester resins, epoxy resins, and phenolic resins.

In addition, liquid resins contain curing agents such as BPO and TBPO, curing accelerators such as cobalt naphthenate and dimethylaniline, fillers such as clay, carbonaceous acid, and mica, and pigments such as carbon black and titanium white. It may include. There is no particular limitation on the method of impregnating the liquid resin, and a conventional method can be used. For example, in an impregnating tank containing liquid resin, preferably through a guide roll,
The amount of resin impregnated can be controlled to a predetermined value by passing the fiber bundle to impregnate it with resin, and then passing the fiber bundle through a die to squeeze out excess resin.

As mentioned above, this fiber bundle does not remain twisted even after being drawn out, has a high resin impregnation rate, is uniformly impregnated with resin, has good workability, and does not become tangled when drawn out. Also, it does not cause fluff.

Main fiber bundle containing resin (resin-containing fiber bundle)
is used to manufacture FRTP, etc.

For example, a resin-containing fiber bundle using a thermoplastic resin as the resin is dried if necessary, cut and piled up in a conventional manner to form a pine-like material, and this pine-like material is pressurized and heated to form a plate. It is possible to produce a resin body like a body.

Further, a resin body such as a tubular body or a rod-shaped body can be manufactured by using a resin-impregnated fiber bundle using a thermosetting resin as the resin and using a filament winding method (FW method) or a pultrusion method.

[Effect]

Glass fiber bundles for resin reinforcement are made by adding 0.01 to 2wt% of a binding material as a solid content to the glass fibers pulled out from the bushing.The bundles of glass fibers are dropped in a non-directional manner into a box body without being cut, and then dried. By using this, twisting, tangling, and fuzzing can be prevented during pulling out, and the impregnating properties of the resin can be improved.

In addition, in a fiber-reinforced resin body mainly composed of resin-impregnated glass fiber bundles, the glass fiber bundles are made by adding 0.01 to 2 wt% of a sizing agent as a solid content to the glass fibers pulled out from the bushing and converging them. A homogeneous FRTP is produced by dropping the fiber bundle into a box without cutting it, drying it, pulling it out from the box, and forming a fiber-reinforced resin body using resin-impregnated glass fiber bundles. etc.

〔Example〕

Glass fibers with a diameter of 13μ pulled out from the bushing were given 0.3wt% of the sizing agent shown in the composition as a solid content, and 3200 fibers were bundled.
It was dropped and deposited in a box measuring 50 cm, width 50 cm, and height 50 cm without cutting in any direction, and then heated and dried at 150°C for 1 hour.

This glass fiber bundle was then pulled out and impregnated with PET resin. (Resin dosage, glass fiber
(150 wt%) This glass fiber bundle was cut into a length of 13 mm and pelletized, and the pellet was molded into an ASTM D-256 test piece. Workability during production of the glass fiber bundle was good, and no fuzz was observed. The Izod impact strength of the test piece was 30 kg-cm/cm, and the average glass fiber length in the molded product was 6.5 mm.

Composition Epoxy emulsion 5wt% Aminosilane 0.5wt% Lubricant 0.2wt% [Comparative example] The same glass fiber bundle as in Example 1 was wound into a cylindrical shape according to a conventional method, and then the same glass fiber bundle as in Example 1 was wound up into a cylindrical shape. I did it. Izod impact strength is 27Kg-cm/
cm, and the average glass fiber length was 5.5 mm.

〔Effect of the invention〕

The glass fiber bundle of the present invention has good workability and resin impregnation properties, has little fluff, and does not become tangled or twisted when drawn out.

In addition, the FRTP and FRP of the present invention have poor resin impregnation,
There are no defects associated with twisting of glass fiber bundles.

Claims (1)

[Claims] 1. A sizing agent of 0.01 to 2 wt% as a solid content is added to the glass fibers pulled out from the bushing, and the sifted glass fiber bundles are allowed to fall in a non-directional manner into a box body without being cut, and are then dried. Glass fiber bundle for resin reinforcement. 2. In a fiber-reinforced resin body mainly composed of resin-impregnated glass fiber bundles, the glass fiber bundles are added to the glass fibers pulled out from the bushing as a solid component.
This is a glass fiber bundle obtained by adding 0.01 to 2 wt% of a sizing agent to the bundled glass fiber bundle, which is dropped and deposited in a box without cutting, and after drying, the fiber bundle is pulled out from the box and impregnated with resin. Fiber reinforced resin body.