JPH06240578A - Fixing agent for preventing fray of woven fabric of glass fiber and woven fabric of glass fiber using the same - Google Patents

Abstract

PURPOSE:To obtain a fixing agent for preventing fray of woven fabric of glass fiber having firm adhesion, not to make warp at the end fray, having preventing effect on fray by sealing a fray preventing fixing agent to both selvadge parts of woven fabric of glass fiber. CONSTITUTION:Both selvage parts of woven fabric of glass fiber in fixed width are coated with 2-10wt.% of a fray preventing fixing agent such as a water- based urethane resin based on weight of part to be coated of the woven fabric of glass fiber and the fixing agent is cured to give woven fabric of glass fiber having high bond strength, a flexible coating film, excellent solvent resistance and improved fray preventing effect. By this method, thickness of the part to be coated is not changed and uniform and the water-based urethane resin is advantageously used. This fray preventing fixing agent is suitable as a fixing agent for preventing selvadge fray of glass fiber woven by an air jetting weaving machine useful for copper-clad laminate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ear fray prevention agent for glass fiber fabrics, and more particularly to an ear fray prevention agent for glass fiber fabrics woven by an air jet loom used for copper clad laminates.

[0002]

2. Description of the Related Art Although glass fiber woven fabrics were mostly woven by shuttle looms in the past, the proportion of those woven by unknitted looms such as air jet looms has recently been increasing. Particularly in the field of copper clad laminates that consume a large amount of glass fiber fabric, most of them are woven by an air jet loom. However, in the case of the air jet loom, the weft yarn is cut after each weft insertion, so that the cut ends of the weft yarn are present at both ends of the fabric in a tufted shape. As is well known, a glass fiber woven fabric used for a copper clad laminate is impregnated with a thermosetting resin varnish such as an epoxy resin and then dried to obtain a prepreg. A copper clad laminate is obtained by laminating a plurality of these prepregs, laminating copper foils, and heating and pressing.

When a prepreg is manufactured from a glass fiber woven fabric having tassels woven by a straight loom such as an air jet loom, the following problems occur.

The first problem is that the glass fiber woven fabric contains an excessive amount of resin in the ears, and the ears tend to be thicker than other parts. Is. When prepregs with thick ears are cut to the required length and piled up, the height of the layers of the prepregs piled up becomes higher because the locations where the ears are present are higher. I can't do it. Such a prepreg having a non-uniform thickness over the entire width causes various inconveniences when a product is made using the prepreg. For example, when obtaining a copper clad laminate using a prepreg, there is a drawback that the entire prepreg width cannot be pressed.

A second problem is that when the shapes of both ends of the width of the prepreg are viewed in the length direction, the prepreg is not straight but is uneven due to the ears. When these prepregs with uneven shapes are cut to a certain length and piled up, there is a drawback that the ends are difficult to align. When further aligning the ends, one part of the irregularities is cut off and scattered into the prepreg. If mixed, it will cause defective products.

[0006] The third problem is that the glass fibers in the tassels are cut off during prepreg production,
It is mixed in the varnish and adheres to the surface of the prepreg to cause defective products. Although the problems when the prepreg is manufactured from the glass fiber woven fabric having the tassels have been described above, the first problem may similarly occur in the ears of the glass fiber woven fabric woven by the shuttle loom.

In order to avoid the first and second problems, a method in which the ears are cut and removed after manufacturing the prepreg can be adopted, but in this case, the third problem cannot be avoided, and the glass fiber fabric is also unavoidable. And the yield of the varnish decreases, which is not preferable in terms of cost.

[0008] Furthermore, it is also conceivable to remove the ear portion before making the glass fiber fabric into a prepreg, and some proposals have been made. For example, a method of fusing the selvages with a laser beam and welding the cut ends at the same time, or weaving thermoplastic resin threads into the warp selvages of the glass fiber fabric, and then weaving the thermoplastic resin thread parts. There is a method of heat fusion. However, the method using a laser beam has not been put into practical use because it is not possible to increase the speed of fusing and there is a problem that small balls generated during fusing fall into the varnish during the prepreg process. The method of weaving thermoplastic resin threads into the warp selvages has a problem that it cannot be applied to a special woven fabric because it cannot carry out heating deoiling, which is a normal process for manufacturing glass fiber woven fabrics.

Further, it has been proposed to solve the above problems by applying a hot melt type adhesive to the inner part of the ear of the glass fiber fabric. However, in the case of the hot melt type, in the prepreg process, since the solvent is heated at a temperature of around 150 ° C., depending on the conditions, troubles such as warping of the end warp and entanglement with the rollers of the prepreg device occur. There was something to do. In addition, since the coated edge becomes a little thick, if you cut it to a certain size after stacking it and stack it,
There is also a problem that both end portions are higher than the central portion, which is an obstacle to automation of the laminating process. In order to solve these problems, the inventor of the present application has filed a glass fiber fabric fixing agent composed of an epoxy-amine reactant and an isocyanate.
(Japanese Patent Application No. 4-156430) However, since this fabric fixing agent is soluble in an organic solvent such as methyl cellosolve, safety aspects such as fire and working environment due to solvent vapor, and
There are problems such as waste liquid treatment.

[0010]

SUMMARY OF THE INVENTION A first object of the present invention is that when applied to the cut end of a glass fiber woven fabric, the adhesion of the glass fibers is strong, and the warp at the end does not fray, Another object of the present invention is to provide an anti-fraying adhesive agent for glass fiber fabrics, which does not swell in the solvent used for the thermosetting resin varnish. The second object of the present invention is to
When the prepreg is made by impregnating the thermosetting resin varnish with the glass fiber fabric coated with the anti-raveling adhesive on the cut ends of both ears, the thickness is uniform over the entire width, and both ends of the width form a straight line, It is an object of the present invention to provide a glass fiber woven fabric which has no unevenness in the lateral direction and which does not cause the glass fiber at the end portion to be cut off and adhere to other portions to deteriorate the quality. Furthermore, a third object of the present invention is to use an aqueous solvent as the resin solvent, instead of an organic solvent.

[0011]

In order to achieve the first object, the inventors of the present application have solved the problem by using a water-based urethane resin as a fray preventive fixing agent for a glass fiber fabric. Further, a glass fiber woven fabric for achieving the second object is characterized in that the anti-fray adhesive is applied to both ears in an amount of 2 to 10% based on the weight of the applied portion of the glass fiber woven fabric. . Furthermore, the gist is that the anti-fray adhesive agent for glass fiber fabric for achieving the third object is an aqueous anti-fray adhesive agent.

There are various types of water-based urethane resins such as anion type, cation type and non-ion type, and various types of phase states are provided from water-soluble type to emulsion type. The urethane resin used in the anti-raveling adhesive of the present application is not particularly limited, and any water-based urethane resin can be used. The water-based urethane resin is adjusted to an aqueous solution of 15 to 60%. 20 to 40% is preferable. If the concentration is lower than this, the effect of preventing fraying is weakened, and if the amount used is higher than this, the resin impregnating property at the time of preparing the prepreg is adversely affected. Further, in order to enhance the preventive effect, a crosslinking agent may be added in an amount of 2 to 10%.
As for the drying condition, it is sufficient that the water is essentially dried, so that it may be adjusted to the condition at the time of use. However, if the temperature exceeds 200 ° C., the resin may deteriorate, which is not preferable. The anti-fray adhesive fixing agent liquid thus prepared is applied to the anti-fray portion of the glass fiber fabric. The amount of the anti-raveling adhesive applied is 2 to the applied portion of the glass fiber fabric.
It is 10% by weight (solid content). The application method is preferably a roller method, but a brush method or the like is also possible. The anti-fray adhesive is applied to any position as long as it is intended to prevent fraying of the glass fiber fabric, but it is used for copper-clad laminates and is a tufted woven by an air jet loom. In the case of the glass fiber woven fabric having the above, it is preferable to apply the inside of both ears in the warp direction in a width of about 10 mm.

The glass fiber woven fabric coated with the anti-raveling adhesive is continuously introduced into the heating section to dry the water,
The ears are fixed by urethane resin. The heated glass fiber woven fabric is further continuously slurried by about 1
Cut the center of the anti-fray adhesive applied to 0 mm width. This cutting takes place simultaneously on both ears of the fabric. Therefore, the cut glass fiber woven fabric is about 5 m on both ends.
With the m-width anti-fray adhesive applied, the ears, including the tassels, will be removed from the fabric.

The woven fabric used for the glass fiber woven fabric coated with the anti-raveling adhesive of the present invention is a glass fiber woven fabric which is degreased after weaving and further treated with a surface treatment agent such as a silane coupling agent. However, it is also possible to perform the anti-raveling treatment at a stage before the surface treatment after deoiling, and then perform the surface treatment thereafter. In the case of a woven fabric made of glass yarn that uses a degreasing-free sizing agent, which is used in some cases, the degreasing process is not necessary and the surface treatment agent is also included in the sizing agent. No process is required. Therefore, the woven glass fiber fabric can be subjected to anti-raveling treatment.

[0015]

Since the anti-raveling adhesive of the present invention is a urethane resin, the coating film has flexibility and exhibits sufficient raveling strength. Further, since it is water-based, it has excellent workability and safety, and can cope with environmental problems. Further, in the glass fiber woven fabric coated with the anti-raveling adhesive of the present invention, the coating portion of the anti-raveling adhesive has flexibility, so that the coated portion does not break or crack. Further, since the strength of the coating film is high, the effect of preventing fraying can be exhibited with a small coating amount. Therefore, there is almost no difference in thickness between the coated part and the uncoated part, so even if the glass fiber fabric is cut into a certain length and stacked, there is almost no difference in height between the end and the center. There is no.

[0016]

【Example】

Example 1 An anti-fraying adhesive solution was prepared as follows. A water-soluble urethane resin (HUX-232 Asahi Denka Kogyo Co., Ltd.) was prepared to be a 20% aqueous solution. The adhesive solution obtained in 1 was applied to both ears of the glass fiber fabric along the warp with a width of 10 mm by a roller coater, and then heated at 130 ° C. for 60 seconds. The amount of the fixing agent applied was 4.2% with respect to the applied portion of the glass fiber woven fabric. WEA18W-BZ2 (manufactured by Nitto Boseki Co., Ltd.) was used as the glass fiber woven fabric. Cut the center part of the part of the glass fiber woven fabric on which the anti-fray adhesive was applied along the warp, pull one of the warp yarns at the end, and measure the adhesive strength to measure the ear fray strength. (G). Also, in various solvents for 72 hours (25
(° C.), the condition of the coated part was observed, and the solvent resistance was evaluated. The results are shown in Table 1. ○ in Table 1
Indicates that the applied part has not changed, and x indicates that the warp in the applied part has frayed.

Example 2 Water-soluble urethane resin in Example 1 (HUX-232 Asahi Denka Kogyo Co., Ltd.)
Example 1 was repeated except that the concentration was changed to 30%.
The results are shown in Table 1. [Example 3] The water-soluble urethane resin (H
UX-232 Asahi Denka Co., Ltd.) Concentration 40%
Example 1 was repeated except that The results are shown in Table 1. [Example 4] The epoxy type cross-linking agent (HUX-X) was added to Example 1.
Example 1 except that 4% of W Asahi Denka Kogyo Co., Ltd. was added
It carried out similarly to. The results are shown in Table 1. Comparative Example 1 Water-soluble urethane resin (H
UX-232 Asahi Denka Kogyo Co., Ltd.) Concentration 10%
Same as Example 1 except that The results are shown in Table 1.

[0018]

[Table 1]

[0019]

The anti-raveling adhesive of the present invention has excellent productivity because it can be applied to a glass fiber woven fabric and then dried. Further, since it has a urethane bond, it has high adhesive strength, and the coating has flexibility and excellent solvent resistance. Therefore, the glass fiber woven fabric coated with the anti-fray adhesive of the present invention has excellent edge fraying property, and even when impregnated with an epoxy resin varnish at the time of manufacturing a prepreg, it causes fraying during heating and drying. Never. or,
Since the coating itself is flexible, the coated part does not crack or break during handling. Furthermore, since the adhesive strength of the coating film is high, it is possible to reduce the coating amount very much. Therefore, there is almost no difference in thickness between the portion to which the anti-fray adhesive agent is applied and the portion to which the anti-fray adhesive agent is not applied. . As a result, when a prepreg is produced using the glass fiber woven fabric of the present invention and cut into a certain size and stacked, a difference in height between the end portion and the central portion hardly occurs. Furthermore,
In addition to the advantages described above, the adhesive of the present invention is water-soluble or water-dispersed, and therefore has the advantage of not having a disaster prevention problem such as a fire, working environment, and waste liquid treatment. is doing.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location D03D 5/00 Z 7199-3B 15/00 E 7199-3B

Claims (2)

[Claims] 1. An anti-fraying adhesive agent for glass fiber fabrics, which comprises an aqueous urethane resin. 2. The anti-fraying adhesive according to claim 1, wherein the glass fiber fabric is applied to a fixed width of both ears, relative to the weight of the applied portion.
A glass fiber woven fabric characterized by being applied and cured at 2 to 10%.