JPH0726010B2 - Polyester composition having antistatic property - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyester composition having antistatic properties, and more specifically to a polyester composition exhibiting excellent antistatic properties regardless of atmosphere. Is.

[Prior Art] Polyester, especially polyethylene terephthalate, has excellent mechanical properties, chemical resistance, heat resistance, electrical characteristics, and transparency, so that it is suitable for clothing, industrial fibers, magnetic tapes, electrical insulating materials, capacitors, packaging. As a film of materials,
Widely used.

However, while polyester has the above-mentioned excellent characteristics, it has high volume resistivity and surface resistance, and has the drawback that it is easily charged due to friction and the like, and dust is likely to adhere to it, resulting in electrostatic damage.

For example, in the case of a film, the film is electrically charged during film formation, resulting in good winding and wrinkles, which significantly deteriorates the film quality, and when the obtained film is processed into a magnetic tape or the like, dust or the like may be attached due to charging. , Missing the magnetic layer,
This can cause dropouts and pinholes during vapor deposition.

As a method for removing static electricity generated during film forming, it is common to use a static elimination bar or the like, but it is difficult to completely eliminate static electricity by this method. On the other hand, as a method of modifying the polyester itself, Japanese Patent Publication No. 58-39655 proposes a method of blending a polyalkylene glycol and a sulfonic acid metal salt derivative. However, with this method
Insufficient antistatic property, and it is difficult to obtain stable antistatic property such as change of antistatic property when formed into fiber or film, or decrease in antistatic property especially under drying. there were.

[Problems to be Solved by the Invention] The present inventors have arrived at the present invention as a result of intensive studies in view of the above-mentioned problems.

That is, an object of the present invention is to provide a polyester composition having excellent antistatic properties regardless of atmosphere.

[Means for Solving the Problem] The object of the present invention is: (A) 0.1 to 20.0 parts by weight of polyarylene glycol, (B) 0.05 to 20.0 parts by weight of a sulfonic acid metal salt derivative, and (B) to 100 parts by weight of polyester. C) Aromatic amine and / or ammonium salt thereof
It can be achieved by a polyester composition having an antistatic property, which is characterized by containing 0.001 part by weight or more.

The polyester in the present invention is intended for a polyester composed of dicarboxylic acid or its derivative and glycol. The dicarboxylic acid or its derivative is mainly terephthalic acid or its lower alkyl ester, but other acid components such as isophthalic acid and p-
β-oxyethoxybenzoic acid, diphenyl ether 4,
One or more of 4'-dicarboxylic acid, adipic acid, sebacic acid, dodecanedioic acid, azelaic acid, or their lower alkyl or glycol esters can be used in combination.

As glycols, ethylene glycol and tetramethylene glycol-1,4 are mainly targeted, but as other glycol components, for example, propylene glycol, trimethylene glycol, neopentyl glycol, hexamethylene glycol-1,6, pentaethylene glycol.
You may use together 1 type, or 2 or more types, such as 1,5,1,4-cyclohexane diol, 1,4-cyclohexane dimethanol, 1,4-bisoxyethylene glycol, and bisphenol A.

Any method may be used for producing the polyester composed of the above dicarboxylic acid or its derivative and glycol. For example, polyethylene terephthalate composed of a terephthalic acid component and an ethylene glycol component will be explained. Either direct esterification reaction of terephthalic acid and ethylene glycol, direct esterification reaction of dimethyl terephthalate and ethylene glycol, or dimethyl terephthalate and ethylene. A first-step reaction for producing a glycol ester of terephthalic acid or a low polymer thereof by transesterification with glycol or by reacting terephthalic acid with ethylene oxide;
Most commonly, it is produced by a polycondensation reaction of the first stage reaction product.

Examples of the (A) polyalkylene glycol used in the present invention include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like having a molecular weight of 400 or more. Polyethylene glycol having an average molecular weight of 1000 to 20000 is preferable.

The amount of the polyalkylene glycol added is required to be 0.1 to 20.0 parts by weight, preferably 0.5 to 10.0 parts by weight, based on 100 parts by weight of the polyester. If it is less than 0.1 part by weight, the antistatic property is not sufficient, and if it is added in excess of 20.0 parts by weight, mechanical properties and heat resistance are deteriorated, which is not preferable.

The (B) sulfonic acid metal salt derivative used in the present invention is 5-
Metal salt of organic sulfonic acid having ester bond-forming functional group such as sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, sodium 3,5-di (carbo-β-hydroxyethoxy) benzenesulfonate, sodium menylbenzenesulfonate , Sodium decylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodium stearylbenzenesulfonate, potassium octylbenzenesulfonate, potassium dodecylbenzenesulfonate, potassium stearylbenzenesulfonate, sodium octylnaphthalenesulfonate, sodium nonylnaphthalenesulfonate, dodecyl Sodium naphthalenesulfonate, potassium nonylnaphthalenesulfonate, potassium dodecylnaphthalenesulfonate, stearylnaphthalene sulfonate And alkyl aromatic sulfonates such as potassium phosphate can be mentioned. Of these, sodium dedosylbenzenesulfonate and 5-sodium sulfoisophthalic acid are preferably used. The addition amount of these sulfonic acid metal salt derivatives needs to be 0.05 to 20.0 parts by weight, and more preferably 0.1 to 10.0 parts by weight. If it is less than 0.05 parts by weight, the antistatic effect is not sufficient, and if it is added in excess of 20.0 parts by weight, mechanical properties are deteriorated, which is not preferable.

The aromatic amine (C) used in the present invention is preferably a tertiary amine in view of heat resistance and coloring. Specifically, N, N-dimethylaniline, N, N-diethylaniline, N, N-dibutylaniline, N, N-dibenzylaniline, N, N-diethyl-
o-toluidine, N, N-diethyl-m-toluidine, N, N
-Diethyl-pN-methyldiphenylamine, N-benzyl-N-ethylaniline, triphenylamine, N, N,
N ', N',-tetramethyl-p-phenylenediamine and the like are not limited to these. As the ammonium salt, a salt of the amine with a fatty acid such as carbonic acid or acetic acid or an acid such as hydrohalic acid is used. Of these, triphenylamine and N, N, N ', N'-tetramethyl-p-phenylenediamine are preferable.

It is necessary to add 0.01 parts by weight or more of these aromatic amines and / or ammonium salts thereof, preferably 0.01 to 2.0 parts by weight, and more preferably 0.01 to 1.0 parts by weight. If it is less than 0.01 parts by weight, a sufficient antistatic effect cannot be obtained, which is not preferable.

The polyalkylene glycol, sulfonic acid metal salt derivative, aromatic amine and / or ammonium salt thereof may be added at any time. That is, they may be added at any time before or during the transesterification reaction or esterification reaction, before or during the polycondensation reaction, in the molten state after the polycondensation reaction, in the pellet state, or before the molding.

Further, these may be added at the same time, separately, or may be mixed in advance and then added. It is also possible to use a method in which a high concentration master polymer is prepared in advance and then mixed.

Further, (A) the polyalkylene glycol is used after the completion of the transesterification reaction or the esterification reaction and before the completion of the polycondensation reaction, and the (B) sulfonic acid metal salt derivative is used before the completion of the polycondensation reaction, (C) the aromatic amine and / or The ammonium salt is preferably added after the end of the transesterification reaction or the esterification reaction and before the end of the polycondensation reaction.

In the polyester composition of the present invention, if necessary, a flame retardant, a heat stabilizer, an ultraviolet absorber, a pigment, a dye, a fatty acid ester, an organic lubricant such as wax, or glass fiber, glass beads, asbestos, clay, wollastenite. , Mica, titanium oxide, calcium carbonate, kaolin,
Reinforcing agents such as siloids and carbon black, and various fillers may be blended.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples.
The physical properties in the examples were measured as follows.

A. Intrinsic viscosity of polymer Measured at 25 ° C using o-chlorophenol as a solvent.

B. Triboelectrification A sheet of 10 cm x 10 cm is rubbed with a polyethylene terephthalate cloth and placed on a number of 3 mm x 3 mm pieces of paper,
The number of pieces of paper attached to the film when the sheet was lifted was shown.

C. Surface resistance of film Measured with a R-503 type super-insulator manufactured by Kawaguchi Electric Co., Ltd.

Example 1 100 parts by weight of dimethyl terephthalate and ethylene glycol 6
The transesterification reaction was carried out with 0 part by weight of calcium acetate as a catalyst. After the transesterification reaction, 0.04 parts by weight of orthophosphoric acid, 0.03 parts by weight of antimony trioxide, 2.0 parts by weight of polyethylene glycol (MW4000), 1.0 part by weight of sodium dodecylbenzenesulfonate, and N, N, N ', N'
-Tetramethyl-pphenylenediamine dihydrochloride (hereinafter
0.5 parts by weight (TMPD) was added and polycondensation reaction was carried out by a conventional method to obtain a polyester composition having an intrinsic viscosity of 0.62.

The obtained polyester composition was dried with hot air at 180 ° C. for 4 hours and then melt-extruded to obtain an unstretched sheet having a thickness of 150 μm. Next, the unstretched sheet was biaxially stretched at 95 ° C. and heat-treated at 220 ° C. for 1 minute to obtain a film having a thickness of 14 μ. The triboelectrification property and surface resistance value of the sheet and film are shown in Table 1, and it is understood that the polyester composition of the present invention has excellent antistatic property.

Comparative Example 1,2 TMPD was not added after the transesterification reaction, or TM
An unstretched sheet and a biaxially stretched film were obtained in the same manner as in Example 1 except that PD, sodium dodecylbenzenesulfonate and polyethylene glycol (MW4000) were not added. The results are shown in Table-1, and it is understood that all of them are easily charged by friction and have a very large surface resistance value and poor antistatic properties.

Comparative Example 3,4 After completion of the transesterification reaction, polyethylene glycol and TM
PD or TMPD with sodium dodecylbenzene sulfonate
In the same manner as in Example 1 except that
An axially stretched sheet was obtained. The results are shown in Table-1. It can be seen that the antistatic properties are inferior to those of the present invention.

Examples 2 to 9 An unstretched sheet and a biaxially stretched film were obtained in the same manner as in Example 1 except that the types and addition amounts of polyalkylene glycol, aromatic amine and sulfonic acid metal salt derivative were changed. It can be seen that the polyester composition of the present invention has excellent antistatic properties and retains its performance especially in a dry atmosphere.

[Effects of the Invention] The polyester composition of the present invention has excellent antistatic properties and exhibits stable antistatic properties irrespective of the atmosphere. Therefore, the polyester composition is effectively used in the fields of films, fibers and the like. When used in the field of films such as magnetic tapes, where the requirement for preventing the attachment of dust and the like is severe, the effect is more remarkably exhibited.

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Claims (1)

[Claims] 1. A polyalkylene glycol of 0.1 to 20.0 parts by weight, (B) a sulfonic acid metal salt derivative of 0.05 to 20.0 parts by weight, and (C) an aromatic amine and / or ammonium thereof, relative to 100 parts by weight of polyester. salt
A polyester composition having an antistatic property, which is characterized by containing 0.001 part by weight or more.