JPH06108355A - Production of glass fiber bundle mat - Google Patents

Abstract

PURPOSE:To provide a glass fiber bundle mat having excellent fittability to a mold, excellent and balanced wet-out and wet-through properties and suitable for the production of uniform FRP. CONSTITUTION:A strand produced by using a collecting agent composed mainly of an easily water-soluble film-forming agent is temporarily wound to form a roll and dried with heat. The strand is unwound from the roll, cut and deposited to form a mat. The mat is imparted with water and a binder and dried with heat to obtain the glass fiber bundle mat.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a glass fiber bundle mat, which is particularly suitable as a reinforcing material composed of reinforcing fibers used in FRP production.

[0002]

2. Description of the Related Art FRP is manufactured by impregnating a reinforcing material with a liquid thermosetting resin, and heating the resin if necessary to cure the thermosetting resin. The RTM method, the RIM method, the pultrusion method and the like are known as a molding method for obtaining an FRP having a required shape. Glass fibers are most commonly used as reinforcing fibers. As a glass fiber reinforcing material, a sizing agent is attached to a large number of glass fibers pulled out from a bushing, and the resulting glass fiber bundle (strand) is brought into contact with the surface of a rotating cylinder (pulling wheel) and shaken. A continuous strand mat (CSM) consisting of continuous strands is known, which is formed by curving and depositing on a moving conveyor, forming a curved shape, applying a binder, and heating the strands to bond the strands together. . (Refer to Japanese Utility Model Publication No. 43-234) In addition, after the strand is once wound as a cake and dried, the strand is pulled out from the cake and cut into a predetermined length to form a cut product (CS) of the strand, and the CS is moved. Chopped strand mat (C)
M) is known.

[0003]

The prior art has the following problems. (1) The strands that make up the CSM are in contact with the surface of the pulling wheel, are shaken off, and are deposited in a curved shape in a continuous state. Also, since the strands have a substantially circular cross-sectional shape, they are bulky. The density is low. For this reason,
When a liquid thermosetting resin is applied to the CSM surface to impregnate the CSM with the resin, the CSM has a small resistance to the flow of the resin, and the resin is uniformly impregnated within a short time. That is, C
SM has good Wet Thru. However C
Since the strands constituting the SM are continuous and the strands are bound to each other by the binder, the movement of the strands is restrained. Therefore, when a resin-impregnated CSM is pressed against a mold to manufacture an FRP having a desired shape, the mold familiarity tends to be insufficient, and a curved surface having a small radius of curvature is obtained, or an FRP having a complicated shape is obtained. Is difficult.

(2) When using CM, the mold familiarity is good,
F with a curved surface with a small radius of curvature or a complicated shape
Although the RP can be obtained, the CS constituting the CM has a flat shape because it is used after being once wound as a cake, and the CS is cut into short pieces. For this reason, CM has a large bulk density and a large flow resistance to the liquid resin, and Wet Thru is not good.

(3) In order to obtain a homogeneous FRP industrially, the Wet Thru of the glass fiber bundle mat is good, and the liquid resin penetrates uniformly between the strands constituting the mat as quickly as possible. However, it is also important that the resin quickly penetrates into the strands and uniformly permeates between the glass fibers forming the strands. That is, Wet Out must be good. However, it should be noted here that the Wet Out does not have to be unnecessarily large, but it is necessary that the Wet Out have a proper size in harmony with the Wet Thru. Wet
If Out is too large, the liquid resin will soak into the strands of the mat surface layer before it penetrates between the strands, causing the strands to open into monofilaments and degrading Wet Thru, resulting in a homogeneous FRP.
Is difficult to obtain.

(4) Therefore, as a mat of glass fiber bundles, it has a good mold fit and is Wet Thru, Wet.
It is desirable that both outs are good and the sizes of both are in harmony, but it was difficult to obtain a glass fiber bundle mat having such properties. INDUSTRIAL APPLICABILITY The present invention solves the above-mentioned problems of the prior art, and is well suited for molds, Wet Thru, and Wet Out, and is suitable for industrial production of a homogeneous FRP in which Wet Thru and Wet Out are harmonized. It is an object of the present invention to provide a highly suitable method for producing a mat of glass fiber bundles.

[0007]

In order to achieve the above object, in the present invention, a glass fiber drawn from a bushing is provided with a sizing agent whose main component is a water-soluble film-forming agent, It is bundled into a glass fiber bundle, and this fiber bundle is once wound into a wound body, heated and dried, and then the fiber bundle is drawn out from the wound body and cut into a predetermined length to obtain a cut glass fiber bundle. A glass fiber bundle mat is manufactured by depositing the cut pieces into a mat-like material, adding moisture and a binder, heating and drying the cut pieces, and bonding the cut pieces together with the binder. In a preferred embodiment of the present invention, a conductive polymer containing a quaternary ammonium salt is used as a film-forming agent that is easily soluble in water, and the amount of water added is 5 to 100 g of the glass fiber bundle. 50 gr.

Next, the present invention will be described more specifically. As the glass fiber bundle, a sizing agent is added to glass fibers having an average diameter of 8 to 20 µ, preferably 10 to 15 µ
It is desirable to use 1,000, preferably 60 to 300, bundles having a weight per 1,000 m of 10 to 300 gr, preferably 15 to 100 gr. As the sizing agent, an aqueous liquid containing a film-forming agent that is easily soluble in water as a main component is used. As the film-forming agent which is easily soluble in water, soluble starch, polyethylene oxide, triethylene glycol and the like can be used, but it is particularly preferable to use a conductive polymer containing a quaternary ammonium salt.

As the conductive polymer containing a quaternary ammonium salt, polyvinylbenzyltrimethylammonium chloride, N, N-dimethyl-substituted 3.5-methylpiperidinium chloride-resin, poly-4-vinyl-N-methylpyridinium Examples thereof include chloride, quaternized polyethyleneimine, and quaternized polyepichlorohydrin, and polyvinylbenzyltrimethylammonium chloride and N, N-dimethyl-substituted 3.5-methylpiperidinium chloride resin are most preferable.

The amount of the easily water-soluble film forming agent in the sizing agent is 0.1 to 15% by weight, preferably 1 to 1 as a solid content.
It is suitable to be 0 wt%. In the sizing agent,
It is also desirable to include a lubricant such as a mineral oil emulsion. The amount of the sizing agent added is 0.01 to 1.5 wt% of the glass fiber as a solid content, preferably 0.1 to
It is suitable to be 1.0 wt%. If this amount is too small, the effect of the present invention is not sufficient, and if this amount is too large, it may take too long to dissolve the sizing agent in water, which is industrially undesirable.

The strand obtained by adding and bundling the above-mentioned sizing agent is once wound around a collet rotating at high speed to form a cake, which is then heated and dried. The heating temperature and the heating time are determined in correlation with each other, but usually 8 to 24 at 100 to 150 ° C.
It is about hr. Next, a strand is drawn out from the cake and cut into 2.5 to 160 cm, preferably 5 to 100 cm to form CS, and the CS is dropped and deposited on a moving conveyor to form a mat-like material. The amount of CS deposited is 50-1,
000 gr / m ² , preferably 80 to 800 gr / m ^2.
Is appropriate.

Moisture and a binder are added to the mat-like material. The order of application is not particularly limited, and both may be applied at the same time, but it is preferable to add the binder after adding water, and the yield of the binder can be improved. As the binder, it is desirable to use a saturated polyester resin containing no crosslinking agent. Use a powdered binder,
Moreover, the amount of addition is 1 to 20 wt% of CS, preferably 2
It is suitable to be 10 wt%. If this amount is too small, the workability (handleability) of the CM is lowered, and if this amount is too large, the Wet Out property of the CM to the resin is lowered too much, which is not preferable.

There is no particular limitation on the method of applying water and the time of application. Although it is desirable to spray the moisture toward the mat-like material, it may be sprayed toward the CS during the fall. The amount of water added is appropriately 5 to 50 gr, preferably 8 to 30 gr per 100 g of CS. If the amount of water added is too small, the effect of the present invention tends to be insufficient, and if this amount is too large, the shape of the strands tends to collapse.

The mat-like material to which moisture and a binder have been added is heated and dried to obtain CM. The heating temperature and the heating time are determined in correlation with each other, but usually at 150 to 300 ° C, 1 to
It is about 30 minutes. When water is added to CS, a film-forming agent that is easily soluble in water is used. Therefore, the sizing agent containing the film-forming agent as a main component dissolves in water, and the individual glass fibers forming CS are bonded. The relative position of the glass fiber in the CS moves so that the shape of the CS becomes almost circular due to the slack and the interfacial tension of the produced sizing agent solution. In this state, heating and drying are performed, and while CS has a circular cross section, CSs are bonded with a binder to obtain CM of the present invention.

Since the CS forming the CM of the present invention has a circular cross section, the Wet Thru is improved, and the surface of the CS is covered with a thin film of the film forming agent due to migration accompanying heating and drying. The thin film of the film-forming agent is C
Liquid thermosetting resin attached to M is CS from the CS surface
Wet Ou acts as a resistance when seeping inside
The wett is not excessively large despite the decrease in t and the use of the film-formed film that is easily soluble in water.
Thru and Wet Out are in harmony, and by using the mat of the present invention, a homogeneous FRP can be obtained,
Productivity is also improved.

[0016]

The glass fiber pulled out from the bushing is provided with a sizing agent containing a film-forming agent that is easily soluble in water as a main component, and is bundled into a glass fiber bundle. The glass fiber bundle is once wound into a roll body. None, after heating and drying, pull out the fiber bundle from the above-mentioned wound body, cut it to a predetermined length to make a glass fiber bundle cut product, deposit this cut product into a mat-like product, attach moisture and a binder. After applying, heating and drying, the cut products are combined with a binder to improve Wet Thru and We.
To Out and Wet Thru are harmonized to industrially manufacture a glass fiber bundle mat that is extremely suitable as a reinforcing material for FRP.

[0017]

Example 1 2.5 wt% of polyvinylbenzyltrimethylammonium chloride as a film forming agent, 1.0 wt% of mineral oil emulsion as a lubricant, and 1.0 wt% of a coupling agent as a film forming agent on glass fiber with an average diameter of 11 μm drawn from a bushing. As a solid component, 0.4 wt% of a sizing agent containing 0.5 wt% of acrylic silane was added, and 90 bundles were bundled to obtain a strand having a weight of 30 gr per 1,000 m. This strand was once wound as a cake, heated at 130 ° C. for 12 hours and dried. Pull the strands from the cake and cut into 15 cm lengths, 45
Drop it on a conveyor that moves at a rate of 0 gr / m ² ,
It was a mat-like material. Moisture was sprayed from the nozzle toward the mat-like material at a rate of 45 gr / m ² , and the unsaturated polyester resin powder was spread as a binder at a rate of 23 gr / m ² . Then, it was heated at 250 ° C. for 5 minutes, and the CSs were bonded with a binder to produce CM.

[0018]

Example 2 A CM was produced in the same manner as in Example 1 except that N, N-dimethyl-substituted 3.5-methylpiperidinium chloride resin was used instead of the film forming agent of Example 1.

[0019]

COMPARATIVE EXAMPLE 1 In the process of Example 1, a CM was manufactured under the same conditions except that only the spray of water was omitted.

[0020]

COMPARATIVE EXAMPLE 2 The same procedure as in Example 1 was carried out except that the polyvinyl acetate emulsion was used instead of the film forming agent in Example 1.
Was manufactured.

[0021]

Example 1 Example 1.2, Comparative Example 1.2 Using CM, an unsaturated polyester resin containing a curing agent relative to CM has a resin weight of 70% of the total amount of the resin weight and the CM weight. FRP was prepared by the RTM method. The bending strength, quality, and mold familiarity of the obtained FRP are as shown in Table 1.

[Table 1]

[0022]

The effect of the invention is that the mold familiarity is good, and Wet Thru,
Wet Out is good, and a glass fiber bundle mat with a good balance between the two can be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location D06M 15/347

Claims (3)

[Claims] 1. A glass fiber drawn from a bushing,
A sizing agent whose main component is a film-forming agent that is easily soluble in water,
The glass fiber bundle is bundled, and the fiber bundle is once wound to form a wound body, which is dried by heating, and then the fiber bundle is pulled out from the wound body and cut into a predetermined length to obtain a cut glass fiber bundle. A method for producing a glass fiber bundle mat, comprising depositing the cut pieces into a mat-like material, adding moisture and a binder, heating and drying the cut pieces, and binding the cut pieces together with the binder. . 2. The method for producing a glass fiber bundle mat according to claim 1, wherein the water-soluble film-forming agent is a conductive polymer containing a quaternary ammonium salt. 3. The amount of water added is 10 by weight of the glass fiber bundle.
The method for producing a glass fiber bundle mat according to claim 1, wherein the content is 5 to 50 gr with respect to 0%.