JPS58149330A - Electroconductive conjugate fiber - Google Patents

Abstract

PURPOSE:Electroconductive conjugate fiber that consists of a fiber-forming polymer and a mixture of cuprous iodide and a thermoplastic polyester copolymer composed specifically, thus showing extremely good color tones, sufficient yarn strength and high electroconductivity. CONSTITUTION:The objective electroconductive conjugate fiber is composed of (A) a fiber-forming copolymer mainly consisting of polyester, polamide or polyolefin and (B) a mixtrure of (i) a powder of cuprous iodide with (ii) a thermoplastic polyester copolymer consisting of 30-80mol% of aliphatic dicarboxylic acid such as malonic acid, 70-20mol% of aromatic dicarboxylic acid such as phthalic acid and at least one of alkylene glycols such as ethylene glycol and 1,3-propanediol. The share of the component B is preferably 1-50% in the cross section f the resultant electroconductive conjugate fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to conductive fibers, particularly to novel conductive composite fibers containing cuprous iodide as a conductive substance.

Synthetic fibers such as polyester fibers and polyamide fibers have low conductivity, so static electricity is generated due to friction.

When fabrics made of such synthetic fibers are used, they are often charged with high potentials reaching as high as 100%, and various problems occur due to the adhesion of dust and discharge. .

In order to solve this problem, it is known to mix conductive fibers into textile products, and conductive -1 fibers include metal fibers and metal-plated fibers.

Fibers coated with polymer dope containing conductive substances,
Fibers containing carbon black have been proposed.

However, all of these conventional conductive and electrically conductive fibers have serious drawbacks and are not satisfactory. For example, metal fibers do not have bending recovery properties, so bending during use or processing can reduce their electrostatic performance, and they may be mixed with other fibers or cross-knitted.

It has many drawbacks, such as not being easy to mix and match, and furthermore, having a color tone unique to gold S. Metal-plated fibers require a uniform and continuous plating layer to be formed on the fiber surface, so the fiber surface must be smooth, which greatly limits the types of fibers that can be applied. The treatment must be carried out precisely, resulting in many drawbacks such as extremely high manufacturing costs, low durability as the plating layer easily peels off during use or processing, and the appearance of a color characteristic of metals. have. Fibers coated with a polymer dope containing conductive and/or conductive substances also have the same disadvantages as the metal-plated fibers mentioned above in terms of manufacturing cost and peeling.Furthermore, fibers containing carbon blanks are colored black with carbon black. However, when mixed with synthetic fibers, the appearance is significantly impaired, which has the fatal disadvantage of limiting its field of use.

As a result of intensive study to provide conductive fibers free from the above-mentioned drawbacks, the present inventors have determined that a thermoplastic resin containing component (A) consisting of a conductive substance and a formable thermoplastic resin and cuprous iodide. When we tried to manufacture conductive composite fiber using component (B), we found that the undrawn yarn showed sufficient conductivity, but when stretched to increase yarn strength, the conductive performance decreased, and the stretching ratio was reduced. As the temperature increases, the conductive performance deteriorates significantly, making it impossible to draw at a sufficient magnification, making it impossible to obtain a conductive composite fiber with excellent yarn strength and conductivity.

Therefore, as a result of repeated studies on the change in conductivity due to stretching of a thermoplastic polymer containing cuprous iodide in component (B), we found that this polymer has a fixed proportion of aromatic dicarboxylic acid and aliphatic By using a thermoplastic copolymerized polyester consisting of an acid component consisting of a dicarboxylic acid and a fullylene glycol component, the resulting conductive composition (Bl J
Although the conductivity for ff1 is completely insufficient,
Composite fibers spun and drawn using this component (B) lack conductive performance immediately after being drawn, but the conductive performance improves over time and has sufficient performance as a conductive fiber after 10 to 30 days. The present inventors have discovered that the desired conductive composite fiber can be obtained with excellent yarn strength and conductivity, and have completed the present invention.

That is, the present invention comprises component (A) consisting of a fiber-forming polymer;
and a mixture of cuprous iodide and a thermoplastic copolyester, and the thermoplastic copolyester has a
A conductive material formed from component (B), which is a thermoplastic copolymer polyester composed of 80 molar group dicarboxylic acid component, 70 to 20 molar group dicarboxylic acid component, and at least one fullkylene glycol component. This relates to composite fibers.

The polymer serving as component (A) constituting a part of the conductive fiber of the present invention may be any fiber-forming polymer that can be melt-spun. Specific examples of such polymers include polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as nylon 6 and nylon 66, polyolefins such as polyethylene and polypropylene, and copolymers containing these as main components. Examples include merging. Further, the polymer constituting the component (A) may contain optional additives, such as a matting agent 9 coloring agent, an II stabilizer, a dyeability improver, etc., as necessary.

The component (B) constituting the conductive portion of the conductive fiber of the present invention is composed of fine iodide steel powder and a thermal iHJ plastic polymer. The polymer constituting component (B) contains an acid component consisting of an aromatic dicarboxylic acid component and a molar dicarboxylic acid component of 30 to 80 mol of the total acid component, and at least one fullkylene glycol component. A thermoplastic copolymerized polyester composed of It doesn't have to be. In the case of a copolymerized polyester in which the ratio of aliphatic dicarboxylic acid components to the total acid component is less than 30 moles or more than 80 moles, the conductivity of the component (B) constituting the conductive part is lower than that of the copolymerized polyester described above. However, the conductivity is significantly reduced by stretching, and the reduced conductivity cannot be recovered even with time, making it impossible to obtain the desired conductive composite fiber with excellent yarn strength and conductivity. Can not.

The aliphatic dicarboxylic acids mentioned here include malic acid, succinic acid, Daltal powder, adipic acid, pimelic acid, sperinic acid, azelain@, sebacic acid, etc., and the aromatic dicarboxylic acids include phthalic acid.

Inphthalic acid, terephthalic acid, naphthalenedicarbone I
I can give you my hometown. Also, ethylene glycol is an alkylene glycol.

1.3-propanediol, 1.4-butanediol,
Examples include 1.5-hebutanediol and 1.6-hexanediol.

To mix the polymer in the Bl component described above and cuprous iodide, any method can be employed as long as it can be dispersed well.

The amount of cuprous iodide mixed varies depending on the desired electrical conductivity, and is generally difficult to specify, but in order to impart sufficient electrical conductivity to the composite fiber, it is preferably 50% by weight or more. On the other hand, if the mixed amount of cuprous copper is too large, (B
) The content is preferably 80% by weight or less since it becomes difficult to adjust the components and spin. Component (B) may also contain optional additives, such as matting agents, if necessary.

It may contain a coloring agent and an oxidation stabilizer.

The shape of the conjugate fiber composed of the components (A) and (B) may be any shape as long as the component (B) is continuous along the fiber axis direction. However, the core-sheath type in which component B) is completely surrounded by component (A) is
) The antistatic performance is slightly inferior to the one in which some of the components are exposed on the fiber surface, so this is not a problem for carpet applications, but
For clothing applications that require more severe performance, it is preferable that component (B) has a low tx (or a shape in which a portion of it is exposed on the fiber surface).

In addition, the combination of polymers used for components (A) and (B) may be arbitrary in the case of a complete core-sheath type, but in the case of a partially exposed type, the same combination may be used to prevent peeling. It is preferable to use polymers of this type.

In addition, the ratio of component (A) and component (B) in the cross section of the fiber can be varied over a very wide range, but (Bl
If the proportion of the components becomes too large, the strength of the resulting conductive fiber will decrease, so (
The area occupied by component B) is preferably 50% or less. Also,
The lower limit of this component (B) is not necessary as long as the component (B) is continuous along the fiber axis direction, but
Usually, it is preferable that the area in the cross section of the fiber is 1 inch or more, particularly 3% or more.

K is a special method for producing such composite fibers.

It is not necessary to adopt these conditions, and the melt spinning method and conditions for producing a two-component composite fiber can be arbitrarily applied depending on the component (A).

In the present invention, the fibers obtained by spinning are stretched to obtain sufficient strength. Any method and conditions for this stretching may be used as appropriate.

The conductive composite fiber of the present invention does not have sufficient conductive performance when normally spun and drawn, but it gradually improves by aging at room temperature, and after 10 to 30 days, it will exhibit sufficient conductive performance. become.

The conductive fiber of the present invention uses cuprous iodide powder, which is expensive on its own, as a conductive substance, and forms a common synthetic fiber (
Because it contains a (trans) component, it has an extremely good color tone and sufficient strength, and can be dyed into any color by conventional methods, and its conductive performance does not deteriorate during processing or use. These fibers can overcome all the drawbacks of conventional conductive fibers, and can be applied to any field where conductive performance is required.

The conductive fibers of the present invention will be explained in further detail with reference to Examples below. The volume resistivity measurement conditions for the conductive compositions and conductive fibers in Examples were 20°C.

30cm RH, 1kV DC voltage. The conditions for measuring the volume resistivity of the conductive fine powder were 20°C and 30°RH.

3v DC voltage, <ookg/- under pressure.

Example 1 (a) 49 parts by weight of dimethyl terephthalate, 58 parts by weight of dimethyl sebacate, 64 parts by weight of ethylene glycol, and 0.06 parts by weight of calcium acetate hydrate,
The mixture was gradually heated in a nitrogen atmosphere, and methanol produced as a result of transesterification from around 160°C was removed from the system via a rectification column. After heating for about 3 hours to complete distillation of methanol, 0.039 parts by weight of triple-purified antimony, 0.033 parts by weight of phosphorous acid, and 0.2 parts by weight of silicone oil were added to the mixture, and the temperature was raised to 280°C. After warming and stirring for 30 minutes, remove the stopper and transfer the system to a reduced pressure.
A time polycondensation reaction was carried out to obtain sebacin@SOmolti copolymerized polyethylene terephthalate.

100 parts by weight of this copolyester and 250 parts by weight of cuprous iodide (volume resistivity 5 x 10 Ω/cR) were melted at 280°C for 30 minutes under a nitrogen stream at normal pressure to give a volume resistivity of 2.
．． A conductive composition of 3×10′Ω·α was obtained.

(b) The above conductive composition is used as the component (B), polyethylene terephthalate having an intrinsic viscosity of o and 6 s di/I is used as the component (A), and a side-pie-side type spinning hole (0
, 3ml) using a spinneret with 12 holes, the spinning temperature was 280°C, the spinning speed was 400*/min, 450 denier, and the area ratio of component (A) and component (B) in the cross section of the fiber was 7:1. An undrawn conjugate fiber was obtained in which approximately 15% of the surface was a Bl component.Then, it was drawn 4.0 times at a drawing temperature of 100°C.The electrical resistance value of the obtained drawn fiber was 5 immediately after drawing.
．． 5 x 10"Ω/cIIL. When this fiber was left at room temperature for 30 days, the strength was 323 y and the elongation was 30.
A conductive composite fiber with an electrical resistance value of 8.9×10 8 Ω/flaw was obtained.

Example 2 (a) Example 1 except that 44 parts by weight of dimethyl adipate was used instead of 58 parts by weight of dimethyl sebacate.
Adipine@SOmolti copolymerized polyethylene terephthalate was obtained in the same manner as in (a).

Example 1-(a) except for using this copolymerized polyester
) Volume resistance value 3. A conductive composition with I x 10'Ω·α was obtained.

(b) Spinning and drawing were performed in the same manner as in Example 1-(a) except that the above conductive composition was used as the component (B).

The electrical resistance value of the obtained drawn composite fiber is 4.3×10”
Ω/α). When this fiber was wrapped at room temperature for 10 days, the strength was 3189. Elongation 24%, electrical resistance value 9.3
A conductive composite fiber of 10Ω/a was obtained.

Comparative Example 1 (a) Same as Example t-(b) except that 74 parts by weight of dimethyl terephthalate and 29 parts by weight of dimethyl sebacate were used instead of 49 parts by weight of dimethyl terephthalate and 58 parts by weight of dimethyl sebacate. This operation yielded 25 mol sebacic acid copolymerized polyethylene terephthalate.

Example 1- except for using this copolymerized polyester
Perform the same operation as in (a) to obtain a volume resistance of 3゜2 x 103Ω.
・A highly conductive composition was obtained.

(b) The above conductive composition (all except for the Bl component).

Spinning and drawing were performed in the same manner as in Example 1-(b).

The electrical resistance value of the obtained drawn composite fiber was 10Ω/min or more, and did not improve even after 30 days or more.

Procedural amendment dated January 7, 1980, Commissioner of the Japan Patent Office 1, Indication of the case, Patent Application No. 1987-31680 2, Name of the invention Conductive composite fiber 3, Person making the amendment Relationship to the case Patent applicant Osaka City Higashi 1-11 Minamihonmachi, Ward (300) Teijin Ltd. Representative Tomo Tokusue 5, Subject of amendment (1) Line 114, Line 8877886 - Line 11, Line 7 11C [
(2) Correct the text "maqmJ" to "malonic acid-1" (2) The text "1Ω/cM sword" on page 13, line 7 of the same page should be corrected as "malonic acid-1".
Ω/3”, corrected.

(3) Page 13, line 15, “Kit-ka)”
1- (a) Correct it as J.

that's all

Claims (1)

[Scope of Claims] +11 Component (A) consisting of a fiber-forming polymer, and a mixture of Iodized steel and a thermoplastic copolyester, and the thermoplastic copolyester has a molecular weight of 30 to 80%.
A conductive material formed from component (B), which is a thermoplastic copolymer polyester composed of a molar aliphatic dicarboxylic acid component, a 70 to 20 molar dicarboxylic acid component, and at least one fullkylene glycol component. Composite fiber. (2) The conductive conjugate fiber according to claim 1, wherein the area ratio occupied by the component (B) in the cross section of the conductive conjugate fiber is 1 to 50%. (The content of iodized steel in the component 31 (B) is 50 to 80
The conductive composite fiber according to claim 1 or 2, which is % by weight.