JPH0813343A - Antifray fixing agent for glass cloth, glass fiber fabric using the same and their production - Google Patents

Abstract

PURPOSE:To obtain the subject fixing agent, consisting essentially of a reactional product of a specific epoxy resin with an a mine compound containing hydroxyl group and capable of preventing warp yarns from fraying by applying thereof to selvedge parts of a glass fiber fabric. CONSTITUTION:This antifray fixing agent consists essentially of a reactional product of an epoxy resin having 1500-3000 epoxy equiv. and 2000-4000 molecular weight with an amine compound containing hydroxyl group (e.g. ethanolamine or diethanolamine) and an isocyanate-based curing agent, e.g. tolylene diisocyanate or hexamethylene diisocyanate. This glass fiber woven fabric is obtained by applying a treating liquid containing the antifray fixing agent in a solvent to a prescribed width of selvedge parts of the glass fiber fabric woven especially by an air jet loom, etc., then hot-curing the reactional product and thereby making warp yarns in the selvedge parts hardly fray. The amount of the applied antifray fixing agent is 2-10% based on the weight of the parts to be coated. This antifray fixing agent is sparingly soluble in organic solvents. The selvedge parts are not frayed even by impregnating the woven fabric with the epoxy resin varnish or using the organic solvents in preparing a prepreg.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an anti-fray adhesive agent for glass fiber fabric. The anti-fray adhesive of the present invention is
It is particularly preferably used for preventing anti-fraying of a glass fiber woven fabric woven by an air jet loom or the like used for a copper clad laminate.

[0002]

2. Description of the Related Art Glass fiber woven fabrics were previously woven by shuttle looms, but recently, the proportion of those woven by air jet looms is increasing. In particular, 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 an air jet loom, the weft thread is cut after each weft insertion,
The weft cutting ends are present in tufts at both ears of the fabric. 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 plurality of the prepregs are laminated, copper foils are laminated, and heated and pressed to obtain a copper-clad laminate.

The following problems occur when a prepreg is manufactured from a glass fiber fabric having tufts woven by an air jet loom or the like.

The first problem is that the glass fiber woven fabric contains excess resin in the tuft portion, and the ear portion tends to be thicker than other portions. 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 at the places where the ears are present and the height is uniform as a whole. do not become. Such a prepreg having a non-uniform thickness over the entire width brings various inconveniences when it is used to manufacture a product. 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 has irregularities due to the tufts. When these prepregs with irregularities on both ends are cut to a certain length and piled up, there is a drawback that the edges are difficult to align.When further aligning the edges, some of the irregularities scatter off and mix into the prepreg. And cause defective products.

The third problem is that the glass fibers of the tufted ear are cut off during the production of prepreg and are mixed in the varnish and fixed on the surface of the prepreg, causing defective products. is there.

As described above, the first problem may similarly occur in the ear of the glass fiber fabric in which the prepreg is manufactured from the glass fiber fabric having the tufts.

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 woven fabric is unavoidable. And the yield of the varnish decreases, which is not preferable in terms of cost.

Further, it is possible to consider removing the ear portion from the glass fiber fabric before forming the prepreg, and some proposals have been made. For example, a method of fusing the tufted ear with a laser beam and at the same time fusing the cut end,
There is a method in which a thermoplastic resin thread is woven into the warp selvage portion of a glass fiber woven fabric, and the thermoplastic resin thread portion is heat-sealed after weaving. 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 yarn of the thermoplastic resin into the warp selvage has a problem that it cannot be applied to a special woven fabric because it cannot perform the heat deoiling which is a usual process in the production process of the glass fiber woven fabric.

On the other hand, a proposal has been made to try to solve the above problems by applying an anti-raveling adhesive to the inner part of the ear of the glass fiber fabric (for example, Japanese Patent Laid-Open No. 5-222676). . However, in this case, when the epoxy resin varnish is impregnated in the prepreg step, the epoxy resin varnish is heated while containing the organic solvent. For this reason, there are cases where troubles such as the portion where the anti-fray sticking agent is applied are dissolved in the organic solvent and the warp at the end is frayed and entangled with the roller of the prepreg device. Therefore, there has been a demand for the development of a fray-preventing sticking agent which has a strong adhesive force and is less likely to dissolve the coated portion in an organic solvent.

[0011]

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 is An object of the present invention is to provide an anti-fray adhesive which does not fray and does not easily swell or melt even if a solvent used for a thermosetting resin varnish is used.

A second object of the present invention is to obtain a uniform thickness over the entire width when a thermosetting resin varnish is impregnated with a glass fiber woven fabric having an anti-fraying adhesive applied to the cut ends of ears to form a prepreg. The width of both ends is straight, there is no unevenness in the lateral direction, and the glass fiber woven fabric enables the prepreg without the glass fibers at the ends being cut off and adhering to other parts to deteriorate the quality. And to provide a manufacturing method thereof.

[0013]

[Means for Solving the Problems] In order to achieve the above objects, the present inventors have made and studied various anti-raveling adhesives. As a result, surprisingly, when a reaction product of a certain type of epoxy resin with a hydroxyl group-containing amine compound and an isocyanate curing agent are used, the thermosetting resin varnish swells or melts even when impregnated. And not
I found that the adhesiveness is good. Furthermore, it has been discovered that it is therefore possible to produce glass fiber fabrics whose ears do not become thick. The present invention has been achieved based on such findings.

The anti-fray adhesive agent for the glass fiber fabric which achieves the first object has an epoxy equivalent of 1500 to 330.
0, a reaction product of an epoxy resin having a molecular weight of 2000 to 4000 and a hydroxyl group-containing amine compound, and an isocyanate curing agent as essential components.

The glass fiber fabric which achieves the second object is
This anti-fray adhesive is applied to a certain width of the ears of the glass fiber fabric in an amount of 2 to 10 with respect to the weight of the coated part of the glass fiber fabric.
% Coating and curing.

The reaction product of an epoxy resin and a hydroxyl group-containing amine compound (hereinafter sometimes referred to as an epoxy-amine reactant), which is an essential component in the anti-raveling adhesive of the present invention, usually has an epoxy equivalent of 1500 to 500. 330
It was obtained by reacting an epoxy resin of No. 0 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 the epoxy equivalent is 150 as described above.
The molecular weight is limited to 0 to 3300 and 2000 to 4000.

If the molecular weight or epoxy equivalent is smaller than the above range, solvent resistance becomes poor. Also, a large amount of anti-sticking agent is required to obtain sufficient adhesive strength. further,
If the molecular weight or the epoxy equivalent is larger than this, the coated part becomes brittle and cracks or breaks due to impact.

The hydroxyl group-containing amine compound that is reacted with the epoxy resin is preferably a hydroxyl group-containing primary amine or secondary amine compound, and specific examples thereof include:
Monoethanolamine, mono-n-propanolamine,
Monoisopropanolamine, monobutanolamine,
Examples include diethanolamine, methylaminoethanol, ethylaminoethanol, dipropanolamine and the like.

The reaction between the epoxy resin and diethanolamine is carried out as follows, for example. 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. The solvent to be used may be one that can dissolve the epoxy resin and the hydroxyl group-containing amine compound, for example,
Examples include diacetone alcohol and isopropyl cellosolve. Then, the hydroxyl group-containing amine compound is dropped into the epoxy resin solution to carry out the reaction. When the reaction is completed, the reaction 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.

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. .

The anti-fray adhesive of the present invention contains an isocyanate curing agent as an essential component for reacting with the hydroxyl group of the epoxy-amine reactant to form a urethane bond and curing the epoxy-amine reactant. Isocyanate curing agent used, as long as it reacts with a hydroxyl group to form a urethane bond, the type does not matter, tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 4, Examples thereof include polyisocyanates such as 4-dicyclohexylmethane diisocyanate and trimethane triisocyanate. Isocyanates have the drawback of being decomposed by reacting with water, and therefore, the -NCO group blocking agent of the above isocyanates is blocked from the viewpoint of storage stability and complete reaction with the epoxyamine reactant. Blocked isocyanates blocked with (for example, phenol, oxime, lactam, malonic acid ester, ethyl acetoacetate, etc.) are preferable. The amount of the isocyanate-based curing agent used is preferably an amount such that 1 or 2 isocyanate groups are present with respect to 1 hydroxyl group in the epoxyamine reactant. If the amount used is less than this, the reaction is not sufficiently performed, and the effect of preventing fraying becomes weak. If it is more than this, the reaction becomes difficult to be performed. The curing temperature is 160
The curing is completed in 10 to 60 seconds at ˜240 ° C.

The anti-fray adhesive solution 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 10% by weight (solid content) based on the applied portion of the glass fiber fabric. As a coating method, a roller method is preferable, but a brush or the like may be used. The anti-fray adhesive may be applied to any position as long as it is a position to prevent fraying of the glass fiber fabric, but it is a tuft woven by an air jet loom used for copper-clad laminates. In the case of a glass fiber woven fabric having ears, it is preferable to apply the inside of both ears to a width of about 10 mm in the warp direction.

The glass fiber fabric coated with the anti-raveling adhesive is continuously introduced into the heating section, the solvent is dried,
Further, a curing reaction of the anti-fray adhesive agent 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 to
The temperature is 200 ° C., and the heating time is 30 seconds to 1 minute, and the reaction is completed. After the heating, the glass fiber woven fabric is further cut by a slitter at about the central portion of the anti-fray adhesive applied to a width of about 10 mm. This cutting takes place simultaneously on both ears of the fabric. Therefore, the cut glass fiber woven fabric is in a state where the anti-fraying 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.

As the woven fabric used for the glass fiber woven fabric to which the anti-raveling adhesive of the present invention is applied, a glass fiber woven fabric which has been deoiled after weaving and further treated with a surface treatment agent such as a silane coupling agent is used. It is desirable that the anti-fraying treatment is performed after deoiling and before the surface treatment.
After that, surface treatment may be performed. Also, in the case of woven fabrics made of glass yarn using a sizing agent that does not require deoiling, part of the sizing agent does not require a deoiling step, and a surface treatment agent is also included in the sizing agent. No process is required. Therefore, the glass fiber woven fabric after the weaving can be subjected to the anti-raveling treatment.

[0026]

【Example】

[Example 1] (1) The anti-raveling adhesive solution was prepared as follows. B) An epoxy-amine reactant obtained by reacting 1 mol of a bisphenol A type epoxy resin (epoxy equivalent: 1750 to 2100, molecular weight: 2900) with 2 mol of diethanolamine. B) Blocked isocyanate (ethyl acetoacetate block of isocyanurate of hexamethylene diisocyanate NCO 10.2%, solid content 80%). B) One hydroxyl group of the epoxy-amine reactant b)
The isocyanate group of the blocked isocyanate curing agent is 2
The solution was prepared so that the solid content was 20%, and the solid content was diluted with methyl cellosolve to obtain an anti-fray adhesive fixing agent solution.

(2) The adhesive solution obtained in the above (1) is applied to both ears of the glass fiber fabric by a roller coater with a width of 1
It was applied along the warp at 0 mm, and then heated at 180 ° C. for 30 seconds. The coating amount of the fixing agent was 2.6% with respect to the coated portion of the glass fiber woven fabric. Glass fiber fabric is W
EA18W-BZ2 (manufactured by Nitto Boseki Co., Ltd.) was used.

(3) The glass fiber woven fabric obtained in the above (2) is cut along the warp at the center of the portion to which the anti-raveling adhesive is applied, and one of the warp yarns at the end is pulled,
The adhesive strength was measured and taken as the ear fray strength (g). Also,
It was immersed in various solvents for 72 hours (room temperature), and the state of the coated part was observed to evaluate the solvent resistance. The degree of insolubility of the fixing agent in the solvent was defined as the degree of insolubility and expressed by the following formula. Insolubility (%) = [weight after solvent immersion (g)] / [weight before solvent immersion (g)] The results are shown in Table 1.

[Table 1]

[Embodiment 2] The epoxy resin used in Embodiment 1 has an epoxy equivalent of 2400 to 3000 and a molecular weight of 37.
The same procedure as in Example 1 was performed except that the value was changed to 50. Table 1 shows the results.

Example 3 Example 3 was repeated except that the ratio of isocyanate groups to hydroxyl groups was changed to 1.0. Table 1 shows the results.

[Example 4] The same procedure as in Example 2 was repeated except that the ratio of isocyanate groups to hydroxyl groups in Example 2 was changed to 1.0. Table 1 shows the results.

[Comparative Example 1] In Example 1, an epoxy resin having an epoxy equivalent of 400 to 500 and a molecular weight of 90 was used.
0, and the same procedure as in Example 1 except that the ratio of isocyanate groups to hydroxyl groups was 0.5. Table 1 shows the results.

[Comparative Example 2] The same procedure as in Example 1 was repeated except that the epoxy resin used in Example 1 had an epoxy equivalent of 400 to 500 and a molecular weight of 900. Table 1 shows the results.

Comparative Example 3 The procedure of Example 3 was repeated, except that the epoxy resin used in Example 3 had an epoxy equivalent of 400 to 500 and a molecular weight of 900. Table 1 shows the results.

[0035]

The adhered portion of the glass fabric coated with the anti-raveling adhesive of the present invention is less soluble in the organic solvent than the one using the conventional anti-raveling adhesive. Therefore, when making a prepreg, even if it is impregnated with an epoxy resin varnish and an organic solvent is used, it does not fray.

In the glass fiber woven fabric coated with the anti-raveling adhesive of the present invention, since the coating film of the anti-raveling adhesive has flexibility, the coated portion does not break or break. Also, because the adhesive strength of the anti-fray adhesive is great, a small amount of application,
The effect of preventing fraying can be exhibited. Therefore, since there is almost no difference in thickness between the coated part and the uncoated part, prepreg of the glass fiber woven fabric is cut into a certain length, and even if they are stacked, the difference in height between the end part and the central part does not occur. rare.

Claims (3)

[Claims] 1. A glass fiber fabric comprising a reaction product of an epoxy resin having an epoxy equivalent of 1500 to 3300 and a molecular weight of 2000 to 4000 and a hydroxyl group-containing amine compound, and an isocyanate curing agent as essential components. Anti-fray adhesive. 2. The anti-fray adhesive according to claim 1, which is applied and cured in a fixed width of an ear portion of the glass fiber fabric in an amount of 2 to 10% based on the weight of the coated portion of the glass fiber fabric. Characteristic glass fiber fabric. 3. The anti-fray adhesive according to claim 1, which is applied and cured in a fixed width of the ear of the glass fiber fabric in an amount of 2 to 10% of the weight of the coated part of the glass fiber fabric. A method for producing a glass fiber woven fabric characterized.