WO2007105494A1

WO2007105494A1 - Conductive composite fiber and method for producing same

Info

Publication number: WO2007105494A1
Application number: PCT/JP2007/053909
Authority: WO
Inventors: Tadayoshi Koizumi; Kazuhiko Tanaka; Masao Kawamoto; Hitoshi Nakatsuka; Nobuhiro Koga; Kenichi Yoshioka
Original assignee: Kuraray Co., Ltd.
Priority date: 2006-03-10
Filing date: 2007-03-01
Publication date: 2007-09-20
Also published as: EP1995359A4; JP4859916B2; EP1995359A1; US20090047516A1; CN101437992A; TW200745394A; JPWO2007105494A1

Abstract

Disclosed is a conductive composite fiber having an elongation (DE) of 100-350%, wherein a conductive layer (A) composed of 60-80% by weight of a thermoplastic resin and 20-40% by weight of a conductive particle, and a protective layer (B) composed of 50-95% by weight of polyethylene terephthalate and 5-50% by weight of polyethylene-2,6-naphthalate are combined. Consequently, this conductive composite fiber has excellent conductivity. In addition, this conductive composite fiber is small in changes over time in fiber properties such as elongation and boiling water shrinkage during transportation or storage, although it has a certain or more elongation.

Description

Specification

Conductive conjugate fiber and method for producing the same

Technical field

[0001] The present invention relates to a conductive conjugate fiber, and particularly to a conductive conjugate fiber in which a conductive layer made of thermoplastic resin and conductive particles and a protective layer made of a polyester cover are combined. Further, the present invention relates to a suitable method for producing such a conductive conjugate fiber.

Background art

[0002] Conventionally, among various known conductive fibers, a conductive layer composed of a thermoplastic resin composition containing conductive particles such as carbon black, and conductive particles. Conductive conjugate fibers having a protective layer made of a thermoplastic rosin that does not contain any are widely used. This is obtained by composite spinning of a thermoplastic resin composition containing conductive particles and a thermoplastic resin containing no conductive particles, and the conductive layer is formed on the surface or inside of the fiber. It arrange | positions so that it may continue in a longitudinal direction. Such conductive composite fibers are described in, for example, Patent Documents 1 to 4.

[0003] In order to obtain sufficient conductive performance by a conductive layer comprising a thermoplastic resin composition containing conductive particles, it is necessary to mix a large amount of conductive particles in the thermoplastic resin composition. . However, when a large amount of conductive particles are blended, there is a problem that the spinnability and stretchability deteriorate rapidly. If it is forcibly stretched, the conductive carbon black structure will be destroyed even if the conductive layer is cut in the fiber or if it is not cut, and the conductive fiber will be damaged during actual use. When a slight external force is applied to the conductive layer, the conductive layer may be easily cut and the conductive performance may be lost. Therefore, when producing a conductive conjugate fiber, there are fears that the yarn properties such as elongation and boiling water shrinkage may change over time even when the fiber cannot be sufficiently drawn. In particular, when producing conductive composite fibers that are required to have a certain degree of elongation or boiling water shrinkage for use as a blended yarn, the change in physical properties over time is more remarkable. It was a problem.

[0004] In Patent Document 5, polyethylene terephthalate and polyethylene naphthalate are blended. A highly shrinkable polyester fiber made from the prepared polyester rosin composition is described. It is described that the high-shrinkage polyester fiber exhibits a high shrinkage rate and shrinkage stress and is excellent in storage stability at a high temperature of 70 ° C or higher. However, Patent Document 5 describes a high-shrinkable fiber consisting of only the above-mentioned polyester resin composition, and is a fiber made of a resin composition containing only a large amount of conductive particles. It is not described, but it is not described as a composite fiber.

Patent Document 1: Japanese Patent Laid-Open No. 57-29611

Patent Document 2: JP-A-58-132119

Patent Document 3: Japanese Patent Laid-Open No. 9-279416

Patent Document 4: Japanese Unexamined Patent Publication No. 2003-278031

Patent Document 5: Japanese Patent Laid-Open No. 2001-288618

Disclosure of the invention

Problems to be solved by the invention

[0006] The present invention has been made to solve the above-described problems, and has excellent conductivity that lasts for a long period of time, and has a strength equal to or greater than a certain level, but also during transportation and storage. It is an object of the present invention to provide a conductive conjugate fiber having a small change in mechanical properties such as elongation and contraction rate of boiling water with time. Another object of the present invention is to provide a method for producing such a conductive conjugate fiber.

Means for solving the problem

[0007] The above-mentioned problems include a conductive layer (A) comprising 60 to 80% by weight of thermoplastic resin and 20 to 40% by weight of conductive particles, 50 to 95% by weight of polyethylene terephthalate and polyethylene 2, 6-naphthalate 5 This is solved by providing a conductive conjugate fiber characterized in that it is composited with a protective layer (B) of ˜50% by weight and has an elongation (DE) of 100 to 350%.

[0008] At this time, it is preferable that the thermoplastic resin constituting the conductive layer (A) is polybutylene terephthalate or polyamide. It is also preferable that the weight ratio (AZB) of the conductive layer (A) to the protective layer (B) is 5Z9 5 to 50Z50. It is also preferable that the boiling water shrinkage (Wsr) is 20 to 60%. In addition, when stored under conditions of 60 ° C and 80% RH, the elongation (DE) force after 60 days from spinning and the elongation (DE) after 1 day after spinning should be 1.3 times or less, 60 days after spinning The boiling water shrinkage (Wsr) after the spinning is 0.3 times higher than the boiling water shrinkage (Wsr) one day after spinning.

60 1

And that the boiling water shrinkage (Wsr) after 60 days from spinning is not less than 10%.

60

This is also suitable. Further, a carpet using a fiber obtained by stretching such a conductive conjugate fiber is a preferred embodiment of the present invention.

[0009] The above-mentioned problems, thermoplastic榭脂60-80 wt% and the conductive particles 20 to 40 wt% or Ranaru resin composition and (a), polyethylene terephthalate 50-95 wt ^_0/0 and polyethylene - 2 , 6-Naphthalate 5% to 50% by weight of a resin composition (b) comprising a composite spinning, comprising a molten resin composition (a) and a molten resin composition This can also be solved by providing a method for producing a conductive conjugate fiber characterized in that (b) is merged, melted and discharged from a composite spinneret, and wound at a speed of 1500 to 3000 mZ. At this time, the following (1) to (5) are preferably performed in that order, and the following (2) and (3) are preferably performed before the discharge yarn first contacts the roller or guide.

(1) The melted resin composition (a) and the melted resin composition (b) are merged and melted and discharged from the composite spinneret.

(2) The discharged molten resin composition is once cooled to a temperature below the glass transition point.

(3) Next, run in the heating device and heat-treat

(4) Add oil afterwards

(5) Winding up at a speed of 1500-3000mZ

The invention's effect

[0010] The conductive conjugate fiber of the present invention has excellent conductivity that lasts for a long period of time, and also has a certain degree of elongation, but the elongation and boiling water shrinkage during transportation and storage. The change of physical properties over time is small. Therefore, the physical properties of the fiber are stable even in long-distance transportation such as international transportation and long-term storage, and the subsequent process such as blending, twisting, weaving, knitting, etc. is good. A homogeneous product can be obtained. Moreover, according to the manufacturing method of this invention, it is easy to obtain such an electroconductive composite fiber. Brief Description of Drawings

FIG. 1 is a graph showing the results of measuring the elongation (DE), boiling water shrinkage (Wsr), and electrical conductivity performance over time for the composite fiber obtained in Example 1. FIG. 2 is a graph showing the results of measuring the elongation (DE), boiling water shrinkage (Wsr), and electrical conductivity performance over time for the composite fiber obtained in Example 2.

FIG. 3 is a graph showing the results of measuring the elongation (DE), boiling water shrinkage (Wsr), and conductivity performance over time for the composite fiber obtained in Example 3.

FIG. 4 is a graph showing the results of measuring the elongation (DE), boiling water shrinkage (Wsr), and electrical conductivity performance over time for the composite fiber obtained in Example 4.

FIG. 5 is a graph showing the results of measuring the elongation (DE), boiling water shrinkage (Wsr), and electrical conductivity performance over time for the composite fiber obtained in Comparative Example 1.

BEST MODE FOR CARRYING OUT THE INVENTION

[0012] The conductive conjugate fiber of the present invention comprises a conductive layer (A) comprising 60 to 80% by weight of thermoplastic resin and 20 to 40% by weight of conductive particles, 50 to 95% by weight of polyethylene terephthalate and polyethylene-2. , in which 6-naphthalate 5-50 ^_0/0 also force the protective layer (B) and is formed by a composite.

[0013] The thermoplastic resin contained in the conductive layer (A) is not particularly limited as long as it is a fiber-forming thermoplastic resin. Usually, a thermoplastic polyester or a thermoplastic polyamide is preferably used. Further, the melting point of the resin constituting the conductive layer (A) is preferably 200 ° C. or more, and the point of practical durability is also preferable. The melting point is more preferably 210 ° C or higher and 250 ° C or lower.

[0014] The thermoplastic polyester used in the conductive layer (A) includes, for example, terephthalic acid, isophthalic acid, naphthalene 2,6 dicarboxylic acid, 4,4'-dicarboxydiphenyl, 5-sodium sulfo Aromatic dicarboxylic acids such as isophthalic acid; dicarboxylic acid components such as azelaic acid, sebacic acid and other aliphatic dicarboxylic acids, and ethylene glycol, polyethylene glycol, propylene glycol, 1,4 butanediol, polyethylene glycol, polytetramethylene Fiber-forming polymers formed using diol components such as aliphatic diols such as glycol; aromatic diols such as ethylene oxide adducts of bisphenol A or bisphenol S; and alicyclic diols such as cyclohexanedimethanol. Mention may be made of esters. Among them ethylene terephthalate units or butylene terephthalate units is a general purpose polyester 80 mole ^_0/0 or more, especially 90 mol ^_0/0 or more content Polyester that prefers U ヽ.

[0015] In particular, polybutylene terephthalate, that is, a polyester containing 80 mol% or more of butylene terephthalate units is preferable because conductive particles can be easily kneaded and easily crystallized, so that high conductive performance can be obtained. Force that polyethylene terephthalate can be used Addition of a large amount of conductive particles will lower the spinnability during melt spinning, and it may be possible to use copolymerized polyethylene terephthalate to improve spinnability. When copolymerized polyethylene terephthalate is used, the crystallinity is generally lowered, and the conductive performance is lowered. From the above, polybutylene terephthalate, which is a polyester that easily forms crystals, is particularly excellent. Polyethylene 2, 6 naphthalate may be blended with polybutylene terephthalate.

[0016] The thermoplastic polyamide used in the conductive layer (A) is polyhexamethylene adipate.

(Nylon 6, 6), poly ε-force prolatatam (nylon 6) or a copolymer thereof is preferably used. Such a thermoplastic polyamide is suitably used like polybutylene terephthalate because it is easy to knead a large amount of conductive particles.

[0017] The conductive particles contained in the conductive layer (Α) are not particularly limited as long as they are conductive particles, and conductive carbon black, conductive metal oxide particles, metal particles, and the like can be used. . Of these, conductive carbon black is preferably employed from the viewpoint of the balance between conductive performance and cost. The particle diameter of the conductive particles is not particularly limited as long as it can be spun, but an average particle diameter of 0.01 to 1 μm is preferable.

[0018] The conductive carbon black used in the present invention, 10 one ^³ ~ 10 ^{3 Ω} · «Monogayo having an inherent electrical resistance of the eta,. When carbon black is completely dispersed in the form of particles, the conductivity is generally poor, and when a chain structure called a structure is formed, the conductivity is improved and the conductive carbon black is improved. It will be called. Therefore, in conducting the polymer with conductive carbon black, it is important to disperse the carbon black without destroying the structure. For this reason, even when a sufficient stretching operation cannot be performed, a fiber having a large dimensional stability is likely to be obtained.

[0019] In addition, the conductive metal oxide particles are not black unlike carbon black! It is also possible to impart conductivity to the colored fiber, which is useful in terms of design. The conductive metal oxide particles used in the present invention are white or colorless fine particles of metal oxide, or a state in which the metal oxide is coated on the surface with inorganic fine particles as nuclei. A fine particle. Many metal oxides are semiconductors close to insulators and often do not exhibit sufficient conductivity. However, as a conductivity enhancer (doping agent) for metal oxides, antimony oxide for tin oxide, aluminum, potassium, etc. for zinc oxide are known. For example, the specific resistance of acid 匕 tin with an average particle size of 0: m is about 10 ³ Ω 'cm, but the specific resistance of the solid solution of acid 匕 antimony and acid 匕 tin is 1 ~: ίΟ Ω 'cm and enhanced conductivity. From the standpoint of overall performance, it is necessary that the ratio of acid-antimony in the solid is 0.01 to 0.10 (weight ratio). If the coating amount of antimony and antimony is small, the electrical conductivity is insufficient, and conversely if it is large, it tends to move away from the direction of the target white system. As the conductive particles used in the present invention, the coated zinc oxide and tin oxide are preferable because of their excellent conductivity, whiteness, etc., but other metal oxides are used. In

[0020] In the present invention, one type or a mixture of two or more types of conductive particles can be used. At this time, conductive carbon black and conductive metal oxide particles may be used in combination. Furthermore, metal particles or the like may be used. In addition, various additives may be blended within a range not impairing the effects of the present invention.

[0021] The conductive layer (A) of the present invention comprises 60 to 80% by weight of thermoplastic resin and 20 to 40% by weight of conductive particles. If the content of conductive particles is less than 20% by weight, the conductivity may be insufficient. The content of the conductive particles is preferably 23% by weight or more, and at this time, the content of the thermoplastic resin is 77% by weight or less. On the other hand, if the content of the conductive particles exceeds 40% by weight, spinnability and stretchability may be deteriorated. The content of the conductive particles is preferably 33% by weight or less, and at this time, the content of the thermoplastic resin is 67% by weight or more.

[0022] The protective layer (B) of the present invention are those made of polyethylene terephthalate 50 to 95 wt% and Poryechire down one 2, 6-naphthalate 5-50 ^_0/0. The protective layer (B) is composed mainly of polyethylene terephthalate and polyethylene 2, 6 naphthalate. Therefore, it is possible to suppress changes in fiber properties with time after spinning. In the case of conductive composite fibers, the resin composition used in the conductive layer contains a large amount of conductive particles, so the contribution of the conductive layer to the overall mechanical performance of the composite fiber is much smaller. The mechanical properties of the protective layer are particularly important.

[0023] The polyethylene terephthalate used in the protective layer (B) is a polyester containing 80 mol% or more, preferably 90 mol% or more of ethylene terephthalate units. The third component may be copolymerized within the range without hindering the object of the present invention. Examples of the copolymer component preferably used include acid components such as isophthalic acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, sulfoisophthalic acid sodium salt, and sulfoisophthalic acid tetrabutyl phosphate salt, and diethylene glycol. 1, 4 butanediol, 1,6 hexanediol, neopentyl glycol, cyclohexane 1,4-dimethanol, 2,2 bis [4 (2 hydroxyethoxy) phenol] propane, etc. .

[0024] The polyethylene 1,2 naphthalate used in the protective layer (B) is a polyester containing 80 mol% or more, preferably 90 mol% or more of ethylene 1,2,6-naphthalate units. Even if the third component is copolymerized within the range not impairing the object of the present invention, there is no problem. As the copolymer component preferably used, those described in the description of the polyethylene terephthalate can be used in addition to terephthalic acid.

[0025] Polyethylene terephthalate or polyethylene 2,6-naphthalate used for the protective layer (B) contains inorganic fine particles having an average particle diameter of 0.01 to 1 / ζ πι at a ratio of 0.05 to 10% by weight. It is preferable from the viewpoint of spinnability or knitting. That is, when the content of the inorganic fine particles is less than 0.05% by weight, loops, fluff, fineness spots, etc. are likely to occur in the obtained conductive fiber. It causes thread. More preferably, the inorganic fine particles are contained at a ratio of 0.2 to 5% by weight. There are no particular restrictions on the method of adding the inorganic fine particles, and it is possible to add and mix the inorganic fine particles so that they are uniformly mixed in the polyester at any stage up to just before melt spinning. Oh ,. A typical example of such inorganic fine particles is titanium oxide.

[0026] protective layer (beta) is polyethylene terephthalate 50-95 wt ^_0/0 and polyethylene 2, 6 - but also made naphthalate 5 to 50 weight ^_0/0 force. If the polyethylene 1, 2, 6 naphthalate content is less than 5% by weight, changes in fiber properties with time after spinning cannot be sufficiently suppressed. The content of polyethylene 2,6 naphthalate is preferably 10% by weight or more, and more preferably 15% by weight or more. At this time, the content of polyethylene terephthalate is preferably 90% by weight or less, and more preferably 85% by weight or less. On the other hand, polyethylene - 2, 6 when the amount of naphthalate exceeds 50 weight ^_0/0, the filter pressure when spinning Nag only production cost increases is high, reeling is difficult, resulting conductive The elongation of the composite fiber also decreases. The content of polyethylene 2,6 naphthalate is preferably 40% by weight or less, and more preferably 30% by weight or less. In this case, the content of polyethylene terephthalate is preferably Ri der 60 weight ^_0/0 or more, and more preferably 70 wt% or more.

[0027] The conductive conjugate fiber of the present invention comprises 60 to 80% by weight of thermoplastic resin and conductive particles 20

榭脂composition comprising 40 wt ^_0/0 (a), polyethylene terephthalate 50-95 wt ^_0/0及beauty polyethylene - 2, 6-naphthalate 5-50 ^_0/0 consisting榭脂composition (b) It is manufactured by spinning together. That is, the melted resin composition (a) and the melted resin composition (b) are merged and melt-discharged from the composite spinneret to produce a conductive composite fiber.

[0028] The method for producing a conductive conjugate fiber of the present invention can use a general melt spinning apparatus used for producing a conjugate fiber. At this time, it is possible to form a conductive layer (A) by supplying pellets of a resin composition (a) obtained by previously melt-kneading thermoplastic resin and conductive particles to a melt spinning apparatus to form a conductive layer (A). Point power is also preferable. In addition, polyethylene terephthalate and polyethylene 2,6 naphthalate may be previously melt-kneaded to obtain pellets of the resin composition (b) and supplied to a force melt spinning apparatus to form the protective layer (B). The protective layer (B) may be formed after supplying each pellet to the melt spinning apparatus and obtaining the resin composition (b) in the apparatus! / ヽ.

[0029] The winding speed at this time is preferably 1500 to 3000 mZ. When the winding speed is less than 1500 mZ, both the elongation and the boiling water shrinkage rate become too large, and the dimensional stability is significantly reduced. The winding speed is more preferably 1800 mZ or more, and even more preferable Is over 2000mZ. On the other hand, if the winding speed exceeds 3000 mZ, yarn breakage may occur during spinning, and both elongation and boiling water shrinkage will be too small. In particular, when producing a conductive composite fiber that is required to have a certain degree of elongation or boiling water shrinkage for use as a blended fiber yarn, it is preferable to reduce the winding speed. More preferably, it is 2600 mZ or less, and more preferably 2400 mZ or less.

[0030] At the time of spinning, the spinning yarn may be cooled by blowing cold air or the like to wind up the force, but in order to effectively prevent cutting of the conductive layer (A), It is preferable to employ the following spinning method. That is, the following (1) to (5) are performed in that order, and the following (2) and (3) are preferably performed before the discharge yarn first contacts the roller or guide. .

(3) Next, run in the heating device and heat-treat

(4) Add oil afterwards

(5) Winding up at a speed of 1500-3000mZ

[0031] A feature of the above method is that the melted and discharged composite polyester filament is cooled and then heated and stretched using a heating zone such as a tube heater, and from the melt discharging to the heating and stretching. Without any substantial contact with the rollers or guides. By using such a method, the draw ratio is automatically adjusted in the zone in the heating device from the discharged molten polymer, where the conductive fibers are not drawn forcibly between the rollers or the guide rollers. Therefore, the conductive layer (A) is not stretched so as to be cut. In addition, the conductive layer (A) is stretched and crystallized appropriately, and the amorphous portion is in a state where molecular motion is possible, and as a result, tension is applied to the conductive layer (A). Even if a force is applied, the conductive layer (A) has a large room for extending without being cut, and the conductive performance is not lost. The heating temperature at the time of heat stretching is in the temperature range from the glass transition temperature of the resin constituting the resin composition (a) to the melting point and below, and the resin composition (b) It is preferable that the temperature is higher than the glass transition temperature and lower than the melting point of polyethylene terephthalate, which is the main component of

[0032] The cooling method of (2) above is that the temperature of the cooling air is about 20 to 30 ° C, the humidity of the cooling air is about 20 to 60% RH, and the blowing speed of the cooling air is 0.4 to lmZ. By setting it to about 2 seconds, it is possible to obtain high-quality fibers without causing fineness spots and performance spots. Further, the length of the heating zone used in the above (3) is 0.6 m or more and 4 m or less, and the temperature of the heating zone is in the range of 150 ° C. or more and 220 ° C. or less for uniform and smooth stretching. Desirable above.

[0033] In the conductive conjugate fiber of the present invention thus obtained, the weight ratio (AZB) of the conductive layer (A) to the protective layer (B) is preferably 5Z95 to 50Z50. When the weight ratio (ΑΖΒ) is less than 5/95, the conductivity becomes insufficient and the conductive layer (Α) is likely to be cut immediately. The weight ratio (ΑΖΒ) is more preferably 10Z90 or more, and further preferably 15Z85 or more. On the other hand, when the weight ratio (ΑΖΒ) exceeds 50Ζ50, the strength becomes insufficient and the change in fiber properties with time tends to increase. The weight ratio (ΑΖΒ) is more preferably 40 to 60 or less, and further preferably 30 to 70 or less.

[0034] The elongation (DE) of the conductive conjugate fiber of the present invention is 100 to 350%. If the elongation (DE) is less than 100%, the stretching may be too strong and the conductive layer (wrinkles) may be cut, and the required elongation or boiling water may be required when used as a mixed yarn. Can not have shrinkage. The elongation (DE) is preferably 150% or more, more preferably 180% or more, and even more preferably 200% or more. On the other hand, when the degree of elongation (DE) exceeds 350%, when the combined yarn is drawn with other fibers, stretch spots are formed and it is easy to cut in the subsequent processing step. The elongation (DE) is preferably 300% or less, and more preferably 250% or less. Here, the elongation (DE) is a value measured according to JIS L1013.

[0035] Further, the boiling water shrinkage (Wsr) of the conductive conjugate fiber of the present invention is preferably 20 to 60%. When the boiling water shrinkage rate (Wsr) is less than 20%, the workability of the combined yarn is lowered when used as a blended yarn. The boiling water shrinkage (Wsr) is more preferably 25% or more, and further preferably 30% or more. On the other hand, when the boiling water shrinkage rate (Wsr) exceeds 60%, for example, when a woven fabric is used, streaks due to shrinkage spots are generated and the texture is poor. The boiling water shrinkage (Wsr) is more preferably 50% or less, and even more preferably 40% or less. It is below. Here, the boiling water shrinkage (Wsr) is a value measured according to JIS L1013.

[0036] The conductive conjugate fiber of the present invention has a certain degree of elongation, but has little change over time in fiber properties such as elongation and boiling water shrinkage during transportation and storage. In particular, the change in fiber properties is small even when kept at high temperatures.

[0037] Specifically, when stored under conditions of 60 ° C and 80% RH, the spinning force is also the elongation (DE) force after 60 days 1.3 times the elongation (DE) after one day from spinning. Is preferably: 1

60 1

It is more preferable that it is 2 times or less. Here, the reason for starting from one day after spinning is to cancel the change in the degree of elongation (DE) due to the absorption of water and the temperature change, and to grasp the change in fiber properties over time more accurately. . Usually, the elongation (DE) is 0.9 of the elongation (DE).

60 1 or more times.

[0038] When stored under conditions of 60 ° C and 80% RH, boiling water shrinkage 60 days after spinning

It is preferable that the (Wsr) force is not less than 0.3 times the boiling water shrinkage (Wsr) one day after spinning.

60 1

Yes, it is more preferably 0.5 times or more, and even more preferably 0.7 times or more. Here, the reason for starting one day after spinning is the same reasoning force as in the case of the above elongation. Usually, boiling water shrinkage (Wsr) is 1.05 times or less of boiling water shrinkage (Wsr).

60 1

The When stored under conditions of 60 ° C and 80% RH, the spinning force is preferably 10% or more after boiling water reduction (Wsr), more preferably 15% or more. Masugu 2

60

More preferably, it is 0% or more.

[0039] The conductive conjugate fiber of the present invention is used in various forms and for applications that require various static elimination properties. For example, the conductive multifilament of the present invention is mixed with the nonconductive multifilament, and the conductive multifilament is 1 to 30 so that the conductive multifilament becomes the side yarn and the nonconductive multifilament becomes the core yarn. % The yarn can be mixed and used to increase the yarn length. As the core yarn, a polyester-based multifilament is preferable. The total thickness of the non-conductive multifilament used as the core yarn is preferably in the range of 20 to 120 dtex. In the case of a blended yarn, entanglement is generally applied so that the core yarn and the side yarn are not separated. After the entanglement is imparted, twist may be imparted to the blended yarn.

[0040] Further, a non-conductive multifilament may be used as a core yarn, and a conductive multifilament may be wound around the spiral. The thickness of the core yarn is the same as that of the above mixed fiber It is also the same that polyester multifilament is suitable as the core yarn. Multifilament yarns using such conductive fibers can be used for fabrics such as woven fabrics and knitted fabrics.

, 5mn! It is driven as a part of warp and Z or weft at a rate of ~ 50mm. As a result, the resulting woven or knitted fabric has a charge removal performance.

[0041] When the fibers are mixed in this way, a mixed yarn having excellent performance can be obtained by having an appropriate elongation (DE) and boiling water shrinkage (Wsr). And since the change over time of fiber properties over a long period of time, such as during transportation and storage, is small, fiber properties are stable during long-distance transportation such as international transportation and long-term storage. For example, it is possible to obtain a homogeneous product with good process passability such as mixed fiber, twisted yarn, weaving, and knitting.

[0042] The knitted or knitted fabric obtained as described above is used for applications that require long-term static elimination, for example, as a dust-proof garment worn in a clean room or in a chemical plant. It can be used as static proof working wear for workers engaged in workplaces that may explode due to static electricity, such as workers and workers handling chemicals. Furthermore, the conductive fiber of the present invention can be used as a part of a pile of a pet for removing electricity and further as a removing brush for a copying machine.

[0043] An application in which the conductive conjugate fiber of the present invention is particularly preferably used is a carpet that is liable to generate static electricity. The conductive conjugate fiber of the present invention is suitably used as a neutralizing fiber for carpets. For example, in the case of a nylon carpet, add 2 to 10 conductive composite fibers of the present invention to an unstretched or semi-stretched nylon multifilament yarn of about 1000 to 10000 dtex and align it, and the aligned yarn is 2 to 4 times. The drawn yarn thus obtained is made into a woven fabric or a knitted fabric, into a cut pile carpet or a loop pile carpet. The conductive conjugate fiber of the present invention has an appropriate degree of elongation (DE) and has little change with time in the fiber physical properties, so that the process passability in the drawing process is good. It takes a lot of time to produce a conductive conjugate fiber and produce a carpet with a lot of force, and it is often transported over a long distance. Therefore, the conductive conjugate fiber of the present invention is preferably used. . In particular, it is suitable for a so-called tufted carpet in which the drawn yarn is laid into a base fabric as a pile yarn, a latex is applied to the back surface to prevent the pile from coming off, and a makeup lining is attached. Example Hereinafter, the present invention will be described in more detail using examples. The test method in this example is as follows.

[0045] (1) Time course of elongation (DE)

The elongation (DE) was measured according to JIS L1013. Measure the elongation (DE) immediately after spinning

0

And store under the conditions of 60 ° C and 80% RH, measure the degree of elongation (DE) after one day from spinning, and then store under the above conditions, and after about 90 days after an appropriate period. It was measured. For the elongation (DE) 60 days after spinning, the data measured just 60 days later

60

If not, the elongation was calculated as a linear change between the elongation measured before and the elongation measured thereafter.

[0046] (2) Time course of boiling water shrinkage (Wsr)

Boiling water shrinkage (Wsr) was measured according to JIS L1013. After measuring the boiling water shrinkage (W sr) immediately after spinning, store it under the conditions of 60 ° C and 80% RH, and collect boiling water one day after spinning.

0

The shrinkage rate (Wsr) was measured, and after that, it was stored under the above conditions, and measured until about 90 days after an appropriate period. About boiling water shrinkage (Wsr) 60 days after spinning,

60

When there was no data measured after 60 days, the elongation was calculated as linearly changing between the elongation measured before and the elongation measured after that.

[0047] (3) Conductive performance

The conductive performance was determined as follows based on the period during which the composite fiber stored under the conditions of 60 ° C and 80% RH maintained a resistance value of 10 " ⁸ Ω Zcm or less. Was determined by Toa Denpa Kogyo Co., Ltd.'s super insulation meter “SM8220” and “SME8350”.

○: The above resistance value is maintained for at least one year after spinning.

Maintain the above resistance for 6 months or more and less than 1 year after spinning.

X: The resistance value can only be maintained for less than 6 months after spinning! /.

[0048] Example 1

As a raw material for the conductive layer (A), pellets of the resin composition (a) containing 25% by weight of conductive carbon black and having a polyethylene terephthalate (PBT) force were used. Further, as a raw material for the protective layer (B), a polyester containing 3% by weight of titanium oxide with an average particle diameter of 0.4 m. 10 parts by weight of polyethylene 2,6 naphthalate (PEN) pellets were blended with 90 parts by weight of terephthalate (PET) pellets. The conductive layer (A) and the protective layer are formed such that the conductive layer (A) made of the resin composition (a) forms a sheath and the protective layer (B) made of the resin composition (b) forms a core. Composite spinning was performed at a weight ratio (AZB) to (B) of 20Z80, and spinning was performed at a spinning temperature of 285 ° C. to obtain a conductive multifilament of 38 dtexZ2f.

[0049] As the spinning method, the melt of the resin composition (a) and the resin composition (b) are merged and melt-discharged from the composite spinneret, and the discharged molten polymer is-less than the glass transition point. Then, it is run in a heating device, stretched and heat treated, and then an oil agent is applied, and then the above-mentioned discharge yarn is first used as a roller or a roller by winding at a speed of 2200 mZ. The stretching heat treatment was performed before contacting the guide. As the cooling method, a cooling air of 25 ° C. and 60% RH was blown against the fiber immediately under the nozzle at a speed of 0.5 mZ seconds. As a stretching heat treatment method, a heating tube having a diameter of 3 cm and a length of lm was provided at a position 1.5 m immediately below the nozzle, and the inside of the tube was kept at 180 ° C. The fiberization processability was good and no problem. The composite fiber thus obtained was measured over time for elongation (DE), boiling water shrinkage (Wsr), and conductive performance. The results are shown in Fig. 1, and the composition and evaluation results of the composite fibers are summarized in Table 1.

[0050] Example 2

In Example 1, as the raw material for the protective layer (B), 80 parts by weight of the same polyethylene terephthalate pellets as used in Example 1 were used for the same polyethylene-2,6-nana as used in Example 1. A conductive multifilament was obtained in the same manner as in Example 1 except that 20 parts by weight of phthalate pellets were blended and used. The composite fiber thus obtained was evaluated in the same manner as in Example 1. The results and the composition of the composite fiber are shown in Fig. 2 and Table 1.

[0051] Example 3

In Example 1, as the raw material for the protective layer (B), 70 parts by weight of the same polyethylene terephthalate pellets used in Example 1 were used for the same polyethylene-2,6-nana as used in Example 1. A conductive multifilament was obtained in the same manner as in Example 1 except that 30 parts by weight of phthalate pellets were blended and used. The composite fiber thus obtained was evaluated in the same manner as in Example 1. The results and the composition of the composite fiber are shown in Fig. 3 and Table 1. [0052] Example 4

In Example 1, as the raw material for the protective layer (B), the same polyethylene-2,6-nana as used in Example 1 was used for 50 parts by weight of the same polyethylene terephthalate pellets used in Example 1. A conductive multifilament was obtained in the same manner as in Example 1 except that 50 parts by weight of phthalate pellets were blended and used. The composite fiber thus obtained was evaluated in the same manner as in Example 1. The results and the composition of the composite fiber are shown in Fig. 4 and Table 1.

[0053] Comparative Example 1

In Example 1, conductive multifilaments were obtained in the same manner as in Example 1 except that only the same polyethylene terephthalate pellets used in Example 1 were used as the raw material for the protective layer (B). The composite fiber thus obtained was evaluated in the same manner as in Example 1. The results and the composition of the composite fiber are shown in FIG. 5 and Table 1.

[0054] Example 5

In Example 2, conductive multifilaments were obtained in the same manner as in Example 2 except that the spinning speed was changed from 2200 mZ to 1800 mZ. The composite fiber obtained in this way was measured for elongation (DE) and boiling water shrinkage (Wsr) immediately after spinning.

0 0

Measured over time. The evaluation results are shown in Table 2 together with the composition of the composite fiber.

[0055] Example 6

A conductive multifilament was obtained in the same manner as in Example 2 except that the spinning speed was changed from 2200 mZ to 2900 mZ in Example 2. The composite fibers thus obtained were evaluated in the same manner as in Example 5. The results are shown in Table 2 together with the configuration of the composite fibers.

[0056] Example 7

In Example 2, instead of using polyethylene terephthalate pellets as the raw material for the protective layer (B), modified polyethylene terephthalate pellets containing 8 mol% of isophthalic acid component with respect to the total dicarboxylic acid component were used, and the spinning speed was 2200 mZ. A conductive multifilament was obtained in the same manner as in Example 2 except that the component force was changed to 2500 mZ. The results of evaluating the composite fibers thus obtained in the same manner as in Example 5 are shown in Table 2 together with the configuration of the composite fibers.

[0057] Example 8 In Example 1, as a raw material for the conductive layer (A), a pellet of a resin composition (a) having a nylon 1-6 (NY) strength containing 35% by weight of conductive carbon black was used, and the protective layer (B) The same polyethylene terephthalate pellets used in Example 1 as 85 parts by weight of the same polyethylene terephthalate pellets as used in Example 1, and 15 parts by weight of the same polyethylene 2,6-naphthalate pellets used in Example 1 are used as raw materials. Then, a conductive multifilament was obtained in the same manner as in Example 1 except that the spinning speed was changed from 2200 mZ to 2500 mZ. The composite fibers thus obtained were evaluated in the same manner as in Example 5. The results are shown in Table 2 together with the composition of the composite fibers.

[0058] Example 9

In Example 1, the spinning speed was changed from 2200 mZ to 2500 mZ, so that the conductive layer (A) having the same composition as in Example 1 forms a core, and the same protective layer (B) as in Example 1 forms a sheath. In addition, a conductive multifilament was obtained in the same manner as in Example 1 except that the composite spinning was performed with the weight ratio (AZB) of the conductive layer (A) to the protective layer (B) being 45Z55. The composite fibers thus obtained were evaluated in the same manner as in Example 5. The results are shown in Table 2 together with the composition of the composite fibers.

[0059] Example 10

In Example 1, the spinning speed was changed from 2200 mZ to 2500 mZ, the conductive layer (A) with the same composition as in Example 1 formed an island, and the protective layer (B) with the same composition as in Example 1 formed the sea. As in Example 1, except that composite spinning was performed with a weight ratio (AZB) of the conductive layer (A) to the protective layer (B) of 20Z80 to obtain a sea-island type composite fiber having four islands. In the same manner, a conductive multifilament was obtained. The composite fibers thus obtained were evaluated in the same manner as in Example 5. The results are shown in Table 2 together with the configuration of the composite fibers.

[0060] Comparative Example 2

In Example 1, as the raw material for the protective layer (B), 97 parts by weight of the same polyethylene terephthalate pellets used in Example 1, and the same polyethylene-2,6-nana as used in Example 1 were used. Conductive multifilaments were obtained in the same manner as in Example 1 except that 3 parts by weight of phthalate pellets were blended and the spinning speed was changed from 2200 mZ to 2500 mZ. The composite fiber thus obtained was evaluated in the same manner as in Example 5. Table 2 shows the composition of the fibers.

[0061] Comparative Example 3

In Example 1, as the raw material for the protective layer (B), the same polyethylene-2,6-nana as used in Example 1 was used for 40 parts by weight of the same polyethylene terephthalate pellets used in Example 1. A conductive multifilament was obtained in the same manner as in Example 1 except that 60 parts by weight of phthalate pellets were blended and the spinning speed was changed to 2200 mZ and 2500 mZ. The results of evaluating the composite fibers thus obtained in the same manner as in Example 5 are shown in Table 2 together with the configuration of the composite fibers.

[0062] Comparative Example 4

In Example 1, as the raw material for the protective layer (B), only the same polyethylene terephthalate pellets used in Example 1 were used, and the spinning speed was changed from 2200 mZ to 2900 mZ. Thus, a conductive multifilament was obtained. The composite fiber thus obtained was evaluated in the same manner as in Example 5, and the result of the composite fiber composition

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[0063] [Table 1]

[0064] [Table 2]

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[0065] Table 1 and Table 2 Karawaryokuru so on,榭脂composition constituting the protective layer (B) (b) is, Poryechi terephthalate 50 95 weight ^_0/0 and polyethylene 2, 6 naphthalate 5 50 fold J %, The changes over time in the elongation (DE), boiling water shrinkage (Wsr), and conductive performance of the conductive composite fiber are reduced (Examples 1 to 10). In contrast, when the content of polyethylene 2, 6 naphthalate protective layer (B) that make up the榭脂yarn且成product (b) is Ru 5 wt ^_0/0 less Dare, the conductive composite fibers Changes over time in elongation (DE), boiling water shrinkage (Wsr), and electrical conductivity increase (Comparative Examples 1, 2, and 4). That is, the effect of adding polyethylene 2, 6 naphthalate to the resin composition (b) constituting the protective layer (B) is clear.

Conductive multifilament yarn obtained in Example 1 (38dtexZ2f) and 3500dtex unstretched multifilament yarn with nylon 6 and 6 force are drawn together and stretched 2.6 times to produce drawn multifilament yarn. did. A base fabric was produced using the conductive multifilament yarn obtained in Example 1 as a component. The stretched multifilament yarn was stabbed into the base fabric as a pile yarn, a synthetic rubber latex was applied to the back surface, and a decorative lining was attached to produce a tufted carpet. In this manufacturing process, particularly the drawing process, no breakage of the conductive composite fiber was observed, and it was strong that the conductive composite fiber would not cause trouble in the manufacturing process. Even if the resulting carpet was laid on the floor surface of a dry room in winter and walked repeatedly on it, no static electricity was generated. In addition, there was no discomfort due to static electricity even when touching the carpet.

Claims

The scope of the claims

[1] Conductive layer (A) comprising 60 to 80% by weight of thermoplastic resin and 20 to 40% by weight of conductive particles, 50 to 95% of polyethylene terephthalate and ^{0 to} ₀ of polyethylene 2,6 5 to 50% by weight of naphthalate And a protective layer (B) comprising a conductive composite fiber characterized by having an elongation (DE) of 100 to 350%.

[2] The conductive conjugate fiber according to claim 1, wherein the thermoplastic resin constituting the conductive layer (A) is polybutylene terephthalate or polyamide.

[3] The conductive conjugate fiber according to claim 1 or 2, wherein the weight ratio (AZB) of the conductive layer (A) to the protective layer (B) is 5Z95 to 50Z50.

[4] The conductive conjugate fiber according to any one of claims 1 to 3, wherein the boiling water shrinkage (Wsr) is 20 to 60%.

[5] When stored under conditions of 60 ° C and 80% RH, the spinning force also shows the elongation (DE) after 60 days.

60. The conductive conjugate fiber according to any one of claims 1 to 4, which is not more than 1.3 times the degree of elongation (DE) one day after spinning.

[6] Boiling water shrinkage (Wsr) 60 days after spinning when stored at 60 ° C and 80% RH

The force according to any one of claims 1 to 5, which is not less than 0.3 times the boiling water shrinkage (Wsr) one day after spinning.

60 1

A conductive composite fiber as described above.

[7] Boiling water shrinkage (Wsr) 60 days after spinning when stored at 60 ° C and 80% RH

The conductive composite fiber according to any one of claims 1 to 6, which is 10% or more.

60

[8] A carpet using a fiber obtained by stretching the conductive conjugate fiber according to any one of claims 1 to 7.

[9] The thermoplastic榭脂60-80 wt% and the conductive particles 20 to 40% by weight consists榭脂composition and (a), polyethylene terephthalate 50-95 wt ^_0/0 and polyethylene 2, 6 naphthalate 5 A method for producing a conductive composite fiber comprising a composite spinning of 50% by weight of a resin composition (b), comprising: a molten resin composition (a) and a molten resin composition (b). A method for producing a conductive composite fiber, characterized in that the composite composite fiber is melted and discharged from a composite spinneret and wound up at a speed of 1500 to 3000 mZ.

[10] The following (1) to (5) are performed in that order, and the following (2) and (3) The method for producing a conductive conjugate fiber according to claim 9, wherein the method is performed before contact with one roller or a guide:

(3) Next, run in the heating device and heat-treat

(4) Add oil afterwards

(5) Wind up at a speed of 1500-3000mZ.