JPH06341065A - Antifraying binder for glass fiber woven cloth and glass fiber cloth using the same - Google Patents

Abstract

PURPOSE:To provide an antifraying binder which has excellent antifraying effect at the cut edges of glass cloth without change in thickness at the coated parts and can be used in an aqueous system at an increased curing speed. CONSTITUTION:The antifraying binder comprises (A) a reaction product of an epoxy resin of 150 to 1,000 epoxy equivalents and 500 to 2,000 molecular weight and a hydroxyl group-containing amine, (B) a water borne isocyanate type curing agent and (C) a reaction-accelerating catalyst. The glass fiber cloth is obtained by applying the antifraying binder to both selvages in a certain width.

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 woven fabrics, and more particularly to an ear fray prevention adhesive agent for glass fiber woven fabrics woven by an air jet loom or the like 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.

The following problems occur 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 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 the threads of the thermoplastic resin into the warp selvages cannot perform the heat deoiling which is a normal step as the manufacturing process of the glass fiber woven fabric.
There is a problem that it can only be applied to special 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 may occur. It happened. 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, there are problems in terms of safety such as fire, working environment due to solvent vapor, and 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-fray adhesive agent for glass fiber fabrics, which does not swell in the solvent used for the thermosetting resin varnish. A second object of the present invention is to provide a uniform thickness over the entire width when a thermosetting resin varnish is impregnated with a glass fiber woven fabric having anti-fraying adhesive applied to the cut ends of both ears. With a glass fiber woven fabric that makes it possible to make a prepreg without both ends of the width being straight, there is no unevenness in the lateral direction, and the glass fibers at the ends are cut off and attached to other parts and the quality is not deteriorated. To provide. Furthermore, a third object of the present invention is to use an aqueous solvent as the resin solvent, instead of an organic solvent.
A fourth object of the present invention is to accelerate the reaction rate of these resins and improve work efficiency.

[0011]

[Means for Solving the Problems] An anti-fraying adhesive agent for a glass fiber fabric for achieving the first object comprises an epoxy resin having an epoxy equivalent of 150 to 1000 and a molecular weight of 500 to 2000 and a hydroxyl group-containing amine compound. It is a gist that the reaction product and an aqueous isocyanate type curing agent are used. Further, the glass fiber woven fabric for achieving the second object is coated with the anti-fray adhesive fixing agent at both ears in an amount of 2 to 10% of the weight of the coated portion of the glass fiber woven fabric and cured. And Furthermore, the anti-fraying adhesive agent of the glass fiber woven fabric for achieving the third object, the resin solubilized by reacting the hydroxyl group-containing amine compound with the epoxy resin, and the water-based isocyanate type curing agent as essential components Is the gist. Further, the anti-fraying adhesive agent for the glass fiber fabric that achieves the fourth object is a resin solubilized by reacting an epoxy resin with a hydroxyl group-containing amine compound and an aqueous isocyanate type curing agent,
The gist is to add a catalyst that accelerates the reaction rate as an essential component.

The reaction product (hereinafter referred to as epoxy-amine reactant) of the epoxy resin and the hydroxyl group-containing amine compound, which is an essential component in the anti-raveling adhesive of the present invention, has an epoxy equivalent of 150 to 1000 and a molecular weight of 500 to 2000.
It is obtained by reacting the epoxy resin of 1) with a hydroxyl group-containing amine compound. The epoxy resin which is a raw material of the epoxy-amine reactant may be a bisphenol type or a novolac type, but as described above, the epoxy equivalent is limited to 150 to 1000 and the molecular weight is limited to 500 to 2000. The reason is that if the epoxy equivalent or molecular weight is smaller than this range, sufficient adhesion between glass fibers cannot be obtained, and if it is larger than this range, the coated part becomes brittle and the impact This is because it will be cracked or broken by.

The hydroxyl group-containing amine compound used in the reaction with the epoxy resin is preferably a hydroxyl group-containing primary amine or secondary amine, and specific examples thereof include
Monoethanolamine, mono-n-propanolamine,
Monoisopropanolamine, monobutanolamine,
Examples include diethanolamine, methylaminoethanol, ethylamine ethanol, dipropanolamine and the like. The reaction between the epoxy resin and diethanolamine is performed as follows. A solvent is added so that the epoxy resin has a concentration of about 50%, and the mixture is heated until the boiling point of the solvent is reached. Any solvent may be used as long as it can dissolve the epoxy resin and diethanolamine, and examples thereof include diacetone alcohol and isopropyl cellosolve. Then, diethanolamine is added dropwise to carry out the reaction. When the reaction is completed, the mixture is cooled to room temperature to obtain an epoxy-amine reactant which is an essential component of the anti-fray adhesive of the present invention. It is soluble in water because the terminal group is a hydroxyl group. In this reaction, the epoxy rings at both ends of the epoxy resin are preferably reacted with a hydroxyl group-containing amine compound, respectively, whereby an epoxy-amine reactant having hydroxyl groups derived from the amine compound at both ends is obtained.

In the anti-fray adhesive of the present invention, an aqueous isocyanate type curing agent for curing the epoxy-amine reactant by reacting with the hydroxyl group of the epoxy-amine reactant to form a urethane bond is an essential component. contains. The water-based isocyanate type curing agent used may be of any type as long as it reacts with a hydroxyl group to form a urethane bond. There are the following two types of such water-based isocyanate type curing agents. 1) Forced emulsification type: a urethane prepolymer having an isocyanate group blocked with a hydrophobic blocking agent,
Forcibly emulsified with an emulsifier. 2) Self-emulsifying type: A self-emulsifying urethane prepolymer blocked with a blocking agent having a hydrophilic group without using an emulsifier. With the above structure, water can be used as a solvent, and since it is a block type, it has excellent storage stability.

The amount of the water-based isocyanate type curing agent used is preferably 1 to 2 isocyanate groups per 1 hydroxyl group in the epoxy-amine reactant. If the amount used is less than this, the reaction is not sufficiently performed and the effect of preventing fraying becomes weak. If the amount is larger than this, the reaction becomes difficult to be performed. Curing temperature is 1
The temperature is 40 to 200 ° C., and the curing is completed in 20 seconds to 1 minute. In addition, a catalyst is added to further accelerate the reaction temperature in the anti-fray adhesive of the present invention. This catalyst is generally triethyleneamine, naphthex zinc,
Examples include stanna octoate. The reaction promoting catalyst as described above is added to the block type isocyanate curing agent at a concentration of 1 to 10%. By adding such a catalyst, the dissociation temperature of the blocking agent of the blocked type isocyanate is lowered and the reaction rate is increased. Therefore, the curing time is reduced from 140 to 200 ° C to 120 to 180 ° C, and the curing time is also shortened by 10 to 30 seconds as compared with the case where the resin is applied under the condition without a catalyst, and the productivity is improved. Can be achieved. In the anti-raveling adhesive of the present invention, the above-mentioned two kinds of essential components are dissolved in water before use. The amount of the solvent is preferably 10 to 20 times that of the epoxy-amine reactant. As a solvent, it is possible to use only water,
It is also possible to mix an organic solvent such as water-soluble alcohol or acetone.

The anti-fray adhesive agent solution thus prepared is applied to the anti-fray portion of the glass fiber fabric. The application amount is such that the solid content of the anti-fray adhesive agent is 2 to 10% by weight ratio with respect to the application portion of the glass fiber woven fabric. A roller method is preferable as the coating method, but a brush method or the like is also possible. The anti-raveling adhesive is applied at any position as long as it is intended to prevent fraying of the glass fiber fabric, but it is used for the copper clad laminate which is the second invention of the present invention. In the case of a glass fiber woven fabric having tassels woven by an air jet loom or the like, it is preferable to apply the inner side of both ears to a width of about 10 mm in the warp direction. The glass fiber woven fabric coated with the anti-raveling adhesive is subsequently introduced into the heating section to dry the water, and further, the curing reaction of the anti-raveling adhesive is performed. The heating conditions in this case vary depending on the type, addition amount, and concentration of the curing agent, but as described above, the heating temperature is 140 ° C. to 200 ° C. and the heating time is 30 seconds to 1 minute. To do. The heated glass fiber woven fabric is then further continuously slitted by about 10 mm.
Cut approximately the center of the anti-fray adhesive applied across the width. This cutting takes place simultaneously on both ears of the fabric. Therefore, the cut glass fiber woven fabric is in a state in which the anti-fray adhesive having a width of about 5 mm is applied to both ends, and the ears including the tufted ears are removed from the woven 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 deoiled after weaving and further treated with a surface treatment agent such as a silane coupling agent. Although it is desirable, after deoiling, perform anti-fray treatment at the stage before surface treatment,
After that, surface treatment may be performed. 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.

[0018]

The anti-fray adhesive of the present invention comprises a reaction product (epoxy-amine reactant) of an epoxy resin and a hydroxyl group-containing amine compound and an aqueous isocyanate type curing agent, and the former is cured by the latter. As a result, a cured product having the characteristics of an epoxy resin and the characteristics of a urethane resin can be obtained, so that it has an excellent effect of preventing fraying and also has solvent resistance. Further, since this reaction is a urethane bond, the curing reaction product has a coating property, and the coating film has flexibility despite being a three-dimensional cured product. Further, the curing reaction is also carried out very quickly, so that the productivity is excellent. Since the water-based isocyanate type curing agent is a block type, the reaction hardly progresses at room temperature, and there is no problem in the pot life of the fray prevention adhesive agent solution. Further, since the epoxy-amine reactant, the isocyanate type curing agent and the catalyst are water-soluble or water-dispersible, water can be used as a solvent.

In the glass fiber woven fabric coated with the anti-raveling adhesive of the present invention, the coating film of the anti-raveling adhesive has flexibility, so that the coated portion does not break or break. Further, since the strength of the coating film is high, the effect of preventing fraying can be exhibited with a small amount of coating. 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. Furthermore, since the anti-fray adhesive of the present invention has a three-dimensional structure, fray does not occur even when it is impregnated with an epoxy resin varnish to form a prepreg.

[0020]

【Example】

Example 1 An anti-fraying adhesive solution was prepared as follows. A) An epoxy-amine reactant obtained by reacting 1 mol of a bisphenol A type epoxy resin (epoxy equivalent: 450 to 500 molecular weight: 900) with 2 mol of diethanolamine. B) Forced emulsification type blocked isocyanate (Elastron BN69, Dai-ichi Kogyo Seiyaku Co., Ltd. NCO 7.0)
%) C) Amine-based catalyst [Elastron Catalyst 69, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] b) per 1 hydroxyl group of epoxy-amine reactant b) blocked isocyanate curing agent has 2 isocyanate groups
1% of the amine catalyst of c) is added to the blocked isocyanate to obtain a solid content of 2
The solution was diluted with water to 0% to obtain an anti-fray sticking agent 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 heat-cured at 180 ° C. for 15 seconds. The coating amount of the fixing agent was 3.8% with respect to the coated portion of the glass fiber woven fabric. WEA18W-BZ2 [manufactured by Nitto Boseki Co., Ltd.] was used as the glass fiber woven fabric. The center portion of the anti-raveling agent-applied part of the glass fiber woven fabric obtained in the above was cut along the warp, one of the warp yarns at the end was pulled, the adhesive strength was measured, and the ear fray strength (g) And In addition, the solvent resistance was evaluated by immersing in various solvents for 72 hours (room temperature) and observing the state of the coated part. The results are shown in Table 1. In Table 1, ∘ indicates that the coated portion did not change, Δ indicates that the warp in the coated portion was slightly frayed, and x indicates that the warp in the coated portion was frayed.

Example 2 Example 2 was repeated except that the amount of the catalyst added in Example 1 was 3% based on the blocked isocyanate. The results are shown in Table 1. Example 3 The procedure of Example 1 was repeated, except that the amount of the catalyst added in Example 1 was 5% with respect to the blocked isocyanate. The results are shown in Table 1. [Example 4] The same procedure as in Example 1 was carried out except that the amount of the catalyst added in Example 1 was 10% with respect to the blocked isocyanate. The results are shown in Table 1. [Comparative Example 1] The same procedure as in Example 1 was carried out except that the catalyst in Example 1 was not added. The results are shown in Table 1.

[0022]

[Table 1]

[0023]

EFFECT OF THE INVENTION Since the anti-fray adhesive of the present invention contains a reaction accelerating catalyst, it has a high curing rate and is excellent in productivity when it is dried and cured after being applied to a glass fiber woven fabric. In addition, it is possible to extend the pot life at room temperature despite the high curing speed. Furthermore, since it has a urethane bond, it has high adhesive strength and the coating has flexibility,
It also has 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. Further, since the coating film itself has flexibility, the coated portion is not cracked or broken 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.
Further, while having the above advantages, the adhesive of the present invention is a water-soluble or water-dispersed system, and therefore does not have a disaster prevention problem such as a fire occurrence, a work environment, and a waste liquid treatment. have.

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Claims (2)

[Claims] 1. A reaction product of an epoxy resin having an epoxy equivalent of 150 to 1000 and a molecular weight of 500 to 2000 and a hydroxyl group-containing amine compound, an aqueous isocyanate type curing agent, and a reaction accelerating catalyst. Anti-fraying adhesive agent for glass fiber fabric. 2. The anti-fray adhesive of claim 1 is applied to a fixed width of both ears of the glass fiber fabric in an amount of 2 to 10% of the weight of the coated part of the glass fiber fabric and then cured. Characteristic glass fiber fabric.