JPH0657665A - Interlocking agent for preventing fray of woven fabric of glass - Google Patents

Abstract

PURPOSE:To obtain an interlocking agent for preventing fray of woven fabric of glass at a cut part suitable for a reinforcing material of resin plate such as board material for electronic material, etc., having much more improved adhesiveness and solvent resistance than a conventional one. CONSTITUTION:An interlocking agent for preventing fray of woven fabric of glass consists essentially of a copolyester which is a polyester comprising a terephthalic acid unit or a 2,6-naphthalenedicarboxylic acid unit as a main constituent component and contains an alicyclic dicarboxylic acid unit having a specific composition as a copolymerization acid component to the aromatic dicarboxylic acid unit.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-fraying adhesive useful for preventing fraying of edges (ears) of glass fabric when the glass fabric is used as a reinforcing material for printed circuit boards and other reinforced plastic products. is there.

[0002]

2. Description of the Related Art At present, a so-called fragment weaving machine, which inserts a weft yarn between warp yarns and cuts it, is generally used for weaving a glass fabric because of its high efficiency. At the both ends (ears) of the woven fabric sewn by this loom, tufts in which only wefts are continuously connected in a tuft are formed, but this tuft is unnecessary and after resin processing, etc. It is necessary to cut and remove it because it lowers the operability in the treatment process. At this time, if the portion is cut without fray-preventing treatment and treated with epoxy varnish impregnation, the warp of the fabric is easily frayed and wrapped around the roll, and the production line is temporarily stopped and treated. It will have to be done and it will be a huge loss.

On the other hand, in order to obtain an arbitrary width not only in the fragment loom but also in the woven fabric woven by the cored loom, it may be used by being divided and cut in the warp direction. At this time, when the fibers are divided by a simple mechanical cutting method, the warp is not prevented from being frayed, and thus the warp is easily frayed and there are many problems in use. Further, when the middle ear is formed and cut on the loom, the ears become tufted and cause the same problem as in the case of the fragment loom.

Therefore, it is necessary to apply some anti-raveling prescription to the portion to be cut of these woven fabrics, but as a means for preventing such fraying, a tufted portion or an end portion of the glass woven fabric is used by using a laser beam. A method has been proposed in which the (ears) are cut while being melt-bonded. Although this method has the advantage that it can be instantly bonded and that it is not attacked by the solvent such as epoxy varnish used during resin processing, it has low adhesive strength and forms a molten ball at the tip of the glass yarn. However, there was a problem such as falling even with a slight squeezing.

Further, a hot-melt resin such as ethylene-vinyl acetate copolymer, dimer acid polyamide, aromatic copolymer polyester is dissolved in an organic solvent to form tufts or edges (ears) of the glass fabric. There is a method of cutting after coating and drying. In this method, the resin is swollen in the organic solvent used for the epoxy varnish, or slightly dissolved, the resins may be eluted in the varnish, and these resins are applied to the glass fabric, After drying
When the glass fabric is wound, there is a problem that the surface resins of the laminated fabrics are fixed (blocked).
In particular, ethylene-vinyl acetate copolymer and dimer acid-based polyamide have poor solvent resistance, and elution into varnish becomes a problem.

For the above reasons, at present, a method of using an aromatic copolyester having a relatively well-balanced performance as a binder is predominant.

[0007]

DISCLOSURE OF THE INVENTION The present inventors consider that a copolymerized polyester effective as an anti-fraying adhesive agent for glass fabrics should be selected as a composition satisfying various conditions as described below. . (1) The anti-fray adhesive firmly permeates the glass fabric and has a strong adhesion with a small adhesion amount. (2) The adhered amount is such that when the adhered glass fabric is wound into a roll, it can be wound into a well-balanced roll, and the cut glass fabrics are laminated to give a non-uniform thickness. Be thin enough not to become. (3) The anti-fray adhesive agent should be applied to a glass fabric, dried, and immediately rolled up without blocking. (4) The resin used as the anti-raveling adhesive is soluble in a certain solvent and can be applied to the glass fabric in a solution state. (A halogen-based organic solvent, especially methylene chloride is generally used as this kind of solvent.) (5) The resin used as the anti-fray adhesive agent is easily decomposed or destroyed in the post-processing, or the resin is processed. When impregnating resin varnish solvent (eg hexane, toluene, ethanol,
Acetone, methyl ethyl ketone, dimethylformamide, etc.) swells or dissolves and loses adhesiveness,
Also, do not contaminate the varnish.

Under the circumstances where such conditions are demanded, there have been proposed adhesives having higher performance than before. For example, the adhesive agent described in JP-B-2-23626 is a typical example. This fixing agent is 40 to 90% of the dicarboxylic acid component.
Mol% is terephthalic acid, 10-40 mol% is at least one dicarboxylic acid component selected from isophthalic acid and saturated aliphatic dicarboxylic acids having 4 to 20 carbon atoms and alkylene having 2 to 10 carbon atoms. The main component is a copolyester composed of at least one glycol component selected from glycols. However, the anti-fray adhesive made of such a polyester resin has relatively excellent solvent resistance, but swells to some extent in a polar solvent such as dimethylformamide, and has adhesiveness to a glass fabric and anti-fray effect. In this respect, it is not yet sufficiently satisfactory, and an ideal polyester resin satisfying all the above four conditions has not been obtained yet. It is an object of the present invention to provide an anti-fraying adhesive agent for glass fabric, which has excellent performance and can solve all of these problems.

[0009]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that the use of a copolyester resin having a specific composition as the main component of a fray-preventing sticking agent The inventors have found that the object can be achieved and arrived at the present invention. That is, the present invention comprises 40 to 90 mol% of an aromatic dicarboxylic acid unit containing 90 mol% or more of a terephthalic acid unit or a 2,6-naphthalenedicarboxylic acid unit and 10 to 60 mol% of an alicyclic dicarboxylic acid unit. A non-fraying adhesive agent for glass fabrics, characterized in that a main component is a copolymerized polyester composed of an acid component and an alcohol component composed of an aliphatic diol unit and / or an alicyclic diol unit. .

The present invention will be described in detail below. The glass fabric anti-raveling copolyester of the present invention has excellent performance as a fixing agent as described above, that is, strong adhesiveness to glass and resistance to swelling / elution in a resin varnish solvent such as epoxy for resin processing. In addition to being excellent in solvent performance, it must be soluble in a halogen-based organic solvent due to the limitation of use in a solution state at that time.

As a result of intensive research as a main agent satisfying such characteristic requirements of the anti-raveling adhesive, it has been revealed that the modified copolyester as described below is most suitable. That is, the copolyester which is the main component of the anti-raveling adhesive of the present invention is a polymeric substance composed of an acid component and an alcohol component, and the acid component is a terephthalic acid unit, or a 2,6-naphthalenedicarboxylic acid unit. Hard acid component consisting of aromatic dicarboxylic acid units containing 90 mol% or more of 40 to 90
Mol% and the soft acid component consisting of alicyclic dicarboxylic acid units is 10 to 60 mol%. Here, the unit of each component represents a residue of the component carboxylic acid excluding the hydroxyl group.

Each of the above acid components exhibits the characteristics of each component in the form of a polymer chain segment formed by binding with an alcohol component. That is, the hard acid component is a component that maintains the crystallinity of the resin and makes a significant contribution to the improvement of solvent resistance, blocking resistance, and adhesiveness, and the soft acid component lowers the crystallinity of the specific solvent. It is a component that imparts appropriate solubility to, and enhances flexibility and fraying strength. In addition, coexistence of both components provides good rubber elasticity, and provides properties as a fabric adhesive.

Aromatic dicarboxylic acid units are preferred as the hard acid component, and terephthalic acid or 2,6-naphthalenedicarboxylic acid units are particularly preferred, and any one of them is required in order to fully exert the effects of the present invention. It is necessary that the unit of occupy 90 mol% or more in the wholly aromatic dicarboxylic acid unit. Examples of aromatic dicarboxylic acids other than the above include isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, diphenic acid and the like.

These subaromatic dicarboxylic acid units are terephthalic acid or 2,6 which is the main aromatic dicarboxylic acid unit.
-It is used as a small amount copolymerization unit with naphthalenedicarboxylic acid, but it is also possible to make both units of the main aromatic dicarboxylic acid unit mutually be a small amount copolymerization unit. That is, terephthalic acid units of 90 mol% or more and 2,6-
Both systems containing less than 10 mol% of naphthalenedicarboxylic acid units, more than 90 mol% of 2,6-naphthalenedicarboxylic acid units and less than 10 mol% of terephthalic acid units are also preferably used.

When the ratio of the subaromatic dicarboxylic acid unit to the main aromatic dicarboxylic acid unit exceeds 10 mol%, the solvent resistance to the resin solvent varnish is remarkably reduced, and the softening point, blocking resistance and fraying of the fixing resin are significantly reduced. It is not preferable because the strength is lowered.

The use of the alicyclic dicarboxylic acid unit as the soft acid component has an important meaning in expressing the effects of the present invention. That is, as compared with the conventionally used saturated aliphatic dicarboxylic acid unit, it is soluble in the halogen-based organic solvent which is the solvent of the present fixing agent by the selection of the above unit, but it is soluble in the other resin solvent described above. The dissolution resistance is further improved, and the fraying strength is remarkably increased. However, the composition ratio of the present soft acid component to all the acid components needs to be in the range of 10 to 60 mol% from the balance of the above-mentioned characteristics. If the soft acid component is less than 10 mol%, the solubility in halogenated organic solvents will decrease, and a solution of 5% by weight or more to obtain sufficient adhesiveness cannot be prepared. descend. On the other hand, when the content of the soft acid component exceeds 60 mol%, the solvent resistance to the above-mentioned resin solvent is lowered, and when the glass fabric is wound up after the adhesive solution is applied and dried, blocking becomes large to cause winding failure.

As the constituent material of the alicyclic dicarboxylic acid unit, a monocyclic aliphatic hydrocarbon, a polycyclic aliphatic hydrocarbon, or those containing one or more double bonds as a basic skeleton A monocyclic aliphatic carbonic acid such as 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,5-cyclooctanedicarboxylic acid, 1,6-cyclodecanedicarboxylic acid, etc. Dicarboxylic acid having hydrogen as a basic skeleton, or hydrogenated naphthalene ring,
Examples of the residue include dicarboxylic acids containing a polycyclic hydrocarbon ring unit such as a norcamphane ring, a dicyclopentadiene ring, a hydrogenated dicyclopentadiene ring, and an adamantane ring, from which hydroxyl groups of both acids have been removed. Among these, in particular, 1,4-cyclohexanedicarboxylic acid unit can maintain an appropriate solvent resistance in spite of the fact that 1,4-cyclohexanedicarboxylic acid as a raw material thereof is inexpensive and lowers the melting point of polyester. Therefore, it is particularly preferable.

As a typical example suitable for practical use, 1,4-
When cyclohexanedicarboxylic acid is used as the soft acid component, the ratio of the total acid component to 5 to 15 mol% is the best balance of performance such as adhesion, solvent resistance and blocking property. preferable.

The alcohol component is an aliphatic hydrocarbon or a diol unit having an alicyclic aliphatic hydrocarbon as a basic skeleton, and includes ethylene glycol, 1,3-propanediol, 1,3-butanediol, 1 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol,
1,12-dodecanediol, 1,20-eicosanediol,
1,4-cyclohexanedimethanol, 1,5-cyclooctanedimethanol, 1,6-cyclodecanedimethanol,
It is possible to select and use one kind or two or more kinds of residues obtained by removing hydrogen from an aliphatic diol such as 1,4-cyclohexanediol or an alicyclic diol. Among these, 1,4-butanediol units are particularly preferable because 1,4-butanediol as a raw material is inexpensive and can impart crystallinity to the polyester and maintain solvent resistance.

The method for producing the copolyester used in the present invention is not particularly limited, and known methods can be adopted. For example, a method of directly esterifying the above-mentioned dicarboxylic acid and glycol, or transesterifying with a dialkyl ester of dicarboxylic acid and glycol, followed by polycondensation can be adopted. In the case of esterification, transesterification, or polycondensation, a known catalyst can be used if necessary.

The anti-fraying adhesive of the glass fabric of the present invention is the above-mentioned copolyester as it is or, if necessary, an adhesion improver, a softening agent, a leveling agent,
An additive such as an anti-blocking agent is mixed and dissolved in a halogen-based organic solvent such as methylene chloride in a usual dissolution tank equipped with a stirrer. As a method of using the anti-raveling adhesive of the present invention in a glass fabric, the adhesive is quantitatively transported by a metering pump or the like, and a roll coater, a bar coater or the like is provided at a planned cutting point or an end (ear) of the glass fabric. The method of continuous coating using the general coating method of can be adopted as the most universal method.

[0022]

EXAMPLES The embodiments of the present invention will be specifically described below with reference to the following examples, but the present invention is not limited to the following examples without departing from the gist thereof.

Example 1 An acid component consisting of 65 mol of terephthalic acid and 10 mol of 1,4-cyclohexanedicarboxylic acid and a glycol component consisting of 1,4-butanediol were placed in a reaction vessel and the esterification reaction was carried out at 150 to 240 ° C. I did it. Next, 0.02 mol of tetra-n-butyl titanate was added as a catalyst and polycondensation reaction was carried out under reduced pressure to obtain a copolyester.

The above-mentioned copolyester is converted into methylene chloride.
It was completely dissolved at a concentration of 5% by weight. This solution was applied to the end of a glass fabric and dried, and the central part of the applied part was cut and wound on a roll. After winding, the roll did not reach the height of the ear, and the winding shape kept an extremely precise and well-balanced shape. No winding defects such as blocking during operation occurred.

The following properties of the glass fabric after winding were measured. -Solvent resistance: A 5 cm × 5 cm glass fabric sample is immersed in the solvent to be measured for 72 hours at room temperature (25 ° C), left to stand in the room for 3 hours and air-dried, and the appearance of the sample is observed. Solvent resistance was ranked according to criteria. ○: No change in appearance, △: Swelling, ×: Melt ・ Fraying strength: Same as above for a 5 cm × 5 cm glass fabric sample having a band-shaped anti-fraying resin coating part at one end The tensile jig was hooked, the other end of the tensile jig and the glass fabric was chucked in a tensile tester, and the tensile strength was measured by pulling at a pulling speed of 1 mm / min.

The following properties of the anti-raveling resin of the present invention were measured.・ Blocking property: 7% from a sheet obtained by uniformly applying a 5 wt% methylene chloride solution of this resin to a glass fabric on one side and drying.
Cut out 2 cm x 7 cm sample pieces and stack them so that the coated surfaces are in contact with each other. Temperature 140 ℃, pressure 10kgf
After heat-pressing at 10 cm / cm ² for 10 minutes and allowing to cool, both sample pieces were peeled off and the presence or absence of a block was examined. Elution rate of DMF: A film of 1 g / m ^{2 was formed} from a 7 wt% methylene chloride solution of this resin by a dry casting method (drying;
150 ℃ × 5 minutes), room temperature, or 70 ℃ in dimethylformamide (DMF) at a bath weight ratio of 1: 200 1
Soak for hours. This film sample was air-dried and then dried at 170 ° C for 2 hours.
The F dissolution rate was calculated. DMF elution rate = (sample weight before immersion-sample weight after immersion) /
Sample weight before immersion × 100 ・ Methylene chloride solubility: 5 parts of this resin fine powder sample was immersed in 95 parts of methylene chloride at room temperature and stirred for 1 hour or more to observe the dissolved state. The results were evaluated as follows. Dissolved: When completely dissolved, insoluble: When at least part of the insoluble part remains. B & R softening point (° C): measured according to the method of JIS-K2531.

Comparative Example 1 65 mol of terephthalic acid, 10 mol of isophthalic acid, adipic acid
Using 25 mol of the acid component and 1,4-butanediol as the glycol component, basically the same operation as in Example 1 was carried out to obtain a copolyester. A 5% by weight methylene chloride solution of this polyester was prepared, and applied to a glass fabric and a winding test were conducted in the same manner as in Example 1. For the above resin and glass fabric samples, solvent resistance, DMF elution rate, methylene chloride solubility, B & R softening point, fraying strength, and blocking property were measured as in Example 1. The observation / measurement results of Example 1 and Comparative Example 1 are summarized in Table 1 above.

[0028]

[Table 1]

As is clear from the results shown in Table 1, the composition is an exemplary composition of the anti-raveling adhesive of the present invention, as compared with Comparative Example 1 which is a representative example of the conventionally proposed anti-raveling adhesive. The copolymerized polyester solution of Example 1 has extremely strong fraying strength and excellent solvent resistance, particularly solvent resistance to DMF, and the anti-fraying adhesive of the present invention has higher performance than conventional products. It was found to be a composition of

Examples 2 and 3 and Comparative Examples 2 and 3 The compositions of the present invention, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, and 1,4-butanediol were variously changed in proportion. The blends of Examples 2 and 3 belonging to the scope of the invention and Comparative Examples 2 and 3 deviating from the scope of the present invention were prepared, and a copolyester was obtained basically by the same operation as in Example 1. Then, a methylene chloride solution having the same concentration as in Example 1 was prepared, and in the same manner as in Example 1, application to a glass fabric and winding test were performed.

For the above resin and glass fabric samples, solvent resistance, DMF elution rate, methylene chloride solubility, B & R softening point, fraying strength, and blocking property were measured in the same manner as in Example 1. Since Comparative Example 2 did not dissolve in methylene chloride, it could not be applied to the glass fabric. Therefore, the solvent resistance and DMF elution rate could not be measured. The observation / measurement results of Examples 2 and 3 and Comparative Examples 2 and 3 are summarized in Table 2.

[0032]

[Table 2]

Examples 2 and 3 shown in Table 2 and Comparative Example 2
As is clear from the comparison of 3 and 3, if the composition of the copolyester deviates from the scope of the present invention, it is not suitable for glass fabric use. The thing of Comparative Example 2 cannot be used in a methylene chloride solution because of insufficient solvent solubility. Further, since the solvent resistance of Comparative Example 3 is not sufficient, it may be eluted in the epoxy varnish. On the other hand, all the polyesters of Examples 1 to 3 having the composition within the range of the present invention have excellent performance.

[0034]

EFFECT OF THE INVENTION The anti-fraying adhesive agent for glass fabric of the present invention has a significantly superior adhesiveness to a glass fabric as compared with the conventional product, does not cause blocking, and is excellent in glass fabric with a small coating amount. Exhibits anti-fray performance. In addition, it has excellent solvent resistance to non-halogenated solvents used in resin varnish when used as a reinforcing material for resin plates such as board materials for electronic materials. It shows much more excellent solvent resistance against aprotic polar solvents such as DMF.

Claims (1)

[Claims] 1. A terephthalic acid unit or 40 to 90 mol% of an aromatic dicarboxylic acid unit containing 90 mol% or more of a 2,6-naphthalenedicarboxylic acid unit and an alicyclic dicarboxylic acid unit
Anti-fray adhesion of glass fabric, characterized in that a main component is a copolymerized polyester composed of an acid component consisting of 10 to 60 mol% and an alcohol component consisting of an aliphatic diol unit and / or an alicyclic diol unit. Agent.