JP7048468B2 - Unstretched conductive composite fiber and method for manufacturing BCF using it - Google Patents
Unstretched conductive composite fiber and method for manufacturing BCF using it Download PDFInfo
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Description
本発明は、延伸後にも優れた導電性を示す未延伸ポリアミド系導電性複合繊維およびそれを用いたＢＣＦの製造方法に関するものである。 The present invention relates to an unstretched polyamide-based conductive composite fiber that exhibits excellent conductivity even after stretching, and a method for producing a BCF using the same.
嵩高連続長繊維（ＢＣＦ：Ｂｕｌｋｅｄ Ｃｏｎｔｉｎｕｏｕｓ Ｆｉｌａｍｅｎｔ）はポリアミド、ポリプロピレン、ポリエステル、ポリ乳酸などの樹脂を紡糸延伸捲縮加工した繊維であり、自動車、家屋、車両、航空機などのカーペットに用いられる。このカーペットには実用的な強度、耐光性、耐へたり性、意匠性、制電性が求められる。カーペットなどの布帛に制電性を与える方法として、帯電防止剤を含む繊維を使用したり、布帛自体に帯電防止加工を施すことがある。しかし帯電防止剤や帯電防止加工は外気の水分によりその効果を発揮するものであり、乾燥した環境であれば、そのカーペットの制電性は損なわれ、不快な静電気を発生することとなる。そこでいかなる環境下でも高い制電性を得る方法として、導電性繊維をカーペットの中に混ぜ込むことがある（特許文献１）。 Bulked continuous fiber (BCF) is a fiber obtained by spinning, stretching and crimping a resin such as polyamide, polypropylene, polyester or polylactic acid, and is used for carpets of automobiles, houses, vehicles, aircraft and the like. This carpet is required to have practical strength, light resistance, sag resistance, design and antistatic properties. As a method of imparting antistatic properties to a fabric such as a carpet, fibers containing an antistatic agent may be used, or the fabric itself may be subjected to antistatic processing. However, antistatic agents and antistatic processing exert their effects by the moisture of the outside air, and in a dry environment, the antistatic property of the carpet is impaired and unpleasant static electricity is generated. Therefore, as a method of obtaining high antistatic property under any environment, conductive fibers may be mixed into the carpet (Patent Document 1).
導電性繊維をカーペットの中に混ぜ込むと方法として、ＢＣＦ製造時にカーボンブラックを含有する導電性繊維を混繊させる方法がある。ＢＣＦの製造は通常、樹脂を溶融して多数の孔を持つノズルから押し出し、複数のローラーを通過させて連続的に延伸、更にエアジェットで嵩高加工を施し、巻取機で巻き取ることで製造される。この工程において、ノズルから押し出され、延伸される前の糸条にボビン等に巻かれた導電糸を繰り出し、ガイドなどを介し混繊させる。ここで、混繊された導電糸は延伸に対し破断しないのはもちろんのこと延伸、嵩高加工後も一定以上の導電性を有していなければならない。また、この導電糸はカーペットに混ぜ込まれた際にカーボンブラック特有の黒筋が目立ってしまっては、カーペットの意匠性が著しく損なわれてしまう。
本発明は、ＢＣＦ製造時に混繊、延伸されても十分な導電性を有しており、カーペットに使用された際に黒筋が目立たない導電糸を提供することをその目的とする。
As a method of mixing conductive fibers into carpet, there is a method of mixing conductive fibers containing carbon black during BCF production. BCF is usually manufactured by melting the resin, extruding it from a nozzle with a large number of holes, passing it through multiple rollers, continuously stretching it, performing bulk processing with an air jet, and winding it with a winder. Will be done. In this step, the conductive yarn wound on the bobbin or the like is unwound on the yarn extruded from the nozzle and before being drawn, and the yarn is mixed through a guide or the like. Here, the mixed conductive yarn must not only not break with respect to stretching, but also have a certain level of conductivity even after stretching and bulk processing. Further, if the black streaks peculiar to carbon black become conspicuous when the conductive yarn is mixed with the carpet, the design of the carpet is significantly impaired.
It is an object of the present invention to provide a conductive yarn which has sufficient conductivity even when mixed and stretched during BCF production and whose black streaks are inconspicuous when used for carpets.
すなわち、本発明は、導電性カーボンブラックを２０質量％以上、４５質量％以下含有するポリアミドからなる導電層と、隠ぺい性無機顔料を５質量％以上含有するポリアミドからなる保護層とを有し、破断伸度が２００～６００％であり、線抵抗値が１．０Ｅ＋０５～９．９Ｅ＋０７Ω／ｃｍであり、全周長に対する導電層の露出周長の割合は８％未満である、未延伸導電性複合繊維をその要旨とする。
上記未延伸導電性複合繊維は、ＢＣＦを製造する際の延伸工程への供給するものであることが好ましい。
上記未延伸導電性複合繊維は、繊維横断面における保護層の外周に３個以上の凸部を有するものであることが好ましい。
本発明は、また、非導電性繊維と導電性繊維と混繊してＢＣＦを製造する方法であって、非導電性繊維を溶融紡糸する第１工程、溶融紡糸して得られた未延伸非導電性繊維と、上記未延伸導電性繊維を混繊して延伸する第２工程、混繊した延伸糸を流体噴射により嵩高加工する第３工程、得られた嵩高加工糸を巻き取る第４工程とを含むＢＣＦの製造方法でもある。
That is, the present invention has a conductive layer made of a polyamide containing 20% by mass or more and 45% by mass or less of conductive carbon black, and a protective layer made of a polyamide containing 5% by mass or more of a concealing inorganic pigment. The elongation at break is 200 to 600%, the linear resistance value is 1.0E + 05 to 9.9E + 07Ω / cm, and the ratio of the exposed peripheral length of the conductive layer to the total peripheral length is less than 8%, unstretched conductivity. The gist is composite fiber.
The unstretched conductive composite fiber is preferably supplied to the drawing step when producing BCF.
The unstretched conductive composite fiber preferably has three or more convex portions on the outer periphery of the protective layer in the cross section of the fiber.
The present invention is also a method for producing BCF by mixing non-conductive fibers and conductive fibers, the first step of melt-spinning non-conductive fibers, unstretched non-stretched obtained by melt-spinning. The second step of mixing and stretching the conductive fibers and the unstretched conductive fibers, the third step of bulk processing the mixed drawn yarn by fluid injection, and the fourth step of winding up the obtained bulky processed yarn. It is also a method for producing BCF including.
本発明によれば、ＢＣＦ製造時に混繊、延伸されても十分な導電性を有しており、カーペットに使用された際に黒筋が目立たない導電糸を提供できる。 According to the present invention, it is possible to provide a conductive yarn which has sufficient conductivity even when mixed and stretched during BCF production and whose black streaks are inconspicuous when used for a carpet.
以下、本発明を詳細に説明する。
本発明は、導電層と、保護層とからなる未延伸導電性複合繊維である。
Hereinafter, the present invention will be described in detail.
The present invention is an unstretched conductive composite fiber composed of a conductive layer and a protective layer.
本発明において、導電層を構成するベースポリマーとなる熱可塑性樹脂は、ポリアミドである。
これらポリアミドとしては、例えば、ポリアミド６、ポリアミド６６、ポリアミド１２、ポリアミド１１、ポリアミド６１０、ポリアミド６１２及びそれらを主体とする共重合体が挙げられ、中でも、ポリアミド６、ポリアミド６６、ポリアミド１２が好ましい。
In the present invention, the thermoplastic resin serving as the base polymer constituting the conductive layer is polyamide.
Examples of these polyamides include polyamide 6, polyamide 66, polyamide 12, polyamide 11, polyamide 610, and a copolymer containing them as a main component, and polyamide 6, polyamide 66, and polyamide 12 are preferable.
本発明の未延伸導電性複合繊維の導電層は、導電性カーボンブラックを２０質量％以上、４５質量％以下含有したポリアミドである。 The conductive layer of the unstretched conductive composite fiber of the present invention is a polyamide containing 20% by mass or more and 45% by mass or less of conductive carbon black.
本発明の導電性複合繊維において、導電層は、導電性カーボンブラックを２０質量％以上、４５質量％以下含有する。カーボンブラックの量が、少な過ぎると導電性及び制電性が得られず、多過ぎると、紡糸の際に、流動性が失われ製糸性が悪くなる傾向がある。中でも、カーボンブラックの含有量は、２５質量％以上、４０質量％以下が好ましい。 In the conductive composite fiber of the present invention, the conductive layer contains 20% by mass or more and 45% by mass or less of conductive carbon black. If the amount of carbon black is too small, conductivity and antistatic properties cannot be obtained, and if it is too large, fluidity is lost during spinning and the spinning property tends to be deteriorated. Above all, the content of carbon black is preferably 25% by mass or more and 40% by mass or less.
本発明において、導電層に用いられる導電性カーボンブラックとしては、ケッチェンブラック、ファーネスブラック、アセチレンブラック、チャンネルブラックなどが挙げられ、優れた導電性を有するカーボンブラックであれば特に限定はされない。 In the present invention, examples of the conductive carbon black used for the conductive layer include Ketjen black, furnace black, acetylene black, channel black, and the like, and the carbon black having excellent conductivity is not particularly limited.
本発明において、保護層を構成する熱可塑性樹脂は、ポリアミドである。
保護層は、通常は、導電材料としてのカーボンブラックを含まない非導電層である。
本発明において保護層となるポリアミドとして、例えばポリアミド６、ポリアミド６６、ポリアミド１２、ポリアミド１１、ポリアミド６１０、ポリアミド６１２などのポリアミド、及びこれらを共重合した物が挙げられるが、溶融紡糸可能なものであれば特に限定されるものではなく、好ましくはポリアミド６、ポリアミド６６である。
In the present invention, the thermoplastic resin constituting the protective layer is polyamide.
The protective layer is usually a non-conductive layer that does not contain carbon black as a conductive material.
Examples of the polyamide used as the protective layer in the present invention include polyamides such as polyamide 6, polyamide 66, polyamide 12, polyamide 11, polyamide 610, and polyamide 612, and copolymers thereof, which can be melt-spun. If there is, the present invention is not particularly limited, and polyamide 6 and polyamide 66 are preferable.
本発明の未延伸導電性複合繊維の保護層は、隠ぺい性無機顔料を含有する。この隠ぺい性無機顔料は導電部分のカーボンブラックの着色を隠ぺいする。 The protective layer of the unstretched conductive composite fiber of the present invention contains a concealing inorganic pigment. This concealing inorganic pigment hides the carbon black coloring of the conductive part.
隠ぺい性無機顔料の含有量は、保護層のポリアミドに対し、５質量％以上であり、より好ましくは、７質量％以上である。隠ぺい性無機顔料の含有量が多過ぎると、導電性複合繊維の製造時の溶融紡糸ノズルの汚れが強くなり、歩留りが低下したり、得られる導電性複合繊維の物性の低下、紡糸装置のガイドなどが摩耗劣化するため、隠ぺい性無機顔料の含有量の上限は、１５質量％程度が好ましい。
上記の範囲で、保護層に、隠ぺい性無機顔料を含有することにより、製糸性や糸物性の低下を招くことなくカーボンブラックの着色を効果的に隠ぺいし、カーボンブラック含有繊維特有の黒スジが目立たず、良好な意匠性を有するものとなる。
The content of the concealing inorganic pigment is 5% by mass or more, more preferably 7% by mass or more, based on the polyamide of the protective layer. If the content of the concealing inorganic pigment is too high, the molten spinning nozzle becomes more dirty during the production of the conductive composite fiber, and the yield is lowered, the physical properties of the obtained conductive composite fiber are lowered, and the guide of the spinning device is used. The upper limit of the content of the concealing inorganic pigment is preferably about 15% by mass, because the content of the hiding inorganic pigment is deteriorated by abrasion.
In the above range, by containing a concealing inorganic pigment in the protective layer, the coloring of carbon black is effectively concealed without causing deterioration of yarn-making property and thread physical characteristics, and black streaks peculiar to carbon black-containing fibers are formed. It is inconspicuous and has good design.
このような隠ぺい性無機顔料としては、例えば、酸化チタン、硫酸バリウム、酸化カルシウム、酸化亜鉛などの増白剤が好適に挙げられ、特に酸化チタンが好ましい。 Examples of such a hiding inorganic pigment preferably include whitening agents such as titanium oxide, barium sulfate, calcium oxide, and zinc oxide, and titanium oxide is particularly preferable.
本発明における隠ぺい性無機顔料は、コスト、白度、繊維とした際の強伸度への影響や、繊維加工機械のガイドなどに対する摩耗性などを鑑みて適宜選択すればよい。 The concealing inorganic pigment in the present invention may be appropriately selected in consideration of cost, whiteness, the influence on the strength and elongation of the fiber, and the wear resistance to the guide of the fiber processing machine.
また、これらの隠ぺい性無機顔料を保護層に含有させる方法は、特に限定するものではないが、あらかじめポリアミドに混練し、コンパウンドとして溶融紡糸しても良いし、樹脂混練物を一度ペレット化することなく混練と溶融紡糸を連続的に行っても良い。また隠ぺい性無機顔料を３０質量％以上含有する高濃度マスターバッチをあらかじめ作製し、溶融紡糸時にドライブレンドにて希釈し、濃度を調整しても良い。 The method of incorporating these concealing inorganic pigments in the protective layer is not particularly limited, but may be kneaded with polyamide in advance and melt-spun as a compound, or the resin kneaded product may be pelletized once. You may continuously perform kneading and melt spinning without kneading. Further, a high-concentration masterbatch containing 30% by mass or more of the concealing inorganic pigment may be prepared in advance and diluted with a dry blend at the time of melt spinning to adjust the concentration.
本発明の未延伸導電性複合繊維の破断伸度は、２００～６００％である。破断伸度が２００％未満であると、ＢＣＦ製造時に混繊され、延伸、嵩高加工された際に糸切れや導電性の低下（線抵抗値の著しい上昇）が生じる。また、破断伸度が６００％を超えると、理由は定かではないが、ＢＣＦとした際に、導電性複合繊維のみがＢＣＦからたるみ、浮き上がったような形態となり、カーペットとする際の製織性、意匠性や導電性の耐久性に悪影響を及ぼす。中でも、２５０～５５０％が好ましい。 The breaking elongation of the unstretched conductive composite fiber of the present invention is 200 to 600%. If the elongation at break is less than 200%, the fibers are mixed during BCF production, and yarn breakage and a decrease in conductivity (significant increase in linear resistance value) occur during drawing and bulk processing. In addition, when the elongation at break exceeds 600%, the reason is not clear, but when BCF is used, only the conductive composite fiber slackens from the BCF and becomes a floating form, and the weaving property when making a carpet, It adversely affects the durability of design and conductivity. Above all, 250 to 550% is preferable.
本発明の未延伸導電性複合繊維の破断強度は、０．４ｃＮ／ｄｔｅｘ以上が好ましく、より好ましくは０．６ｃＮ／ｄｔｅｘ以上である。上限は特にないが、未延伸糸であることと、破断伸度とのバランスを考慮すると上限は２．５ｃＮ／ｄｔｅｘ程度であることが好ましい。この範囲であると、製糸及びＢＣＦ製造時の混繊、延伸、嵩高加工の安定性が得られるため、好ましい。 The breaking strength of the unstretched conductive composite fiber of the present invention is preferably 0.4 cN / dtex or more, and more preferably 0.6 cN / dtex or more. Although there is no particular upper limit, the upper limit is preferably about 2.5 cN / dtex in consideration of the balance between the undrawn yarn and the elongation at break. Within this range, stability of blending, stretching, and bulk processing during silk reeling and BCF production can be obtained, which is preferable.
本発明の未延伸導電性複合繊維の総繊度は、１５～８０ｄｔｅｘが好ましく、より好ましくは２０～６０ｄｔｅｘである。この範囲であると、十分な白度、カーペットとした際の意匠性、導電性、製糸及びＢＣＦ製造時の混繊、延伸、嵩高加工の安定性が得られるため、好ましい。 The total fineness of the unstretched conductive composite fiber of the present invention is preferably 15 to 80 dtex, more preferably 20 to 60 dtex. This range is preferable because sufficient whiteness, designability when used as a carpet, conductivity, and stability of fiber blending, drawing, and bulk processing during silk reeling and BCF production can be obtained.
本発明の未延伸導電性複合繊維のフィラメント数は、特に限定されるのもではないが、１～８ｆが好ましく、より好ましくは１～６ｆであり、白度や単糸の破断強度を鑑み決定する。 The number of filaments of the unstretched conductive composite fiber of the present invention is not particularly limited, but is preferably 1 to 8f, more preferably 1 to 6f, and is determined in consideration of the whiteness and the breaking strength of the single yarn. do.
本発明の未延伸導電性複合繊維の線抵抗値は、１．０Ｅ＋０５～９．９Ｅ＋０７Ω／ｃｍである。この範囲であると、製糸及びＢＣＦ製造時の混繊、延伸、嵩高加工の安定性およびＢＣＦとした際にも十分な導電性が得られ、しいてはカーペットとした際に良好な制電性を示す。
本発明の未延伸導電性複合繊維のパッケージ（巻き姿）は、ボビンやパーンに巻き取られたものであり、そのパッケージ端面はテーパー角が９０°のスクエアエンドでも、テーパー角が９０°未満のテーパーエンドでも良い。また、ある一定の内層のボビン直径まではスクエアエンドで、その位置から外層はテーパーエンドとなるパッケージでも良く、それらは取扱い性や運搬、運送の効率や容易性、ＢＣＦへの混繊する際にパッケージから導電性複合繊維を繰り出す安定性を鑑みて決定すればよい。
The linear resistance value of the unstretched conductive composite fiber of the present invention is 1.0E + 05 to 9.9E + 07Ω / cm. Within this range, sufficient conductivity can be obtained for blending, stretching, and bulk processing stability during silk reeling and BCF manufacturing, and sufficient conductivity can be obtained for BCF, and good antistatic properties for carpets. Is shown.
The package (rolled form) of the unstretched conductive composite fiber of the present invention is wound around a bobbin or a pan, and the end face of the package has a taper angle of less than 90 ° even at a square end having a taper angle of 90 °. It may be a tapered end. In addition, a package may have a square end up to a certain inner bobbin diameter and a tapered end from that position to the outer layer, which are easy to handle, transport, transport efficiency and ease, and when blended into BCF. It may be determined in consideration of the stability of feeding out the conductive composite fiber from the package.
本発明において、繊維横断面は、繊維軸長手方向に垂直な面をいう。
本発明の未延伸導電性複合繊維は、導電層及び保護層が、繊維長手方向に連続していることが好ましい。
In the present invention, the fiber cross section refers to a plane perpendicular to the fiber axis longitudinal direction.
In the unstretched conductive composite fiber of the present invention, it is preferable that the conductive layer and the protective layer are continuous in the fiber longitudinal direction.
本発明の導電性複合繊維の繊維横断面における、保護層／導電層の面積比率は好ましくは１００／１～３／１、より好ましくは５０／１～５／１である。保護層の面積比率が高すぎると、白度が高くなるが、十分な導電性が得られないおそれがある。また、保護層の面積比率が低すぎると、十分な白度が得られなくなるどころか、破断強度及び破断伸度が低下し、ＢＣＦ混繊時における延伸工程にて糸切れが多発するおそれがある。
本発明の導電性複合繊維の繊維横断面の断面形状は、導電層が保護層に完全に包まれている非露出タイプ、導電層が繊維表面の一部または繊維表面全体に露出している露出タイプのいずれでもよい。しかしながら、繊維とした際に十分な白度を有するためには、繊維横断面における繊維表面への導電層の露出長は短いほど好ましく、導電性複合繊維の繊維横断面における全周長に対する導電層の露出周長の割合は８％未満が好ましく、より好ましくは０％、すなわち導電層が非露出である。
また、繊維横断面としては丸断面、三角断面、多葉断面など、特に限定されるものではないが、乱反射により繊維の白度を上げるために多葉断面であることが好ましい。
特に好ましい断面形状として、繊維横断面における保護層の外周に３個以上の凸部を有するものが挙げられる。これにより、光が乱反射し易く、優れた白度を得られやすい。
The area ratio of the protective layer / the conductive layer in the fiber cross section of the conductive composite fiber of the present invention is preferably 100/1 to 3/1, more preferably 50/1 to 5/1. If the area ratio of the protective layer is too high, the whiteness will be high, but sufficient conductivity may not be obtained. Further, if the area ratio of the protective layer is too low, not only a sufficient whiteness cannot be obtained, but also the breaking strength and the breaking elongation are lowered, and there is a possibility that yarn breakage occurs frequently in the drawing step at the time of BCF blending.
The cross-sectional shape of the fiber cross section of the conductive composite fiber of the present invention is a non-exposed type in which the conductive layer is completely wrapped in a protective layer, and the conductive layer is exposed to a part of the fiber surface or the entire fiber surface. It can be of any type. However, in order to have sufficient whiteness when made into a fiber, it is preferable that the exposed length of the conductive layer on the fiber surface in the fiber cross section is short, and the conductive layer with respect to the entire circumference of the fiber cross section of the conductive composite fiber. The ratio of the exposed peripheral length is preferably less than 8%, more preferably 0%, that is, the conductive layer is unexposed.
The cross section of the fiber is not particularly limited, such as a round cross section, a triangular cross section, and a multi-leaf cross section, but a multi-leaf cross section is preferable in order to increase the whiteness of the fiber due to diffused reflection.
A particularly preferable cross-sectional shape is one having three or more convex portions on the outer periphery of the protective layer in the cross section of the fiber. As a result, light is easily reflected diffusely, and excellent whiteness is easily obtained.
本発明の未延伸導電性複合繊維を後述する方法で測定したＬ*値は、６５以上であることが好ましく、より好ましくは７０以上である。この範囲であると、カーペットとした際に導電性繊維の黒筋が目立たない。 The L * value of the unstretched conductive composite fiber of the present invention measured by the method described later is preferably 65 or more, more preferably 70 or more. Within this range, black streaks of conductive fibers are not noticeable when used as a carpet.
このような本発明の未延伸導電性複合繊維は、ＢＣＦを製造する際に、ノズルから吐出される糸条に混繊し、延伸、嵩高加工に対し、破断せず、導電性を維持することができ、ＢＣＦカーペットとした際に、黒筋が目立つことなく良好な制電性を得ることができる。 Such an unstretched conductive composite fiber of the present invention is mixed with threads discharged from a nozzle when BCF is manufactured, and is not broken and maintains conductivity against stretching and bulky processing. Therefore, when a BCF carpet is used, good antistatic properties can be obtained without conspicuous black streaks.
本発明の未延伸導電性複合繊維の好適な製造方法の例を示す。
上記の導電性カーボンブラック、上記のポリアミドを準備し、混練して樹脂組成物を製造する。得られた樹脂組成物を導電層、隠ぺい材を５質量％以上含有するポリアミドを保護層とし、導電層と保護層が繊維横断面で複合された状態で吐出される複合口金と用いて、溶融複合紡糸を行い、導電性複合繊維を製造する。
溶融紡糸の際、紡糸温度は、原料となるポリアミドの融点＋１０℃～８０℃、紡糸速度は、４００～１８００ｍ／ｍｉｎ程度が好ましく、この範囲であると製糸性が安定し、巻き取ったパッケージの形状も良好である。また、ポリアミドは合成繊維の中でも吸水性、吸湿性が高く、特に未延伸であるとその特性は顕著となるため、付与させる油剤や巻取環境温湿度を適宜調整する。
図１はＢＣＦの製造方法の例を示す。溶融紡糸装置１から吐出された非導電性未延伸繊維と、本発明の未延伸導電性複合繊維２をガイド３を介して引き揃えて混繊し、油剤付与ローラー４で油剤付与し、第１ゴデッドローラー５に供給し、第１ゴデッドローラー５と第２ゴデッドローラー６の間で、延伸する。次いで、得られた延伸糸を嵩高加工装置７で流体噴射にて嵩高加工を行い、ワインダー８に巻取り、ＢＣＦ９を得ることができる。また、糸走行やその方向、巻取張力を安定させたり、多段延伸もしくは弛緩させる目的で第２ゴデットローラー６のあとにもローラーを適宜設置しても良い。
未延伸非導電繊維と、未延伸導電性複合繊維の混合比率は、ＢＣＦとなった際の質量比率で、ＢＣＦに対し０．２～５質量％程度未延伸導電性複合繊維を混合することが好ましい。
第１ゴデッドローラー５と第２ゴデッドローラー６との延伸条件の好適な例を挙げると、例えば、第１ゴデッドローラー５の温度は室温でもよいが、延伸の安定性や導電性複合繊維の導電性を維持するためには４０℃以上、第２ゴデッドローラー６の温度は第１ゴデッドローラーの温度よりも高く、好ましくは１１０℃以上、より好ましくは１３０℃以上である。延伸倍率は２．０倍から４．５倍で、ＢＣＦの強伸度や捲縮特性を鑑み決定する。
また、嵩高加工方法は、特に限定されるものではないが、例えば、流体噴射加工（エアジェット）が好適に挙げられる。
このようにして得られたＢＣＦを用いて、公知の諸加工工程を経てタフティングを行い、精練して、染色し、制電性が優れ、黒筋が、目立たない意匠性の良好なカーペットを得ることができる。
An example of a suitable manufacturing method of the unstretched conductive composite fiber of this invention is shown.
The above-mentioned conductive carbon black and the above-mentioned polyamide are prepared and kneaded to produce a resin composition. The obtained resin composition is used as a conductive layer, and a polyamide containing 5% by mass or more of a hiding material is used as a protective layer, and melted by using a composite base ejected in a state where the conductive layer and the protective layer are composited in the cross section of the fiber. Composite spinning is performed to produce conductive composite fibers.
At the time of melt spinning, the spinning temperature is preferably the melting point of the polyamide used as a raw material + 10 ° C to 80 ° C, and the spinning speed is preferably about 400 to 1800 m / min. The shape is also good. Further, polyamide has high water absorption and hygroscopicity among synthetic fibers, and its characteristics become remarkable especially when it is unstretched. Therefore, the oil agent to be applied and the winding environment temperature / humidity are appropriately adjusted.
FIG. 1 shows an example of a method for producing BCF. The non-conductive unstretched fibers discharged from the
The mixing ratio of the unstretched non-conductive fiber and the unstretched conductive composite fiber is the mass ratio at the time of becoming BCF, and the unstretched conductive composite fiber may be mixed by about 0.2 to 5% by mass with respect to the BCF. preferable.
To give a suitable example of the drawing conditions of the
Further, the bulky processing method is not particularly limited, but for example, fluid injection processing (air jet) is preferably mentioned.
Using the BCF thus obtained, tufting is performed through various known processing steps, and the carpet is refined, dyed, has excellent antistatic properties, and has black streaks inconspicuous and has good design. Obtainable.
以下に実施例を挙げて本発明を具体的に説明する。なお、本発明は以下に述べる実施例に限定されるものではない。尚、本発明の実施例及び比較例で得られた導電性繊維及びそれからなる生地の特性・評価は次に示す方法より求めた。 Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to the examples described below. The characteristics and evaluation of the conductive fibers and the fabric made of the conductive fibers obtained in the examples and comparative examples of the present invention were obtained by the following methods.
＜破断強度、破断伸度＞
導電性複合繊維の破断強度及び破断伸度は、ＪＩＳ Ｌ １０１３に準じ、（株）島津製作所製ＡＧＳ－１ＫＮＧオートグラフ引っ張り試験機を用い、試料糸長５ｃｍ、引っ張り速度１０ｃｍ／ｍｉｎの条件で試料が伸長破断したときの強度及び伸度を測定して求めた。
＜繊維の導電性評価（線抵抗値）＞
線抵抗値は、導電性複合繊維を１０ｃｍ採取し、その両端に導電性接着剤でアルミ箔を接着させ、Ａｇｉｌｅｎｔ社製ハイレジスタンスメーター４３３９Ｂを用いて１０ｃｍ長での抵抗値を測定した。測定値を１０ｃｍで割り返し、線抵抗値（Ω／ｃｍ）とした。
＜ニュアンス巻による白度評価＞
未延伸導電性繊維を黒板に、その黒板が透けないよう目付１．２ｇ／ｃｍ２以上で隙間なく、また、繊維を延伸することなく巻きつけ、日本電飾 測色色差計（ＺＥ－２０００）を用い、Ｌ＊値を測定した。Ｌ＊値が６５以上となるとＢＣＦとした際、しいてはカーペットとした際に導電性複合繊維の黒筋が目立たない。
<Breaking strength, breaking elongation>
The breaking strength and breaking elongation of the conductive composite fiber are in accordance with JIS L 1013, and a sample is used under the conditions of a sample yarn length of 5 cm and a tensile speed of 10 cm / min using an AGS-1KNG autograph tensile tester manufactured by Shimadzu Corporation. Was obtained by measuring the strength and elongation at the time of elongation fracture.
<Evaluation of fiber conductivity (line resistance value)>
For the linear resistance value, 10 cm of the conductive composite fiber was collected, aluminum foil was adhered to both ends thereof with a conductive adhesive, and the resistance value at a length of 10 cm was measured using a high resistance meter 4339B manufactured by Agilent. The measured value was divided by 10 cm to obtain a linear resistance value (Ω / cm).
<Whiteness evaluation by nuance volume>
Unstretched conductive fibers are wrapped around a blackboard with a basis weight of 1.2 g / cm 2 or more so that the blackboard does not show through, and the fibers are not stretched. The L * value was measured using. When the L * value is 65 or more, the black streaks of the conductive composite fiber are not conspicuous when the BCF is used and when the carpet is used.
〔実施例１〕
ポリアミド６に導電性カーボンブラックを３５質量％混練した樹脂組成物を芯の導電層、アナターゼ型酸化チタン９．７質量％を含有するポリアミド６を鞘の保護層とし、導電層が保護層に完全に包まれ、保護層は４つの突起（凸部）を有する十字型断面となる口金を用いて溶融複合紡糸機にて複合紡糸を行った。保護層と導電層の繊維横断面における面積比率は１０：１となるようギアポンプを調節し、８ホールのノズルから吐出された複合繊維を８つに分け、油剤を付与し、３５ｄｔｅｘのモノフィラメントとして６８０ｍ／ｍｉｎで回転する８つのボビンに未延伸複合導電繊維を巻き取った。
[Example 1]
The resin composition obtained by kneading the polyamide 6 with 35% by mass of conductive carbon black is used as the core conductive layer, and the polyamide 6 containing 9.7% by mass of anatase-type titanium oxide is used as the protective layer of the sheath, and the conductive layer is completely formed as the protective layer. The protective layer was subjected to composite spinning with a melt composite spinning machine using a base having a cross-shaped cross section having four protrusions (convex portions). The gear pump was adjusted so that the area ratio of the protective layer and the conductive layer in the fiber cross section was 10: 1, the composite fiber discharged from the 8-hole nozzle was divided into eight, oiled, and 680 m as a 35 dtex monofilament. Unstretched composite conductive fibers were wound around eight bobbins rotating at / min.
〔実施例２〕
ポリアミド６に導電性カーボンブラックを３５質量％混練した樹脂組成物を芯の導電層、アナターゼ型酸化チタン９．７質量％を含有するポリアミド６を鞘の保護層とし、導電層が保護層に完全に包まれ、保護層は４つの突起（凸部）を有する十字型断面となる口金を用いて溶融複合紡糸機にて複合紡糸を行った。保護層と導電層の繊維横断面における面積比率は３０：１となるようギアポンプを調節し、８ホールのノズルから吐出された複合繊維を８つに分け、油剤を付与し、３５ｄｔｅｘのモノフィラメントとして６８０ｍ／ｍｉｎで回転する８つのボビンに未延伸複合導電繊維を巻き取った。
[Example 2]
The resin composition obtained by kneading the polyamide 6 with 35% by mass of conductive carbon black is used as the core conductive layer, and the polyamide 6 containing 9.7% by mass of anatase-type titanium oxide is used as the protective layer of the sheath, and the conductive layer is completely formed as the protective layer. The protective layer was subjected to composite spinning with a melt composite spinning machine using a base having a cross-shaped cross section having four protrusions (convex portions). The gear pump was adjusted so that the area ratio of the protective layer and the conductive layer in the fiber cross section was 30: 1, the composite fiber discharged from the 8-hole nozzle was divided into eight, oiled, and 680 m as a 35 dtex monofilament. Unstretched composite conductive fibers were wound around eight bobbins rotating at / min.
〔実施例３〕
ポリアミド６に導電性カーボンブラックを３５質量％混練した樹脂組成物を芯の導電層、アナターゼ型酸化チタン９．７質量％を含有するポリアミド６を鞘の保護層とし、導電層が繊維表面に一部露出し、保護層は４つの突起（凸部）を有する十字型断面となる口金を用いて溶融複合紡糸機にて複合紡糸を行った。保護層と導電層の繊維横断面における面積比率は３０：１となるようギアポンプを調節し、８ホールのノズルから吐出された複合繊維を８つに分け、油剤を付与し、３５ｄｔｅｘのモノフィラメントとして６８０ｍ／ｍｉｎで回転する８つのボビンに未延伸複合導電繊維を巻き取った。導電層は繊維横断面における１つの凹部に露出し、全周長に対する導電層の露出周長の割合は５％であった。
[Example 3]
A resin composition obtained by kneading 35% by mass of conductive carbon black with polyamide 6 is used as a conductive layer of the core, and polyamide 6 containing 9.7% by mass of anatase-type titanium oxide is used as a protective layer of a sheath, and a conductive layer is formed on the fiber surface. The protective layer was subjected to composite spinning with a melt composite spinning machine using a base having a cross-shaped cross section having four protrusions (convex portions). The gear pump was adjusted so that the area ratio of the protective layer and the conductive layer in the fiber cross section was 30: 1, the composite fiber discharged from the 8-hole nozzle was divided into eight, oiled, and 680 m as a 35 dtex monofilament. Unstretched composite conductive fibers were wound around eight bobbins rotating at / min. The conductive layer was exposed in one recess in the cross section of the fiber, and the ratio of the exposed peripheral length of the conductive layer to the total peripheral length was 5%.
〔実施例４〕
ポリアミド６に導電性カーボンブラックを３５質量％混練した樹脂組成物を芯の導電層、ルチル型酸化チタン５０質量％を含有するポリアミド６とアナターゼ型酸化チタン０．３質量％を含有するポリアミドをドライブレンドし、保護層における酸化チタンの総含有量が６．２質量％となるようブレンド比を調整したものを保護層とし、導電層が保護層に完全に包まれ、保護層は４つの突起（凸部）を有する十字型断面となる口金を用いて溶融複合紡糸機にて複合紡糸を行った。保護層と導電層の繊維横断面における面積比率は３０：１となるようギアポンプを調節し、８ホールのノズルから吐出された複合繊維を８つに分け、油剤を付与し、３５ｄｔｅｘのモノフィラメントとして６８０ｍ／ｍｉｎで回転する８つのボビンに未延伸複合導電繊維を巻き取った。
[Example 4]
A resin composition in which 35% by mass of conductive carbon black is kneaded with polyamide 6 is used as a core conductive layer, and a polyamide 6 containing 50% by mass of rutile-type titanium oxide and a polyamide containing 0.3% by mass of anatase-type titanium oxide are dried. The protective layer is made by blending and adjusting the blend ratio so that the total content of titanium oxide in the protective layer is 6.2% by mass. The conductive layer is completely wrapped in the protective layer, and the protective layer has four protrusions (4 protrusions (). Composite spinning was performed with a melt composite spinning machine using a base having a cross-shaped cross section (convex portion). The gear pump was adjusted so that the area ratio of the protective layer and the conductive layer in the fiber cross section was 30: 1, the composite fiber discharged from the 8-hole nozzle was divided into eight, oiled, and 680 m as a 35 dtex monofilament. Unstretched composite conductive fibers were wound around eight bobbins rotating at / min.
〔比較例１〕
ポリアミド６に導電性カーボンブラックを３５質量％混練した樹脂組成物を芯の導電層、アナターゼ型酸化チタン９．７質量％を含有するポリアミド６を鞘の保護層とし、導電層が繊維表面に一部露出し、保護層は４つの突起を有する十字型断面となる口金を用いて溶融複合紡糸機にて複合紡糸を行った。保護層と導電層の繊維横断面における面積比率は３０：１となるようギアポンプを調節し、８ホールのノズルから吐出された複合繊維を８つに分け、油剤を付与し、３５ｄｔｅｘのモノフィラメントとして６８０ｍ／ｍｉｎで回転する８つのボビンに未延伸複合導電繊維を巻き取った。導電層は繊維横断面における１つの凹部に露出し、全周長に対する導電層の露出周長の割合は１６％であった。
[Comparative Example 1]
A resin composition obtained by kneading 35% by mass of conductive carbon black with polyamide 6 is used as a conductive layer of the core, and polyamide 6 containing 9.7% by mass of anatase-type titanium oxide is used as a protective layer of a sheath, and a conductive layer is formed on the fiber surface. The protective layer was partially exposed, and composite spinning was performed with a melt composite spinning machine using a base having a cross-shaped cross section having four protrusions. The gear pump was adjusted so that the area ratio of the protective layer and the conductive layer in the fiber cross section was 30: 1, the composite fiber discharged from the 8-hole nozzle was divided into eight, oiled, and 680 m as a 35 dtex monofilament. Unstretched composite conductive fibers were wound around eight bobbins rotating at / min. The conductive layer was exposed in one recess in the cross section of the fiber, and the ratio of the exposed peripheral length of the conductive layer to the total peripheral length was 16%.
〔比較例２〕
ポリアミド６に導電性カーボンブラックを３５質量％混練した樹脂組成物を芯の導電層、アナターゼ型酸化チタン１．６質量％を含有するポリアミド６を鞘の保護層とし、導電層が保護層に完全に包まれ、保護層は４つの突起を有する十字型断面となる口金を用いて溶融複合紡糸機にて複合紡糸を行った。保護層と導電層の繊維横断面における面積比率は３０：１となるようギアポンプを調節し、８ホールのノズルから吐出された複合繊維を８つに分け、油剤を付与し、３５ｄｔｅｘのモノフィラメントとして６８０ｍ／ｍｉｎで回転する８つのボビンに未延伸複合導電繊維を巻き取った。
[Comparative Example 2]
The resin composition obtained by kneading the polyamide 6 with 35% by mass of conductive carbon black is used as the core conductive layer, and the polyamide 6 containing 1.6% by mass of anatase-type titanium oxide is used as the protective layer of the sheath, and the conductive layer is completely formed as the protective layer. The protective layer was subjected to composite spinning with a melt composite spinning machine using a base having a cross-shaped cross section having four protrusions. The gear pump was adjusted so that the area ratio of the protective layer and the conductive layer in the fiber cross section was 30: 1, the composite fiber discharged from the 8-hole nozzle was divided into eight, oiled, and 680 m as a 35 dtex monofilament. Unstretched composite conductive fibers were wound around eight bobbins rotating at / min.
実施例１～４、比較例１，２で得た未延伸導電性複合繊維パッケージをクリルにセットし、溶融紡糸装置から吐出される９６フィラメントのポリアミド６の糸条に、クリルから繰り出した未延伸導電性複合繊維を、ガイドを介して混繊し、９００ｍ／ｍｉｎで回転する５０℃の第１ゴデットローラー、２８００ｍ／ｍｉｎで回転する１６０℃の第２ゴデットローラー間で連続的に延伸し、さらに１６０℃のエアジェットにて嵩高加工を施したのち、ワインダーにて巻き取った。得られたＢＣＦは１５６０ｄｔｅｘ／９７ｆで、延伸された導電性複合繊維が１フィラメント含まれている。この際、得られたすべての未延伸導電性複合繊維パッケージからの糸の繰り出し（解舒性）、延伸や加工は安定したものであった。また、これら導電性複合繊維が混繊されたＢＣＦを２．５４ｃｍ当たり２本用いて製造されたカーペットは人体帯電圧測定法によると人体帯電圧３．０ｋＶ（絶対値）以下となり、優れた制電性を示した。
実施例１～４を用いて得たＢＣＦは導電性に優れ、また導電性複合繊維が含まれていないＢＣＦと比べ、筋が目立つものではなかった。比較例１，２を用いて得たＢＣＦは導電性複合繊維が含まれていないＢＣＦと比べ、黒もしくはグレーの筋が目立つものとなった。
＜参考例１＞
３３ｄｔｅｘ／３ｆの延伸導電性複合繊維（破断強度２．９ｃＮ／ｄｔｅｘ，破断伸度６５％、線抵抗値３．５Ｅ＋０７Ω／ｃｍ）のパッケージをクリルにセットし、溶融紡糸装置から吐出される９６フィラメントのポリアミド６の糸条に、パッケージから繰り出した延伸導電性複合繊維を、ガイドを介して混繊し、９００ｍ／ｍｉｎで回転する５０℃の第１ゴデットローラー、２８００ｍ／ｍｉｎで回転する１６０℃の第２ゴデットローラー間で連続的に延伸したが、ローラー間で導電性複合繊維の破断を繰り返し、ＢＣＦを安定的に得ることができなかった。
＜参考例２＞
溶融紡糸装置から吐出される９６フィラメントのポリアミド６の糸条を９００ｍ／ｍｉｎで回転する５０℃の第１ゴデットローラー、２８００ｍ／ｍｉｎで回転する１６０℃の第２ゴデットローラー間で連続的に延伸したのち、クリルにセットされた３３ｄｔｅｘ／３ｆの延伸導電性複合繊維（破断強度２．９ｃＮ／ｄｔｅｘ，破断伸度６５％、線抵抗値３．５Ｅ＋０７Ω／ｃｍ）パッケージから繰り出した延伸導電性複合繊維を混繊させ、１６０℃の流体噴射にて嵩高加工を施したのち、ワインダーにて巻き取った。パッケージからの繰り出しは安定せず、糸切れやパッケージの形状崩れを起こしたため、得られるＢＣＦの歩留りが低下した。
The unstretched conductive composite fiber packages obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were set on the krill, and unstretched from the krill on the threads of the 96-filament polyamide 6 discharged from the melt spinning apparatus. The conductive composite fibers are mixed via a guide and continuously stretched between the first godet rollers at 50 ° C. rotating at 900 m / min and the second godet rollers at 160 ° C. rotating at 2800 m / min. After further bulk processing with an air jet at 160 ° C., the fibers were wound up with a winder. The obtained BCF was 1560 dtex / 97f, and one filament of the stretched conductive composite fiber was contained. At this time, the feeding (unwinding property), stretching and processing of the yarn from all the obtained unstretched conductive composite fiber packages were stable. In addition, the carpet manufactured by using two BCFs mixed with these conductive composite fibers per 2.54 cm has a human body band voltage of 3.0 kV (absolute value) or less according to the human body band voltage measurement method, which is an excellent control. Shown electrical.
The BCF obtained using Examples 1 to 4 was excellent in conductivity, and the streaks were not conspicuous as compared with the BCF containing no conductive composite fiber. The BCF obtained by using Comparative Examples 1 and 2 had black or gray streaks conspicuous as compared with the BCF containing no conductive composite fiber.
<Reference example 1>
A package of 33 dtex / 3f stretched conductive composite fiber (breaking strength 2.9 cN / dtex, breaking elongation 65%, linear resistance value 3.5E + 07Ω / cm) is set in the krill, and 96 filaments discharged from the melt spinning device. 1. Although it was continuously stretched between the second Godet rollers, the conductive composite fibers were repeatedly broken between the rollers, and BCF could not be stably obtained.
<Reference example 2>
A 96-filament polyamide 6 yarn discharged from a melt spinning apparatus is continuously rotated between a first godet roller at 50 ° C. rotating at 900 m / min and a second godet roller at 160 ° C. rotating at 2800 m / min. Stretched conductive composite fiber of 33 dtex / 3f stretched conductive composite fiber (break strength 2.9 cN / dtex, breaking elongation 65%, linear resistance value 3.5E + 07 Ω / cm) set in krill after stretching. The fibers were mixed, bulky processed by a fluid injection at 160 ° C., and then wound up with a winder. The feeding from the package was not stable, and the yarn breakage and the shape of the package were deformed, so that the yield of the obtained BCF was lowered.
１ 溶融紡糸装置
２ 未延伸導電性繊維
３ ガイド
４ 油剤付与ローラー
５ 第１ゴデットローラー
６ 第２ゴデットローラー
７ 嵩高加工装置
８ ワインダー
９ ＢＣＦ
1
Claims (4)
A method for producing BCF by mixing non-conductive fibers and conductive fibers, wherein the first step of melt-spinning non-conductive fibers is unstretched non-conductive fibers obtained by melt-spinning. Item 2 The second step of mixing and drawing unstretched conductive fibers according to any one of Items 1 to 3, the third step of bulk processing the mixed drawn yarn by fluid injection, and the obtained bulky processed yarn. A method for producing BCF, which comprises a fourth step of winding.
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| JPH07103489B2 (en) * | 1986-07-01 | 1995-11-08 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | Method for combining and co-stretching antistatic filaments and non-stretched nylon filaments |
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