JPH02216277A - Fixing agent for preventing glass cloth from fraying - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is directed to glass fabrics used to prevent fraying when glass fabrics are used for printed circuit boards and other reinforced plastic products. T! 1] relates to the fraying prevention fixing agent.

BACKGROUND OF THE INVENTION Currently, so-called fragment-m machines, which insert weft threads between warp threads and then cut the weft threads, are often used for weaving glass fabrics due to their high efficiency. Therefore, only the weft yarns are continuously arranged in tufts at both ends (selvages) of the textile, and these tufts are originally unnecessary and are cut and removed. In this case, if you cut it without applying fray prevention and perform treatments such as varnish impregnation,
The warp threads of the III product easily become frayed and wrap around the rolls, requiring the production line to be temporarily stopped for treatment, resulting in great losses.

This method involves cutting the tufts or edges (ears) of the glass object while melting and adhering them using a laser beam, or by dissolving ethylene-vinyl acetate copolymer or dimer acid polyamide in an organic solvent. A method is used in which the adhesive is applied to the tufts or edges (ears) of a glass Ail product, dried, and then cut.

Problems to be Solved by the Invention However, among the above methods, the method using laser beams is widely used because it can bond instantly and is not affected by solvents such as resin varnish, but the adhesive strength is low. There is also the problem that a molten ball forms at the tip of the glass thread and falls off even with the slightest stroke. In addition, in the method of applying and drying a solution of ethylene-vinyl acetate copolymer or dimer acid polyamide, the resin will be absorbed or slightly dissolved in the organic solvent used for the varnish, so the resin will be eluted into the varnish. After coating and drying these resins,
When the glass fabric is wound up, there is a problem that blocking occurs between the resins.

As mentioned above, various methods have been tried to prevent fraying of glass fibers, but no adhesive for preventing fraying of glass fibers that satisfies the following points is known.

(1) Anti-tangling adhesive penetrates well into glass aOJ,
Possesses strong adhesion with little adhesion.

(2) Even if an anti-tangle adhesive is applied to a glass fabric, it is dry-lit, and immediately rolled up, it will not block.

(3) Is the anti-tangle adhesive easily destroyed? B
Do not stain varnish etc. by swelling or dissolving it.

An object of the present invention is to provide an anti-fraying fixing agent for glass ALV having excellent performance that can solve the above-mentioned problems.

Means for Solving the Problems In order to solve the above problems, the anti-fraying fixing agent for glass fabrics of the present invention contains 40-90 mol% of aromatic dicarboxylic acids containing 40-90 mol% of terephthalic acid and 10-90 mol% of oxyacids.
It consists of a copolymerized polyester containing 60 mol% as an acid component and an aliphatic diol as an alcohol component.

The copolymerized polyester which is the anti-fraying fixing agent for glass products of the present invention is composed of 40 to 90 mol% of aromatic dicarboxylic acid containing 40 to 90 mol% of terephthalic acid and 10 to 6 mol% of oxyacid.
0 mol% as an acid component and an aliphatic diol as an alcohol component, it can be prepared by carrying out an esterification reaction in a conventional manner, followed by a polycondensation reaction.

It is necessary that 40 to 90 mol% of the total acid component be prephthalic acid, and if it is less than 40 mol%, solvent resistance will be insufficient. Oxyacid components include ε-caprolactone,
Examples include δ-valerolactone, p-hydroxybenzoic acid, etc., and it is necessary that this oxyacid accounts for 10 to 60 mol% of the total acid component, and if it is less than 10 mol%, it is used for coating on glass fabrics. chlorinated organic solvents (e.g. methylene chloride).

(chloroform, etc.) and adhesion to glass fabrics are low, and if the concentration exceeds 60 mol%, resistance to solvents such as acetone methyl ethyl getone, toluene, hexane, ethanol, dimethylformamide, etc. The blocking property when winding up the fabric is insufficient. Aromatic dicarboxylic acids other than terephthalic acid include isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 44
'-Biphenyldicarboxylic acid, diphenic acid, etc. can be used in an amount of 50 mol% or less, and solvent tolerability and softening point can be controlled. If the aromatic dicarboxylic acid other than terephthalic acid exceeds 50 mol%, the result is less than 40 mol% terephthalic acid, or/and less than 10 mol% oxyacid, in either case as described above. inconvenience will occur.

The alcohol components include ethyl 1/glycol, 1,3-propanediol, 1.3-butanediol, 1,4-butanediol, 1°6-hexanediol, 1.8-octanediol, 1,9 One or more aliphatic diols are selected and used, such as -nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,20-eicosandiol, and 1,4-cyclohexanedimethanol.

There are no particular limitations on the method for producing the copolyester used in the present invention, and known methods can be employed. for example,
The above aromatic dicarboxylic acids and lactones (oxyacids)
It is possible to adopt a method of directly esterifying and glycol, or transesterifying a dialkyl ester of an aromatic dicarboxylic acid, an oxydialkoxyalkyl ester of an oxyacid, and a glycol, followed by polycondensation.

During esterification, transesterification, and polycondensation, a known probe may be used if necessary.

The anti-fray fixing agent for glass fabrics of the present invention is prepared by dissolving the copolymerized polyester in a chlorinated solvent such as methylene chloride or chloroform in a dissolving tank equipped with an ordinary stirring device. This fray-preventing adhesive is applied continuously to the cut points and edges (selvages) of the glass fabric using a roll coater or a metering pump, and then dried in a hot air blower dryer. The ears) were cut, removed, and rolled up.

Effect The adhesive agent for preventing fraying of glass fabrics made of the above-mentioned copolymerized polyester has excellent solvent resistance and adhesion to glass, does not cause blocking, and has a small amount of application. demonstrate.

Example Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 45 moles of terephthalic acid, 40 moles of isophthalic acid, 15 moles of ε-caprolactone and 13 moles of 1,4-butanediol
0 mol was placed in a reaction vessel, o, oi mol of n-butyl titanate was added as a catalyst, and approximately the theoretical amount of water was distilled off at 150 to 245°C to carry out an esterification reaction. Next, 0.03 mol of n-butyl titanate was added and the mixture was heated under reduced pressure for 2 hours.
Polycondensation was carried out at 45° C. for 4 hours to prepare a copolymerized polyester.

The B&R softening point of this copolyester is determined by JIS K.
-2531.

Further, this copolymerized polyester was added to methylene chloride at 5 g/
The solution was dissolved to a concentration of 100 ml, applied to the end of a glass fabric, dried in a hot air dryer, cut the i-end of the applied part, and then wound up into a roll. After -Fl, the glass fabric wound into a roll was rewound onto another roll and the presence or absence of blocking was examined, but there was no blocking portion at all. Furthermore, the tensile adhesive strength of one of the warp threads at the end of the cut section of this glass fabric was measured and found to be 120 g, and the condition was observed after immersing it in various solvents for 72 hours (25°C). Solvent properties were evaluated. The results are shown in Table 1.

Example 2 50 mol of terephthalic acid, 20 mol of isophthalic acid, P(2
A copolymerized polyester was prepared by esterifying and polycondensing 30 moles of -hydroxyethoxy)benzoic acid and 120 moles of ethylene glycol at +r+ as in Example 1, and then B&R softening point as in Example 1. , glass adhesion, blocking properties, and solvent resistance were evaluated.
The results are shown in Table 1.

Example 3 60 moles of terephthalic acid, 15 moles of isophthalic acid, 25 moles of ε-kab I7 lactone and 1 mol of 1,4-butanediol
20 mol was subjected to esterification and polycondensation under the same conditions as in Example 1 to prepare a copolymerized polyester, and then, as in Example 1, the B&R softening point, glass adhesion,
The blocking properties and solvent resistance were evaluated and the results are shown in Table 1.

Example 4 A copolymerized polyester was prepared by esterifying and polycondensing 70 moles of terephthalic acid, 30 moles of ε-caprolactone, and 120 moles of 1,4-butanediol under the same conditions as in Example 1. The B&R softening point, glass adhesion, blocking property, and solvent resistance were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 30 mol of terephthalic acid, 10 mol of isophthalic acid, 10. Esterification and polycondensation of 60 moles of lactone and 100 moles of 1,4-butanediol were carried out under the same conditions as in Example 1 to produce a copolymerized polyester! The B&R softening point, glass adhesion, blocking/n, and solvent resistance were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 960 mol of terephthal, 35 mol of isophthalic acid, 5 mol of ε-caprolactone and 140 mol of 1,4-butanediol
A copolymerized polyester was prepared by esterifying and polycondensing the mole under the same conditions as in Example 1, and then the 13&R softening point, glass adhesion, blocking property, and fusing resistance were evaluated in the same manner as in Example 1. The results are shown in Table 1.

As is clear from the results shown in Table 1, the fraying prevention adhesives of each example were all excellent in B&R softening point, glass adhesion, blocking property, and solvent resistance. The performance of all the samples was poor, and the glass adhesion of Comparative Example 2 was extremely low.

(The following is a blank space) Effects of the Invention As shown in E-E, the anti-fraying fixing agent for glass fabrics of the present invention contains 60 to 90 mol% of aromatic dicarboxylic acid containing 40 to 90 mol% of terephthalic acid and 10 to 40 mol% of oxyacid. % as an acid component and an aliphatic diol as an alcohol component, and contains methylene chloride and 7170.
It dissolves quickly in chlorinated solvents such as holm, and has good workability when applied to glass fabrics.Also, even when it is rolled up immediately after drying, there is no blocking at all, and there is no problem with high edges. It has good adhesion to glass and strong adhesion, and has excellent resistance to organic solvents used in varnishes, etc., making it suitable for mounting when glass fabric is used in various applications. This can greatly improve ease of use.

Agent Hiroshi Mori Moto

Claims (1)

[Claims] 1. A glass fabric made of a copolymerized polyester containing 40 to 90 mol% of an aromatic dicarboxylic acid containing 40 to 90 mol% of terephthalic acid, 10 to 60 mol% of an oxyacid as an acid component, and an aliphatic diol as an alcohol component. Anti-fray fixing agent.