JPS61256A - Electrically conductive polyester composition - Google Patents

Abstract

PURPOSE:An electrically conductive polyester composition having excellent moldability, obtained by dispersing electrically conductive particles in a specified polyester polymer, followed by the solid-phase polymerization thereof. CONSTITUTION:A composition which contains not more than 3wt% extractable low-molecular-weight material, has a resistivity less than 10<7>OMEGA.cm, and is obtained by dispersing electrically conductive particles in a polyester polymer in which the repeating unit of the formula comprises 70% or more of the polyester component, followed by the solid-phase polymerization thereof. The examples of suitable electrically conductive particles include particles of a conductive carbon black, a metal oxide of high whiteness, such as tin oxide or zinc oxide, a metal such as silver or iron or its alloy, a metal compound such as copper sulfide or zinc iodide, etc. The conductivity of the electrically conductive particles in terms of resistivity in the form of powders is preferably less than about 10<4>OMEGA.cm, especially less than 10<2>OMEGA.cm. And the electrically conductive particles should have a sufficiently small particle diameter; usually the average diameter of 1mum or smaller, preferably 0.5mum or smaller.

Description

[Detailed description of the invention]

The present invention relates to a conductive polyester composition having excellent moldability. Polyesters, particularly polyethylene terephthalate, have excellent mechanical properties, dimensional stability, heat resistance, and chemical resistance, and are therefore used in a variety of applications, such as textile products, films, molded products, etc. On the other hand, it is well known that many polyester processed products generate static electricity and become charged, and many proposals have been made for methods of imparting antistatic properties to such polyester processed products. Among these, the method of dispersing conductive particles such as carbon black or metal compounds is attracting attention as the most effective method in that it can provide permanent antistatic properties. However, in order to impart antistatic properties, it is necessary to disperse highly charged carbon black or metal compounds into synthetic polymers, which poses a problem of decreased moldability, especially productivity in the stretching process. . In the case of aromatic polyesters, such as polyethylene terephthalate, the resulting compound is brittle and molten, probably because a small amount of water contained in the conductive particles induces hydrolysis during kneading. It has the disadvantage of extremely poor fluidity. Therefore, there are currently very few antistatically processed products that have been made into Amagawa. The present invention was completed as a result of thorough research to eliminate such defects. An object of the present invention is to provide a conductive polyester composition having excellent moldability. That is, in the present invention, conductive particles are added to a polyester polymer in which repeating units represented by the following formula (I) account for at least 70 mol% of the polyester component.
ifA'li, @Iy Ct, x 6, m-work. This is a conductive polyester composition having an electric resistance of 8% or more and a specific resistance of less than 10'Ω. As the conductive particles used in the present invention, particles of any oil can be used as long as they have a specific resistance in powder form of about 1040°C or less. As suitable conductive particles,
Of course conductive carbon black. Metal oxides such as white-skinned tin oxide, zinc oxide, steel oxide, suboxide steel, indium oxide, zirconium oxide, tungsten oxide, metals such as silver, nitrogen, copper, iron, etc., or alloys thereof, copper sulfide , copper iodide, zinc iodide and other all-island compounds. Many metal oxides are half-solid bodies that are close to insulators and often do not exhibit sufficient conductivity for the purpose of the present invention. However, for example, by adding a small amount (50% or less, especially 25% or more) of a suitable second component (impurity) to the metal oxide, the conductivity can be strengthened and the object of the present invention can be achieved. A product with sufficient electrical conductivity can be obtained. As such conductivity enhancing side, antimony oxide can be used for tin oxide, and metal oxides such as aluminum, potassium, indium, germanium, tin and the like can be used for zinc oxide. Furthermore, a conductive film of the above-mentioned metal, metal oxide or metal compound is applied to the surface of the non-conductive inorganic particles such as titanium oxide, zinc oxide, magnesium oxide, tin oxide, diferric acid, silicon oxide, aluminum oxide, etc. Shisuko particles are also used.
'l? ff+ degree or less, 102 Ω・α arrogance for 9 temples, preferably less than 101 Ω・(:n+ column deviation or less.Actually, a value of about 102 Ω・σ~10=Ω・m can be obtained, and the present research Can it be applied effectively to the purpose?
Those with even better tetraelectricity are even more preferred. The specific resistance (volume resistivity) of a powder book is calculated by placing a sample in an insulating cylinder with a diameter of lσ.
rr, apply a pressure of 200 kQ from the piston to the I current voltage (e.g. 0.[11 to 1000 V)
When measuring by applying ye (with a current of 1 mA or less), the conductivity 'RL+ must be of a particle size with a small charging force and must be lj. Although those having an average particle size of 1 to 211 fn are not suitable for use, those having an average particle size of 1 μm or less, particularly 05 μm or more, and most preferably 08 μm or less are used. However, in the case of carbon black, the particle size is even smaller, that is, the average particle size is usually 0.1 μm or less, 0.02 to 0.
．． A material with a diameter of about 0.05 μm is used. The polyester composite used in the present invention is a thermoplastic formed from a dicarboxylic acid component whose main component is terephthalic acid or an ester-forming derivative of terephthalic acid and a glycol component whose main component is ethylene glycol or tetramethylene glycol. a Polyester Keigata,
@tji (1) is the best JL #! It is preferred that the return units account for at least 70 mol% of the polyester component. Examples of carboxylic acid components to be used in the common vehicle include isophthalic acid, 2,6-naphthalene dicarboxylic acid, adipic acid, and sebacic acid, and examples of ester-forming derivatives include lower alkyl esters of dicarboxylic acids (such as methyl esters). ), diaryl esters (or phenyl esters), and glycol components include cyclohexane.

[, 4 dimethatol, neopentelene gelicol, 2,2-bis(4-hydroxyphenyl)
Examples include propane and polyethylene glycol. Polyester polymers are crystalline and are used for surface point bonding.1. f', '! It is not sold exclusively to wholesalers, and can be pruned as desired. +9II
Fourth, when used as the conductivity hv of conductive composite fibers, the number of finely formed fibers is 1!1 J,, p,
It is preferable from the 5th place of b, or the worse one of the 3rd place of the Japanese child can also be used conveniently. The dispersion of the 84 electrified particles 1 into the +J Liester Kodai color is done by mixing 4 to 4 in the general melting state 8 (wiring), or dispersing the 84 electroconductive particles 1 as much as possible. It is preferable to make it uniform. Whatever is necessary, flow! 11. It is also preferable to add a low viscosity polymer such as plastic powder, waxes, and polyalkylene oxide. Ha, BL child Yuzuki,
Due to its conductivity, particle chain formation, and the properties and lack of crystallinity of the mixed polyester polymer, it is possible to
However, it is within the range of about 80% (mffi) of field damage, and in most cases it is about 20-75%. The mixture obtained by kneading is brittle and has extremely poor fluidity. This is due to the fact that in order to uniformly disperse the conductive particles used in the polyester polymer, the polyester polymer must also be pulverized. However, due to the small amount of moisture contained in the ground conductive particles and polyester polymer (normally, it is difficult to dry the powder sufficiently, It is assumed that hydrolysis is carried out during kneading (which is rarely carried out). In fact, the mixture obtained by kneading often contains 3 to 12 monohA,'17I extracted low molecular weight substances. The conductive polyester composition of the present invention can be obtained by subjecting a mixture of conductive particles dispersed in a polyester polymer to phase polymerization. Tip 1 to improve moldability
It is necessary to keep the amount of low molecular weight substances at 8% or more, and the content is 1.
1. It is preferable to set it to θ% or less. For the surface assembly, the pellet of the above mixture is heated under normal pressure or in an inert gas aeration chamber.
For example, in the above intermediate formation, ethylene glycol with n=2 is used as the main IJ. The polyethylene terephthalate yarn from which the glycol component, which is the older brother, can be obtained is 200 to 24
Solid phase polymerization was carried out at 0°C, and the intrinsic viscosity [η] was expressed as F (11
By controlling the extractable low molecular weight content to 11% or less within the range shown by the formula, moldability is greatly improved. This is a preferred example of the present invention, which can also be applied to other crystalline polyester polymers or copolyesters. However, C is the content of conductive particles (polymerization %), and all viscosity is calculated from the value measured at 20°C in a mixed solvent of phenol and tetrachloroethane (volume ratio 6:4). There are 4 extracted low molecular weight substances! Pulverized sample 1 of electrically conductive polyester composition
2 and chloroform 10- are sealed in a glass ampoule,
After heating at 20°C for 2 hours and cooling, the low molecular weight substances (mainly those with a molecular weight of several thousand or less) dissolved in chloroform were quantified.
Ask by doing. In order for the conductive polyester composition of the present invention to have sufficient conductivity, it is generally necessary to have a specific resistance of 1070. In order to impart antistatic properties to processed products such as millimeters and films, the resistance is preferably 10 4 Ω·α or less, and particularly preferably 10 2 Ω·α or less. Furthermore, the resistivity of the resistivity which also provides an electromagnetic shielding effect is preferably 10°Ω or less, and the resistivity of approximately 1-20·m or less is particularly preferable.
A DC voltage (0,1-1
The conductive polyester composition of the present invention was calculated from the electrical resistance value measured by applying 000 V).
The present invention provides processed products with excellent moldability and properties (including when used as a conductive component of composite fibers or composite films), and has extremely great industrial value. Hereinafter, the present invention will be specifically explained with reference to Examples. % indicates weight % unless otherwise specified. Example 1: Extracted with polyethylene terephthalate having a molecular ffi of 15,000, powder containing 1.8% by weight of a low-molecular compound, 74.5% by weight of conductive carbon black, 25 points of conductive carbon black, and a fluid composition @
As a treatment, 0.5 iL% of magnesium stearate was melt-kneaded 8 times at 280°C in a nitrogen stream at normal pressure to obtain an extracted low molecular weight substance of 5.6%, an intrinsic viscosity of 0.42, a specific resistance of 1, l×
10Ω・m conductive polyester mixture (pellet form)
I got it. Next, A' was crystallized and dried at 180"C for 2 hours under a nitrogen stream, and then the temperature was raised to 285°C, and the temperature was increased to 0.5
Inner phase polymerization was carried out using Ayu Hf for 12 hours to obtain a fat-like polyester composition A. The extracted low molecular weight substance was 0.8% on direct exposure, the intrinsic viscosity was 0.61, and the specific resistance was 4.4XloΩ·sub. Next, in the A7e conductive component, polyethylene terephthalate with a molecular weight of 15.000 containing 0.85% by weight of titanium oxide (referred to as B) was used as a protective component.
A composite structure as shown in Figure 1 was melt-spun. In other words, the composite ratio (volume) of both components divided into conductive fibers is l:10,
It was spun from an orifice with a diameter of 0.25 mm at a spinning temperature of 295° C., and was wound at a speed of 0.000 m/min without cooling or oiling. The yarn was then drawn at 100° C. at 180 times and brought into contact with a hot plate at 170° C., to obtain a drawn yarn Y1 of 20 denier 6 filaments. Further, as a comparative example, drawn yarn Y'1 was obtained using A' as the conductive component. Example 2 1. For titanium oxide particles having a tin oxide film on the surface.
Particles made conductive by mixing and firing 5 mi% of antimony oxide are referred to as D. The average particle size of D is 0.25μm, the content of copper oxide is 15%, the resistivity is 4.8Ω, rust, and the appearance is a light gray color close to white, and the appearance is 1 degree (light reflectance is 83%). 60% D, polyethylene glycol (molecular m6
03) Extracted with 1.5 mol% copolymerized polyethylene terephthalate 2.2% by weight of low molecular weight Jm powder and 1% by weight of magnesium stearate were melt-kneaded in a bath in the same manner as in Example 1 to obtain an extracted low molecular weight Jm. Molecular substance 3.2%, intrinsic viscosity o
, 2i, and a conductive polyester mixture (pellet form) C' having a specific resistance of 8.2×10Ω·α was obtained. Next, C' was subjected to solid phase polymerization in the same manner as in Example 1 (however, at a temperature of 220° C.
15 hours), a conductive polyester composition C was obtained. The extracted low molecular weight substance of C was 0.6%, the intrinsic viscosity was 34, and the specific resistance was 12×1 g2Ω·sub. Next, using C as a conductive component, spinning was carried out in the same manner as in Example 1.
However, the composite structure as shown in Fig. 2, the stretched double seat 2,
6 times), a drawn yarn of 72 denier 24 filaments for ¥2 was obtained. Further, as a comparative example, drawn yarn Yg was obtained using C' as the conductive component. The spinning process (spun yarn breakage, drawn and twisted yarn breakage) and yarn performance (strength, elongation, specific resistance) of these drawn yarns are shown in Table 1. As is clear from Table 1, Yl and Y2 using the conductive polyester compositions A and C of the present invention showed superior silk-spinning processing compared to those not subjected to solid phase polymerization. It was proposed to be a conductive composite edge VTR with thread performance. Table 1

[Brief explanation of the drawing]

Figures 1 and 2 are cross-sectional views of fibers spun using the conductive polyester composition of the present invention, in which components A and C are comprised of the above-mentioned composition. 7. Kanebo Gosen Co., Ltd. - Figure 1 Figure 2 Procedural amendment dated August 2, 1980

Claims (1)

[Scope of Claims] (1) An extractable low-density polymer produced by dispersing conductive particles in a polyester polymer in which repeating units represented by the following formula (I) account for at least 70 mol% of the polyester component and solid-phase polymerizing the polyester polymer. Molecular substance content is 3% by weight or less and resistivity is 10^7
A conductive polyester composition having a resistance of less than Ω·cm. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(n=2 or 4)・
...(I) (2) The composition according to claim 1, wherein the conductive particles are carbon black. (3) Claim 1 in which the conductive particles are metals, conductive metal compounds, or particles having a coating of these on their surfaces.
Compositions as described in Section. (4) Polyester polymer is n=2 in formula (I)
The composition according to claim 1, wherein the extracted low molecular weight content after solid phase polymerization is 1% by weight or less, and the intrinsic viscosity [η] is within the range shown by the following formula (II). . 0.6 ([100-C]/[100])≦[η]≦1.
3 ([100-C]/[100])・・・・・・・・・
(II) However, C is the content of conductive particles (% by weight)