JPH06192965A - Fixing agent for preventing glass fiber woven fabric from fraying and glass fiber woven fabric using the same - Google Patents

Abstract

PURPOSE:To obtain a preventing agent for fraying, excellent in fray preventing effects in preventing a cut end of a glass cloth from fraying and usable in an aqueous system without changing the thickness in a coated part. CONSTITUTION:This fixing agent for preventing a glass cloth from fraying is composed of a reactional product of an epoxy resin having 150-1000 epoxy equiv. and 500-2000 molecular weight with a hydroxyl group-containing amine and a water-soluble isocyanate-based curing agent. Furthermore, this glass cloth is obtained by coating prescribed widths of both selvedges with the fixing agent.

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]

[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. The gist of the invention is that it is composed of a reaction product and a water-soluble isocyanate curing agent. Further, the glass fiber woven fabric for achieving the second object is coated with the anti-fray fixing agent in both ears at 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 contains a resin water-solubilized by reacting an epoxy resin with a hydroxyl group-containing amine compound and a water-soluble isocyanate curing agent as essential components. That is the summary.

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 carried out 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, it is preferable to react the epoxy rings at both ends of the epoxy resin with the hydroxyl group-containing amine compound, respectively.
An epoxy-amine reactant having hydroxyl groups derived from the amine compound at both ends is obtained.

In the anti-fray adhesive agent of the present invention, a water-soluble isocyanate effect 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. Contained as. If the water-soluble isocyanate curing agent used is one that reacts with a hydroxyl group to form a urethane bond,
The type does not matter. There are the following two types of such water-soluble isocyanate-based 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-soluble isocyanate 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. The temperature during curing is 140 to 200 ° C., and the curing is completed in 20 seconds to 1 minute. The anti-fray adhesive of the present invention is used by dissolving the above-mentioned two kinds of essential components in water. The amount of the solvent is preferably 10 to 20 times the amount of the epoxy-amine reactant.

The anti-fray adhesive solution thus prepared is applied to the anti-fray part 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 application 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 with tassels woven by an air jet loom, the inside of both ears is about 10 mm.
It is preferable to apply the width 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 moisture, 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. After heating, the glass fiber woven fabric is further treated by a slitter for about 10 minutes.
Cut approximately the center of the anti-fray adhesive applied to the width of mm. This cutting takes place simultaneously on both ears of the fabric. Therefore, the cut glass fiber woven fabric is about 5 mm on both ends.
With the width anti-fray adhesive applied, the ears, including the tassels, will be removed from the fabric.

The fabric used for the glass fiber fabric coated with the anti-raveling adhesive of the present invention is a glass fiber 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.

[0017]

The anti-fraying adhesive of the present invention comprises a reaction product (epoxy-amine reactant) of an epoxy resin and a hydroxyl group-containing amine compound and a water-soluble isocyanate curing agent, and the former is cured by the latter. By doing so, 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-soluble isocyanate-based curing agent is a block type, the reaction hardly progresses at room temperature, and there is no problem in the pot life of the anti-fray adhesive agent solution. Further, since the epoxy-amine reactant and the isocyanate curing agent are water-soluble, 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.

[0019]

【Example】

Example 1 An anti-fraying adhesive solution was prepared as follows. B) Epikote 1001 (Epoxy equivalent manufactured by Yuka Shell Co., Ltd. Epoxy equivalent 450-500, molecular weight 900) 1 mole of diethanolamine reacted with 2 moles of epoxy-amine reactant b) Forced emulsification type blocked isocyanate (Elastron BN69 Daiichi Kogyo Seiyaku Co., Ltd.) A) Isocyanate group content of 7.0%) c) It is prepared such that the isocyanate curing agent of b) is 2 isocyanate groups per 2 hydroxyl groups of the epoxy-amine reactant of a), and the solid content is 20%. Was diluted with water to obtain a fray-preventing adhesive solution. The adhesive solution of No. 1 was applied to both ears of the glass fiber fabric with a roller coater along the warp with a width of 10 mm, and then 1
It was heat-cured at 80 ° C. for 30 seconds. The amount of the fixing agent applied was 3.8% with respect to the applied portion of the glass fiber woven fabric. Glass fiber fabric is WEA18W-BZ2 (manufactured by Nitto Boseki Co., Ltd.)
It was used. 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 The procedure of Example 1 was repeated, except that the molar ratio of isocyanate groups to hydroxyl groups in Example 1 was changed to 1.5. The results are shown in Table 1. Example 3 The procedure of Example 1 was repeated, except that the molar ratio of isocyanate groups to hydroxyl groups in Example 1 was 1.2. The results are shown in Table 1. [Comparative Example 1] The procedure of Example 1 was repeated, except that the molar ratio of isocyanate groups to hydroxyl groups in Example 1 was changed to 0.5. The results are shown in Table 1.

[0021]

[Table 1] (1) dimethylformamide

[0022]

EFFECT OF THE INVENTION The anti-fray adhesive of the present invention has a high curing rate and therefore has excellent 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. Further, since it has a urethane bond, the adhesive strength is high, and the coating film is flexible and 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 advantages as described above, the adhesive of the present invention is a water-soluble or water-dispersed system, and therefore a disaster prevention problem such as a fire occurrence,
It has the merit of not having problems such as working environment and waste liquid treatment.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number for FI Technical location D03D 15/12 A 7199-3B D06M 13/395 // D06M 101: 00

Claims (2)

[Claims] 1. A fray of a glass fiber woven fabric, which comprises 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, and a water-soluble isocyanate curing agent. Prevent sticking agent. 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%.