JPS61132626A - Conjugated fiber of high conductivity - Google Patents

Abstract

PURPOSE:The title fiber that is composed of the core component of conductive thermoplastic polymer containing conductive particles such as metallic particles and the sheath components of 2 different kinds of nonconductive thermoplastic polymers where one of the two polymer is insoluble in a solvent in which the other polymer dissolves, thus being readily manufactured and showing no metal abrasion. CONSTITUTION:The objective conjugated fiber is made by extruding, through a conjugate spinneret, (A) a conductive thermoplastic polymer, as the core component, containing at least one kind of particles selected from metallic particles, conductive metal compound particles and inorganic particles coated with metal or conductive metal compound, (B) a nonconductive thermoplastic polymer 2 and (C) another nonconductive thermoplastic polymer as the sheath components where a solvent or solution which dissolves or decomposes component C cannot or hardly dissolve the components A and B to give the objective conjugated fiber. After extrusion into fibers, only the component C is dissolved or decomposed and removed to increase its antistatic effect.

Description

[Detailed Description of the Invention] (Field of Application of M Tojo) The present invention is a novel conductive material! Regarding pongee. Specifically, conductive composite 1a that has no metal abrasiveness and is industrially manufactured.
Regarding fiber Cζ.

(Prior art) Hydrophobic 1aIR1 materials such as fibers, polyesters, polyamides, polyacrylonitrile, polyolefins, etc. generate significant static electricity due to friction, etc., and the charging voltage is often 10
kVe! Well, it's well known that it can cause serious injuries. For this reason, many proposals have been made regarding antistatic properties (imparting antistatic properties).

One method is to use a mixture of gold and 4N fibers with chargeability 11ζ, but the antistatic properties decrease due to breakage due to bending during processing and use, and it is difficult to mix, inter-knit, and inter-weave with other NA fibers. However, it has disadvantages such as the unique metallic luster that lowers the quality of the product.

In addition, 1IA fibers plated with metal and fibers coated with conductive substances have many disadvantages, such as extremely high manufacturing costs, often peeling off due to bending or friction during processing or use, and poor durability. evening.

In addition, m-fibers made by dispersing conductive particles such as carbon black or metal powder throughout a thermoplastic polymer have improved spinnability, strength, and elongation when the conductive particles are dispersed to the extent that they impart conductivity. However, it is extremely difficult to obtain a product that can be put to practical use.

In order to eliminate these drawbacks, ## is a composite of a thermoplastic polymer in which conductive particles such as carbon black or metal powder are dispersed and a fiber-forming polymer, either side-by-side or core/sheath.
Special Publication No. 52-81450, Special Publication No. 58-445
798, Special Publication Showa 57-256474! - Proposed in publications, etc. However, in composite m-tsumugi, in which a conductive component containing conductive particles is completely encapsulated with a non-remerged component, the black or gray of carbon black and metal powder is relatively inconspicuous, but the sheath causes a core discharge. It has the disadvantage that it requires dielectric breakdown and has poor antistatic properties. In addition, composite fibers with a conductive component as a sheath and composite fibers in which a conductive component and a non-conductive component are joined side-by-side have excellent corona discharge properties, that is, antistatic properties, because the conductive component is exposed on the fiber surface. The black or gray color of carbon black and metal powder stands out, which lowers the quality of products made by mixing these composite fibers, and also causes damage to other products due to friction.

In contrast to conductive particles exhibiting a black or gray color such as carbon black or metal powder, conductive particles with a higher white discoloration were developed in JP-A-54-
No. 161598, JP-A-56-140028, etc., and it has become possible to obtain fibers with relatively high white discoloration even if the conductive component is exposed on the surface of the M fiber. However, examples of highly conductive particles that cause white discoloration include metal oxides such as tin oxide, zinc oxide, indium oxide, and titanium oxide, and these metal oxide particles are used in large amounts to provide sufficient conductivity. If mixed with other materials, it often causes significant damage to the object being rubbed. For example, there is a tendency for guides, knitting needles, heater plates, and even spinning nozzles to be seriously damaged during the spinning, processing, and weaving and knitting processes. Therefore, even when using conductive particles with high precision, a core-sheath type in which the conductive wL seat is not exposed on the surface is preferable from the viewpoint of abrasion resistance, but there are contradictory problems in that it is inferior from the viewpoint of antistatic property.

(Problems to be Solved by the Invention) The purpose of the present invention is to prevent the obstruction and damage of frictional (M, contact) objects in the process of manufacturing woven products containing fibers and fibers. Therefore, it is an object of the present invention to provide a conductive composite fiber that is industrially easy to manufacture and has excellent antistatic properties.

(Means for solving the problem) The inventors are i? The present invention was completed as a result of intensive research to improve the various defects of the conductive fibers described in II. The present invention comprises metal particles, conductive metal compound particles, and a film of metal or conductive metal compound. A conductive thermoplastic polymer (2) containing at least one type of conductive particle selected from the group consisting of inorganic particles is a core component, and two non-conductive thermoplastic polymers (2) and (C) are a sheath component. It consists of
A solvent or solution that dissolves or decomposes the polymer ((C)
On the other hand, the present invention relates to a conductive composite fiber characterized in that polymers (4) and 03) are insoluble or hardly soluble.

That is, the polymer (4) is a thermoplastic polymer containing at least one conductive particle selected from the group consisting of metal particles, conductive metal compound particles, and inorganic particles having a coating of metal or conductive metal compound. It is a combination and is insoluble or poorly soluble in a solvent or solution that dissolves or decomposes the polymer (6).

The polymer [F]) is a fiber-forming thermoplastic polymer,
In addition, similar to the polymer matrix, a polymer (0 is a thermoplastic polymer, and the polymer matrix (B
) can be selected by combining them.

As the conductive particles used in the present invention, any type of particles can be used as long as they have a specific resistance of about 10Q-CM or less in powder form, and metal oxides and metal oxide films that are highly susceptible to white discoloration can be used. In addition to inorganic particles, there are also relatively highly colored particles such as metal powders (such as silver, nickel, copper, iron, aluminum, or alloys thereof), and metal compounds such as sulfide steel, copper iodide, zinc sulfide, and cadmium sulfide. Can be used.

In other words, when mixed with gray or light-colored products such as clothing and carpets, tin oxide mixed and fired with a bright whitening metal oxide or inorganic particles having a metal oxide film, such as antimony oxide as a second component, Zinc oxide mixed and fired with aluminum oxide as a second component, titanium oxide having a film of isoelectric oxide such as tin oxide or zinc oxide, inorganic particles such as magnesium oxide, silicon oxide, aluminum oxide, etc. are used. can. Products that do not require white color, such as dust collection filters, printing/textile screens, and static elimination brushes
When used, metal powders, sulfide steel, copper iodide, cadmium sulfide, and other relatively highly colored metal compounds can also be used.

The conductivity of conductive particles is determined by the specific resistance in powder form to'xΣ
- Ef is preferably about α or less, particularly about 102Ω·C11 or less, and most preferably about 10Ω·1 or less. actually 10
A conductivity of about 2 Ω·α to 10 −2 Ω·1 can be obtained and can be suitably applied to the purpose of the present invention, but a conductive material with even better conductivity is even more preferable. The specific resistance (volume resistivity) of the powder is determined by filling an insulating cylinder with a diameter of ICI for 5 yr with a sample, applying a pressure of 200 kli from the top with a piston, and applying a DC voltage (e.g. 0.001 to 1000 V) (wt (at a current of 1 mA or less).

Further, the conductive particles must have a sufficiently small particle size. Although particles with an average particle size of 1 to 2 μm are not unusable, those with an average particle size of 1 μm or less, particularly 0.5 μm or less, and most preferably 0.8 μm or less are used. However, particles with a particle size of less than 0.1 μm tend to have poor dispersibility, so particles with a particle size of 0.1 to 1 μm are usually suitable.

The mixing ratio of conductive particles varies depending on the type 81 of the particles, conductivity, particle size, chain-forming ability of the particles, and the properties and crystallinity of the binder polymer to be mixed, but it is usually about 30 to 85% (by weight). The specific resistance (volume resistivity) of the electrical component forming the core must be less than 10Ω・α, and is within the range of 40 to 80% in most cases.
- 1 or less is preferable, and 102Ω/1 or less is preferable.

The polymer that is mixed with the conductive particles to form the conductive polymer (core component) is not particularly limited, and any polymer may be used. For example, there are many thermoplastic polymers such as polyamides, polyesters, polyolefins, polyvinyls, polyethers, etc., and those with fiber forming properties are preferred from the viewpoint of spinnability, but they cannot be used as one of the sheath components.
Tsumugi shadow forming property 1 combination 03 example round nylon 6, nylon 6
6. Polyamides such as nylon 12, polyesters such as polyethylene terephthalate and polybutylene ethylene phthalate, polyolefins such as polyethylene and polypropylene, polyvinyl polymers such as polyvinyl chloride and polyacrylonitrile, and polyurethane are sufficiently spinnable. Good composite fibers can be obtained.

The above-mentioned polymers can usually be used for the polymer G3) constituting one of the sheath components, but it is better to use a polymer that is the same as or has the same content as the polymer that forms the conductive polymer (4). This is preferable from the viewpoint of preventing the union (B) from peeling off. However, the ratio of ffi coalescence) to polymer (4) is high;
For example, 60% or more, polymer (up to) and U/z
Peeling can also be prevented by adding a mutual affinity improver to the polymer (B), and depending on the purpose of use, it may not be accompanied by bending or C11 rubbing, so even different polymers may be sufficient. Sometimes it is used and one question is asked.

Examples of the above-mentioned mutual affinity improving agent include a copolymer of both, a polymer having one or both of terminal Q, l, and/or side chain groups, and copolymers are generally used. For example, in the case of polyethylene and nylon, a gold ion-containing ethylene-methacrylic acid copolymer such as an ionomer is used, and in the case of polyamide and polyester, polyamide and polyether such as polyalkylene glycol or polyester such as polyalkylene terephthalate are used in block form. There are block polyetheramides and block polyesteramides that are bonded to

Another polymer 0Iζ forming the sheath component The thermoplastic polymer used must be chosen depending on the combination of polymers (4) and 03). That is, the combination must be such that polymer (4) and (2) are insoluble or poorly soluble in a solvent or solution that dissolves or decomposes polymer (C).

For example, when polymers (2) and (B) are commonly used fiber-forming polymers (polyamide, polyester, polyacrylonitrile, polyvinyl chloride, polyolefin, polyurethane), for example, benzene, toluene, etc. Polystyrene and its derivatives which are soluble in the WRg agent, polyethylene glycol, polypropylene glycol, vinyl alcohol and their derivatives which are easily soluble in water or weak alkali can be used.

When the polymer matrix and Φ) are a combination of specific polymers, it is necessary to select appropriate polymers depending on the combination. For example, when polymers (4) and [F]) are polyamides or polyolefins, esters, polyethers, and derivatives thereof are soluble in alkaline aqueous solutions, and polymers (2) and (8) are polyesters, polyacrylonitrile, In the case of polyvinyl chloride, polyamides and derivatives thereof are soluble in acids such as formic acid and hydrochloric acid, and in the case of polyurethane, polyesters, polyethers, or polyamides soluble in acids are soluble in alkaline solutions. can be used. Even if polymers (4) and (B) are a combination of different polymers, such as polyamide and polyester, polyamide and polyolefin, polyacrylonitrile and polyvinyl chloride, polyethylene glyfur, polyester, polyether, l-lyamide, polyester, etc. Polymers can be selected according to each combination. However, it is necessary to select an appropriate f 1 mer in consideration of operability such as spinning and the dissolution or decomposition rate of polymer 0.

For example, the combination of polymer (2) and polymer (8) is polyol, high molecular weight polyethylene glycol that is solid at room temperature, and copolymer of preethylene glycol and polyester have excellent spinnability, and water is easy to handle. Alternatively, it is preferable because it is easily soluble in an alkaline aqueous solution, and when the combination of the aggregate and the polymer [F] is polyester and polyolefin, nylon 6 or nylon that is soluble in acids such as sulfuric acid or salt Fl is preferable. In addition to polyamides such as No. 12, water-soluble previnyl alcohol and polyethylene glycol can of course be used.Also, when polymer (2) and polymer (2) are a combination of polyamide and polyester, acid/alkali Iζ can be used.
Polystyrene which is insoluble and soluble in organic solvents such as benzene and toluene is preferred.

Furthermore, even if the temperature is the same as that of polymer (4) and (J or 2), a polymer whose dissolution or decomposition rate is sufficiently higher than that of polymer (4) or (2) can be used. Polymer prisoner, G
Although it varies depending on the composite ratio of 3) and (C), polymer (0
The dissolution or decomposition rate of ) must be at least 8 times that of polymer (2) and polymer (2), preferably 6 times or more, and most preferably 10 times or more.

A core component consisting of conductive polymer ■ and polymers (B) and (0
The composite ratio of the sheath component consisting of is not particularly limited, but the composite ratio of the core component is usually 3 to 80%,
Preferably it is about 6 to 60%.

On the other hand, the composite ratio of polymer ① and 0 is usually 9515 to 40/6
0, but it is necessary to choose the composite ratio depending on the usage situation. For example, when used in carpets, clothing, etc. that are subject to bending, tension, and MB, it is preferable to increase the polymer ratio.When used in areas that are not subject to burrs or scratches, such as filters, it is preferable to increase the polymer ratio. ) can be sufficiently usable even if the ratio is low. Usually woven, knitted,
This is because the polymer ((C)) is removed and used after it is made into products such as nonwoven fabrics and brushes.

Examples of the cross-sectional shapes of the core component, sheath component, and fibers and their composite forms are shown in Fig. 1 and Figs. It can take any form or compound form.

(Effect M of the invention) The major feature of the fiber to be coated according to the present invention is that the final product or case I
Therefore, it is only necessary to remove the polymer (5) during the straight bending process, so the process (for example, spinning,
Guides, needles, plate heaters,
There is no wear and tear on spinning, nozzles, etc., and industrial curves can be manufactured very easily and efficiently.

In addition, during toilet use, polymer a) is removed by a solvent or melting process, and polymer (4), which is a conductive component, contributes to #day-to-day load movement and corona discharge. This occurs easily and can exhibit excellent tlE properties.

The composite fiber of the present invention is in the form of a continuous filament or a staple, and can be mixed with other chargeable fibers to impart Vth control to textile products.

The mixing ratio is usually about 0.1 to 10%, but depending on the purpose, a mixing ratio of 10 to 100% or 0.1 or less may be applied. The mixture is mixed cotton and gold thread.

This can be done by twisting, blending, interweaving, interweaving, or any other known method.

(Example) The effects of the present invention will be specifically explained below using Examples 1 and 7. Parts and percentages refer to Mk ratios unless otherwise specified.

Example 1 Titanium oxide with an average particle size of 0.24 μm was coated with a tin oxide film with a concentration of about 12%. Antimony oxide fine particles (
M1 is a conductive powder obtained by mixing and firing 2% of 0.02 μm in particle size. The average particle size of Powder Mu 1 is 0.25 μm,
It had a specific resistance of 9Ω·α, a reflectance of 82%, and a slightly gray-blue color.

Nylon 6 powder 26R1 with a molecular weight of about ts, ooo and a melting point of 216°C. After mixing 175 parts of E powder and 0.5 parts of magnesium stearate as a dispersant in powder form, the mixture was melt-kneaded twice using a twin-screw mixer to obtain a conductive polymer OF. The volume resistivity of the obtained polymer OPt was 1.5×10Ω·α.

Pl is a polymer obtained by dispersing 1.5% of titanium oxide particles as a matting agent in the same nylon 6 used for CPl. A modified polyester copolymerized with 15% polyethylene glycol having a molecular weight of about 1000 is designated as p.

Composite spinning was carried out as shown in Fig. 1 using CPl as a core component and Pl and P2 as sheath components. Further, composite spinning was carried out in a core/sheath and side-by-side type as shown in FIGS. 9 and 10 using CPl as a fl component and PT as a protective component. OF.

The composite ratio of /PI/P2 and OF t /P t is 10/
80/10 and 10/90.

Melt composite 8 components or 2 components in a 280'C diameter 0.
The undrawn yarns UYI to UY were spun from a 25 ff orifice, cooled, oiled, and removed at a speed of 8007 ff/min to obtain undrawn yarns UYI-UYg of 55 denier/3 filaments at a draw ratio of 2.2. times, 85
The yarn was drawn using a heated roller at 170° C. and then wound under tension at 170° C. to obtain drawn yarns Y1 to Y8 of 25 denier/3 filaments. The obtained yarns Y and ~Y8 were each knitted into a circular knitted fabric made of nylon 6 ordinary yarn (210 denier 154 filament) at intervals of about 6 ff, and after removing the spinning oil with a surfactant, the yarn was woven at 95'C, 2%. Polymer P! is treated with an aqueous solution of II hydroxide). -xs was obtained from the knitted fabric in which the As a control, a knitted fabric containing no conductive yarn was prepared and subjected to the same treatment.
I got it.

The obtained knitted fabric was thoroughly washed with water in Steps 1 to 4, dried at 80'C for 3 hours, and then dried in an atmosphere of 25°C and 88% RH for 6 hours. ! The friction charge had a positive charging voltage. The measurement was performed using the sound of the present invention.
The method proposed in the issue was carried out using a trowel, and a cotton cloth was used as the friction cloth. The charging voltage was measured 10 seconds after friction. The results are shown in Table 1 together with the operability in spinning and drawing conductive yarn.

The first surface conductor W1.5y, the yarn Y8 exposed on the uneven surface is
During spinning, the yarn was bent at the point where it exited the orifice, causing yarn breakage, and during drawing and winding, the traveler was significantly worn and yarn breakage occurred frequently, so it was not possible to wind up 3 to 500 fL. Furthermore, wear was also observed on the plate heater for heat fixation. Yarn Y in which the conductive component is completely encapsulated! Although the operability was good, the antistatic property was not satisfactory.

Example 2 70 parts of the conductive particles Al used in Example 1 and a molecular weight of about 50,
000. Low-density polyethylene 30% with a melting point of 102°C is melt-kneaded in powder form using a twin-screw kneader to form conductive polymer CP! I got it. The volume resistivity of the obtained polymer ap2 was 15.8×10Ω·α.

60 parts of nickel fine powder with an average particle size of 2 μm and a molecular weight of about 17.00 produced by thermally decomposing nickel tetracarbonyl
0, 40 parts of nylon 6 with a melting point of 215°C in powder form,
In addition, zinc oxide powder with an average particle size of 0.15 μm 1 ζ Aluminum oxide and -aluminum oxide with an average particle size of 0.02 μm were mixed and fired, and then further pulverized to obtain an average particle size of 0.22 μm 1 Volume resistivity 20 Ω - α conductive zinc oxide fine powder 75%, molecular weight approximately 16,000. Melting point 257°C
25 parts of polyethylene terephthalate and 0.5 parts of a polyethylene oxide/polypropylene oxide block copolymer as a dispersant were melt-kneaded in the same twin-screw mixer 1 [81] to obtain conductive polymers OF and C1 (C).

Molecular weight approximately 16,000. 0 parts of titanium oxide fine particles were added to 100 parts of polyethylene terephthalate with a melting point of 257°C.
．． Let Ps be the polymer containing 6 moieties.

Melt flow index is 247/10 minutes (200℃
, if 5 kg) of iristyrene is designated as P4.

Average molecular weight approximately 20. OOO,M Let Ps be polyethylene oxide with a solid point of about 60°C.

Conductive polymers OF, ~OP4 and -rimers P1-P6
Perform composite spinning with a composite shape as shown in Figure 6 using
4N yarns Y4 to Y1 were obtained. The combinations and composite ratios of conductive polymer (1) and polymers (2) and (0) are shown in Table 2.

Table 2 Spinning and stretching were performed in the following manner. The eight molten components were combined in a spinning pack, spun through an orifice with a diameter of 0.251111, cooled and oiled, and then spun into a yarn of 100,0 m.
It was wound up at a speed of /min. However, the spinning temperature was 270°C for yarn Y4 and 285°C for yarns Y6 and Y7.

The obtained undrawn yarns were each drawn 2.2 times using a heated roller at 85°C, and heat-fixed using a heat plate at 170°C to obtain drawn yarn Y4 of 30 denier 15 filament.
~Y7 was obtained. Both problems occur during the process of obtaining drawn yarn (thread breakage during spinning/drawing, guides, rollers, etc.)
There were no mechanical problems such as heater plates, etc., and the operability was almost the same as that of ordinary yarn.

The obtained yarn was used to create circular knitted fabrics in the same manner as in Example 1. After removing the spinning oil with a surfactant, the obtained circular knitted fabric was polymerized with 2% sodium hydroxide solution at 95°C for LC4 and 2% sodium hydroxide solution at 95°C, K6 in toluene, and KT in hot water at 98°C. (C) was almost completely removed.

The circular knitted fabric from which the polymer (C) had been removed was thoroughly washed with water, and the frictional charging voltage was measured in the same manner as in Example 1.

As shown in Table 8 Cζ, all had excellent antistatic properties.

Table 8: Polymers (4) and 03) used in yarn Y6 and the pentapolymer are both decomposed in an alkaline aqueous solution, but the decomposition rate for the alkali aqueous solution is 1 for the former and approximately 5 for the latter.
0, polymers 03) and (0) were hardly decomposed and no decrease in strength was observed in the time that was sufficient to almost completely decompose polymer (6).

[Brief explanation of drawings]

@Figures 1 to 8 are specific examples of cross sections of composite fibers of the present invention. However, Fig. 2 shows the polymer (
This is a specific example of a cross section after removing C). FIGS. 9 and 10 are examples of cross-sections of a conventional composite m-miscellaneous structure consisting of two components. In the figure, 1 indicates the conductive polymer (4), 2 indicates the non-conductive polymer (3), and 8 indicates the non-conductive polymer ((C).〃 Kanebo Gosen Co., Ltd. - Procedural Amendments Showa April 10, 1960 Rin Agency Director Shiga Means 1, Indication of the case 1982 Patent Application No. 254849 3, Relationship with the person making the amendment Patent applicant Address 17-4 Sumida 5-chome, Sumida-ku, Tokyo Name (0
96) Representative of Kanebo Co., Ltd. Susumu Okamoto “°yu” Contact address: 1-5-90 Tomobuchi-cho, Bejima-ku, Osaka 684 Kanebo Co., Ltd. Patent Department Tel: (06) Hl-1251 4. Date of amendment order August 26, 1985 (shipment date) 5. Number of inventions increased by amendment None 6. Subject of amendment 7. Contents of amendment (1) Figures 1 to 10 will be amended in the attached circular. Two wells if
Figure 2 Figure 3 Figure 4 Figure 5 Figure 16 Figure 7 Figure 8 Figure 9 Figure 10

Claims (7)

[Claims] (1) Conductive thermoplastic polymer (A) containing at least one conductive particle selected from the group consisting of metal particles, conductive metal compound particles, and inorganic particles having a film of metal or conductive metal compound. It consists of a core component and two types of non-conductive thermoplastic polymers (B) and (C) as a sheath component, and the polymer (A) and A conductive composite fiber characterized in that (B) is insoluble or hardly soluble. (2) Claim 1 in which the conductive metal compound is tin oxide, zinc oxide, indium oxide, copper sulfide or copper iodide.
Fibers as described in Section. (3) The fiber according to claim 1, wherein the metal particles are silver, nickel, copper, or aluminum. (4) The fiber according to claim 1, wherein the thermoplastic polymer forming the polymer (A) and the polymer (B) are the same or the same type of polymer. (5) The fiber according to claim 1, wherein the polymer (A) and/or the polymer (B) contain a mutual affinity improver. (6) The fiber according to claim 1, wherein the polymer (B) is polyamide, polyester, polyether, polyvinyl polymer, or polyolefin. (7) The fiber according to claim 1, wherein the polymer (C) is soluble in water or an aqueous alkaline solution.