JP3958227B2 - Blended yarn - Google Patents

Description

【００７８】
実施例１
導電性カーボンブラック（吸油量；１１５ｃｃ／１００ｇ）を３５質量％含有したナイロン６を導電性ポリマー成分（Ａ）として用い、ポリマー成分（Ｂ）として表１の参考例１に示す熱可塑性ポリアミド（ＰＡ９ＭＴ）を用い、Ａ：Ｂの複合比率１３／８７質量％、図３に示すような４芯芯鞘露出型断面で複合紡糸し、その後延伸を実施し、２５デニール／４ｆ（２７．８ｄｔｅｘ／４ｆ）の導電性複合繊維（Ｌ_２：１フィラメントの繊維断面周長＝８８μｍ）を得た。繊維化工程性は良好で問題なかった。得られた導電性複合繊維において導電性ポリマー層（Ａ）は繊維軸方向に均一に連続されていた。また、該導電性ポリマー層（Ａ）の繊維表面での露出部数は４であり、かつそれぞれ導電性ポリマー層の繊維断面周長方向の露出距離Ｌ_１（μｍ）は周長方向でいずれも０．６μｍであり、０．１≦Ｌ_１（μｍ）≦Ｌ_２／１０の条件を満たしていた。さらに１００Ｖ印加時の電気抵抗値は２×１０^８Ω／ｃｍ・ｆ（すなわち、ｌｏｇＲ＝８．３）で非常に安定しており、低印加電圧下においても優れた導電性能を有するものであった。
得られた導電性繊維と混繊するための分割型複合繊維は、一次平均粒子径０．０４μｍのシリカ１．０質量％含有する還元粘度０．８５（オルソクロロフェノール中濃度１ｇ／ｄｌ，３０℃）のポリエチレンテレフタレート（以下ＰＥＴと略称する）と、還元粘度１．８０（オルソクロロフェノール中濃度１ｇ／ｄｌ，３０℃）のナイロン６を用い、それぞれを個別に溶融押出し、その後それぞれのポリマー部を図２で示されるようなＰＥＴが６層、ナイロン６が５層となる多層型複合形状を形成させる紡糸ヘッドへ供給し、計量部分の径が０．２５mmφ、ランド長０．５mmでしかもノズル孔出口がラッパ状に広がり出口径が０．５mmφになっている２４ホール丸孔ノズルから、紡糸温度２８５℃で溶融紡出した（表２参照）。
【００７９】
紡糸口金直下に長さ１．０ｍの横吹き付け型の冷却風吹き付け装置を設置しておき、口金から紡出した複合繊維を直ちにその冷却風吹き付け装置に導入して、温度２５℃、湿度６５ＲＨ％に調整した冷却空気を０．５ｍ／秒の速度で紡出繊維に吹き付けて、繊維を５０℃以下（冷却風吹き付け装置の出口での繊維の温度＝４０℃）にまで冷却した。
【００８０】
上記で５０℃以下に冷却した複合繊維を、紡糸口金直下から１．６ｍの位置に設置した長さ１．０ｍ、内径３０ｍｍのチューブヒーター（内壁温度１８０℃）に導入してチューブヒーター内で延伸した後、チューブヒーターから出てきた繊維にガイドオイリング方式で油剤を付与し、引き続いて１対（２個）の引き取りローラを介して４３００ｍ／分の引取速度で巻取って、延伸した７５デニール２４フィラメント（８２．５ｄｔｅｘ／２４ｆ）の複合繊維を製造した（表３参照）。得られた導電性繊維（２５質量％）と分割型極細繊維(７５質量％)の割合でエアー絡合、仮撚数３３９０Ｔ／Ｍ、温度１７０℃で仮撚を施し、分割処理を行った。得られたポリエステルおよびポリアミドからなる捲縮加工糸を用いて筒編地を作成し、リラックス、水洗、乾燥、プレセット、アルカリ減量、水洗処理を施して乾燥し、各性能を評価した。結果を表１に示す。ニコチン、潤滑油、糊に対する清掃力もあるものが得られた。更に繊維の断面観察をしたところ、分割度９５％と良好な分割性を示していた。
続いて下記に示す条件でポリエステルを染色処理した。
【００８１】

還元洗浄後に冷水洗を行なった。
【００８２】
織物の帯電電荷量は、３．５μクーロン／ｍ^２であった。２年間実着用し、その間約２５０回繰り返し洗濯を行なった後の帯電電荷量は４．８μクーロン／ｍ^２であり、優れた除電性能、つまり、労働省産業安全研究所発行の静電気安全指針の基準値(以下、単に基準値と略記する)７μクーロン／ｍ^２以下をクリアーしており、耐久性も非常に優れたものであり、ニコチン、潤滑油、糊に対する清掃力も優れたものであった。
【００８３】
【表２】

【表３】

【表４】

【００８４】
実施例２〜４
実施例１と同様の導電性繊維を用い、実施例２は極細繊維の断面形状を図１６の形状とし、実施例３は断面形状を図１８の形状とし、実施例４はＰＥＴとナイロン６の複合比率を３／１としたこと以外は実施例１と同様に実施した。いずれも繊維化工程性、分割性良好であり、布帛の初期帯電電荷量、２５０回洗濯後の帯電電荷量のいずれも基準値をクリヤーし実耐久性に優れたものであり、ニコチン、潤滑油、糊に対する清掃力も優れたものであった。
【００８５】
実施例５〜６
実施例１と同様の導電性繊維を用い、実施例５は実施例１で用いたシリカの代わりに一次平均粒子径０．４μｍの酸化チタンを用い、ＰＥＴ中の酸化チタン含有量を０．５質量％とし、実施例６はシリカの代わりに一次平均粒子径０．６μｍの硫酸バリウムを用い、ＰＥＴ中の硫酸バリウム含有量を１．０質量％としたこと以外は実施例１と同様に実施した。いずれも繊維化工程性、分割性良好であり、布帛の初期帯電電荷量、２５０回洗濯後の帯電電荷量のいずれも基準値をクリヤーし実耐久性に優れたものであり、ニコチン、潤滑油、糊に対する清掃力も優れたものであった。
【００８６】
実施例７〜１０
実施例１と同様の極細繊維を用い、実施例７は導電性繊維の複合断面形状を図１、実施例８は複合断面形状を図６、実施例９は複合断面形状を図２、実施例１０は導電性カーボンのマトリックスポリマーをナイロン１２とすること以外は実施例１と同様に実施した。いずれも繊維化工程性、分割性良好であり、布帛の初期帯電電荷量、２５０回洗濯後の帯電電荷量のいずれも基準値をクリヤーし実耐久性に優れたものであり、ニコチン、潤滑油、糊に対する清掃力も優れたものであった。
【００８７】
実施例１１
導電性能が異なる２種の導電性カーボンブラック（αタイプ吸油量；１８０ｃｃ／１００ｇ、βタイプ吸油量；８０ｃｃ／１００ｇ、混合比α／β＝２／１）を３５質量％含有したナイロン６を導電性ポリマー成分（Ａ）とすること以外は実施例１と同様に繊維化を行ない、２５デニール／４ｆ（２７．８ｄｔｅｘ／４ｆ）の導電性複合繊維（Ｌ_２：１フィラメントの繊維断面周長＝８８μｍ）を得た。繊維化工程性は良好で問題なかった。得られた導電性複合繊維において導電性ポリマー層（Ａ）は繊維軸方向に均一に連続されていた。また、該導電性ポリマー層（Ａ）の繊維表面での露出部数は４であり、かつそれぞれ導電性ポリマー層の繊維断面周長方向の露出距離Ｌ_１（μｍ）は周長方向でいずれも０．６μｍであり、０．１≦Ｌ_１（μｍ）≦Ｌ_２／１０の条件を満たしていた。さらに１００Ｖ印加時の電気抵抗値は１×１０^９Ω／ｃｍ・ｆ（すなわち、ｌｏｇＲ＝９．０）で非常に安定しており、低印加電圧下においても優れた導電性能を有するものであった。
得られた導電性繊維（２５質量％）と実施例１と同じ分割型極細繊維(７５質量％)の割合でエアー絡合、仮撚数３３９０Ｔ／Ｍ、温度１７０℃で仮撚を施した。
得られた混繊糸について、パイル編５．０万本／（２．５４ｃｍ）^２密度の導電性ブラシを作成した。複写機での画像評価結果、異常放電のない非常に優れたものであつた。コピー１００００回繰返し画像評価も良好であり、耐久性も非常に優れたものであった。導電性複合繊維の複合組成、繊維形態、繊維化工程性、電気抵抗値、画像評価結果を表２に示す。
【００８８】
実施例１２〜１４
カーボンブラックの種類、その混合割合及びマトリックスポリマーへの添加量を表２に示すように変更すること以外は実施例１１と同様に繊維化を行なった。いずれも、繊維化工程性及び画像特性に優れるものであった(表２〜４参照)。
【００８９】
比較例１〜４
導電性複合繊維として表２に示すような繊維を製造すること以外は実施例１と同様に実施したが、除電性能または繊維化工程性が不良であった。
【００９０】
比較例５〜６
分割型極細繊維、混繊糸として表２、３に示すような繊維を製造し、実施例１１と同様に画像評価を実施したがいずれも不良であった。（表２〜４参照）
【００９１】
【発明の効果】
本発明においては、導電性カーボンブラックを特定量含有した熱可塑性ポリマーを所定の条件を満足する方法で複合紡糸することで得られる導電性複合繊維と強度と伸度などの力学的特性に優れる高品質のポリエステルとポリアミドによる分割型複合繊維との混繊糸を用いることにより、衣料用途や複写機等の帯電ブラシとして長期間実使用した後でも優れた除電性能を有し、ワイピングクロスとして用いた時に驚異的な拭き取り力を有している混繊糸を提供できるものである。また、本発明の導電性複合繊維は、他の繊維と混用して繊維製品とする場合、染色処理を行なっても、他の繊維に色移りのしない染色堅牢度に優れるものである。
【図面の簡単な説明】
【図１】 本発明に使用される導電性複合繊維の断面形態の一例を示す模式図
【図２】 本発明に使用される導電性複合繊維の断面形態の他の一例を示す模式図
【図３】 本発明に使用される導電性複合繊維の断面形態の他の一例を示す模式図
【図４】 本発明に使用される導電性複合繊維の断面形態の他の一例を示す模式図
【図５】 本発明に使用される導電性複合繊維の断面形態の他の一例を示す模式図
【図６】 本発明に使用される導電性複合繊維の断面形態の他の一例を示す模式図
【図７】 本発明に使用される導電性複合繊維の断面形態の他の一例を示す模式図
【図８】 本発明に使用される導電性複合繊維の断面形態の他の一例を示す模式図
【図９】 本発明外の導電性複合繊維の断面形態の一例を示す模式図
【図１０】 本発明外の導電性複合繊維の断面形態の他の一例を示す模式図
【図１１】 本発明に使用される分割型複合繊維の断面形態の一例を示す模式図
【図１２】 本発明に使用される分割型複合繊維の断面形態の他の一例を示す模式図
【図１３】 本発明に使用される分割型複合繊維の断面形態の他の一例を示す模式図
【図１４】 本発明に使用される分割型複合繊維の断面形態の他の一例を示す模式図
【図１５】 本発明に使用される分割型複合繊維の断面形態の他の一例を示す模式図
【図１６】 本発明に使用される分割型複合繊維の断面形態の他の一例を示す模式図
【図１７】 本発明に使用される分割型複合繊維の断面形態の他の一例を示す模式図
【図１８】 本発明に使用される分割型複合繊維の断面形態の他の一例を示す模式図
【符号の説明】
Ａ：導電性ポリマー層（Ａ）
Ｂ：ポリマー層(Ｂ)[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a fiber excellent in static elimination performance. Specifically, despite having a small amount of conductive carbon black in the fiber, durability is good while maintaining excellent static elimination performance and cleaning performance for a long time as a brush for OA equipment, wiping cloth, etc. Thus, the present invention relates to a conductive fiber capable of forming a high-quality printed image over a long period of time. In addition, the present invention is suitable for apparel suitable for apparel that has reduced dust generation during actual use, maintained excellent electrical conductivity for a long time, and sufficiently satisfies consumption performance, particularly ironing resistance and dyeing fastness. It relates to mixed yarn of fiber and extra fine fiber.
[0002]
[Prior art]
Ultrafine fibers made of split-type composite fibers have a much larger surface area in the same region than normal fibers, and are therefore used as cleaning fabrics because they are easily dusty. However, since the surface area is large, it is difficult to remove dust adhering to the static electricity. In addition, even if countermeasures against static electricity are taken by post-processing treatment such as an antistatic agent, there is no durability and it is difficult to prevent static electricity permanently.
On the other hand, a fabric using conductive fibers has been proposed as an antistatic effect of ultrafine fibers (see Patent Document 1), but the physical properties / performance durability of the conductive fibers, anti-peeling, washing fastness in clothing, dyeing spots There was a problem with the texture.
[0003]
Conventionally, various proposals have been made for conductive fibers having excellent static elimination performance. For example, conductive fibers with metal plating applied to the surface of non-conductive fibers or conductive carbon black as a resin or There are those in which a conductive coating layer is formed by dispersing in rubber and coating this on the fiber surface. However, these can be obtained by methods that are difficult to manufacture because of complicated manufacturing processes, or chemical treatment and actual use in the preparation stage for putting conductive fibers into practical use, for example, in the refining process for weaving and knitting. There was a problem that the electrical conductivity was easily lowered by the external action due to wear and repetitive washing, and the practical use was lost.
[0004]
As other conductive fibers, metal fibers such as steel fibers are known to have excellent static elimination performance, but metal fibers are expensive and difficult to be blended with general organic materials, so spinning properties are poor. This may cause troubles in the process of wetting, weaving, and dyeing, and may easily cause disconnection or falling off due to washing when worn, and may cause sensations based on electrical conductivity, spark problems, fabric melting troubles, etc. It was.
[0005]
Furthermore, as another type of conductive fiber, a method of forming a polymer in which conductive carbon black is uniformly dispersed has been proposed, but it is difficult to produce the fiber because it contains a large amount of conductive carbon black. However, the present situation is that the yield is poor, the cost is high, the fiber properties are remarkably lowered, and it is difficult to produce a product other than using a special process.
[0006]
In order to solve these problems as much as possible, a method has been proposed in which the core component polymer of the core-sheath composite fiber contains conductive carbon black and is wrapped with a sheath made of a normal fiber-forming polymer. (See Patent Document 2). In addition, there is a conductive fiber in which a considerable part of the core component containing conductive carbon black is exposed on the surface of the fiber through the sheath component (see Patent Document 3).
[0007]
In the former case, the core component needs to be 50% or less in order to maintain the fiber physical properties. Therefore, it is sufficient that the non-conductive sheath component surrounds the core component thickly and the carbon black content in the core component is not increased. Performance is not demonstrated. An invention for solving the problem has also been proposed (see Patent Document 4), but since the ratio of the core component containing carbon black exposed to the surface is large, the fiber is inferior in chemical resistance and durability. Peeling between the core component and the sheath component and other troubles are likely to occur. Furthermore, with the aim of improving the static elimination performance of the single core-sheath type conductive fiber and improving durability centering on prevention of delamination between the component layers, the conductive polymer layer containing conductive carbon black and the same polymer as the conductive polymer layer are conductive. There has also been proposed a fiber in which a non-conductive polymer layer not containing carbon is laminated in a multilayered form (Patent Document 5), but in this case as well, the layer containing conductive carbon black is too exposed on the fiber surface. Improvements in chemical resistance and durability are not sufficiently observed.
[0008]
On the other hand, conductive fibers in which a linear polymer containing an organic conductive substance is dispersed in a fiber-forming polymer in a streaky pattern have been proposed (see Patent Documents 6 and 7). Since it is not inside the fiber surface but inside the fiber, durability such as peeling, surface wear and washing is improved.
[0009]
However, in this case, the linear polymer containing the organic conductive substance is dispersed and mixed in a discontinuous state in the length direction in the fiber-forming polymer that is not compatible with the linear polymer. Since it does not contribute, a decrease in fiber strength cannot be avoided. In addition, since the conductive performance varies depending on the dispersion state of the conductive polymer, management of manufacturing conditions and product quality must be extremely difficult. Furthermore, in general, when an incompatible polymer is mixed and dispersed, the dispersed component is not completely encapsulated in the non-dispersed polymer, but is partially exposed to the surface. There is a possibility of dropping out. In addition, the process condition when manufacturing such a fiber, for example, ballooning in spinning discharge is abnormally large, and many base stains and yarn breakage occur, resulting in very low productivity.
[0010]
In addition, the conductive polymer layer is exposed on a part of the fiber surface as a conductive composite fiber that does not wear away with metals in the manufacturing process of fibers and textile products, and does not peel off between composite components or lose conductive components. This type of composite fiber has been proposed (see Patent Documents 8, 9, and 10).
[0011]
However, with the combination of the conductive polymer layer and the non-conductive polymer layer that has been proposed in the past, even if there is no problem in the manufacturing process, when the conductive fiber product is evaluated in actual use over a long period of time, the conductive property due to peeling is still present. There was a problem that the deterioration of sex occurred. In addition, when using conductive fibers for clothing such as uniforms, it is often the case that a small amount of conductive composite fiber is mixed with other fibers to make a garment rather than making clothing with only conductive composite fiber. However, when dyeing such mixed fabrics, conventional conductive fibers are satisfactory as clothing products because they cause a problem of color transfer to other fibers due to poor dyeing fastness even if they are dyed. There was no.
[0012]
Also, representative examples of OA equipment in the case of non-clothing include a copier, a printer, a facsimile, etc. In recent years, technological innovations such as high performance, high speed, miniaturization, and combination are remarkable. In these OA devices, there is a step of removing the toner remaining on the photoconductor after the transfer step. If the cleaning is insufficient, the toner remaining on the photoconductor interferes with the photosensitivity, resulting in the recording quality. Decreases. Known methods for cleaning the toner remaining on the photoreceptor include a method using a contact brush, a method using a rubber blade, a method using a scraped web, a method using an elastic roller, and the like. . Among these methods, there is a method using a brush manufactured using a napped fabric made of conductive fibers having excellent static elimination performance among methods using a contact brush.
[0013]
Humidity dependency (environment) of conductive performance is low, discharge start voltage is low, and it has excellent static elimination performance even under high applied voltage, and there is almost no decline in static elimination performance when it is actually used. The present condition is that there is no conventional conductive composite fiber that maintains the vividness) over a long period of time.
As described above, there has not been proposed a technique that takes into consideration the long-term durability of the conductive performance of the conductive fiber, the peel resistance of the composite component, and the consumption performance.
[0014]
[Patent Document 1]
JP-A-8-109539
[Patent Document 2]
US Pat. No. 3,803,453
[Patent Document 3]
Japanese Examined Patent Publication No. 53-44579
[Patent Document 4]
Japanese Examined Patent Publication No. 53-44579
[Patent Document 5]
JP 52-152513 A
[Patent Document 6]
JP-A-53-147865
[Patent Document 7]
JP 54-34470 A
[Patent Document 8]
JP 54-134117 A
[Patent Document 9]
JP 61-132624 A
[Patent Document 10]
Japanese Patent Laid-Open No. 9-279416
[0015]
The object of the present invention is that even when actually used as a textile product such as a brush or fabric, it is possible to maintain the initial good performance with little variation in the conductive performance while fully utilizing the performance of the ultrafine fiber. It is to provide a blended yarn containing a conductive fiber and to provide a blended yarn that has good durability and exhibits excellent dirt wiping properties in wiping applications.
[0016]
[Means for Solving the Problems]
That is, the present invention provides a conductive fiber having a single fiber fineness of 1 dtex to 15 dtex including a thermoplastic polymer containing 15% by mass to 50% by mass of conductive carbon black, Made of a polyester component containing a polyamide component and inorganic fine particles, obtained by dividing a split-type composite fiber having a cross section in which both components are joined without completely surrounding one component with the other component It is a blended yarn composed of ultrafine fibers having a single fiber fineness of 0.01 to 1 dtex and having an entanglement number of 10 or more.
[0017]
The blended yarn of the present invention can be used not only for clothing such as uniforms, but also for charging brushes and / or static elimination brushes and / or cleaning brushes incorporated in OA devices such as wiping cloths, copying machines, printers and facsimiles. Can do.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
The conductive fiber constituting the mixed yarn of the present invention will be described. It is important that the conductive carbon black contained in the conductive polymer is contained in the component in an amount of 15% by mass to 50% by mass, preferably 20% by mass to 40% by mass. If the content of conductive carbon black is less than 15% by mass, the desired conductivity cannot be obtained, and sufficient static elimination performance cannot be exhibited. On the other hand, when the amount exceeds 50% by mass, no further improvement in conductivity is observed, and not only the flowability of the conductive polymer is remarkably lowered and the spinnability is extremely deteriorated, but also the continuity of the conductive polymer. Therefore, it is difficult to obtain the power, and the antistatic performance becomes unstable.
[0019]
When the conductive carbon black is completely dispersed in the form of particles, the conductivity is poor, and when taking a chain structure called a structure, the conductivity is improved and the conductive carbon black is called conductive carbon black. Therefore, when conducting the polymer with the conductive carbon black, it is important to disperse the conductive carbon black without destroying the structure.
The electrical conduction mechanism of the composite containing conductive carbon black is considered to be due to the contact of the carbon black chain and due to the tunnel effect, but the former is mainly considered. Therefore, the longer the chain of carbon black, the higher the density of the carbon black present in the polymer, the higher the contact probability and the higher the conductivity. According to the examination results of the present inventors, there is almost no effect when the conductive carbon black content is less than 15% by mass, the conductivity is rapidly improved when the content is 20% by mass, and almost saturated when it exceeds 30% by mass.
[0020]
In addition, the conductive fiber used in the present invention is a fiber composed of a single polymer as long as it satisfies the content of the conductive carbon black as described above, and is composed of a combination with another thermoplastic polymer. Although it may be a composite fiber, it is preferably used as a composite fiber from the viewpoint of fiber properties.
[0021]
As for the composite ratio of the conductive polymer layer (A) and the polymer layer (B), the polymer layer (B) exceeds 97% by mass, that is, the conductive polymer layer (A) is less than 3% by mass. It is difficult to spin as a stable composite structure because it is not continuously uniform in the fiber axis direction.
On the other hand, if the conductive polymer layer (A) exceeds 50% by mass, the spinnability of the composite fiber and the fiber properties after stretching are extremely lowered even if the polymer layer (B) has sufficient fiber-forming properties. However, practicality is lost at all.
[0022]
This is because, by containing conductive carbon black, the spinnability of the conductive polymer layer (A) is remarkably lowered, and the low spinnability component occupies more than half of the composite fiber. This is probably because the defect A) appears in the fiber as it is.
For this reason, the composite mass ratio of the conductive polymer layer (A) and the polymer layer (B) is in the range of A: B = 3: 97 to 50:50, preferably 7:93 to 35:65.
[0023]
In the present invention, it is preferable to use a thermoplastic polyamide as the thermoplastic polymer constituting the conductive polymer layer (A). Specific examples of the thermoplastic polyamide include nylon 12, nylon 11, nylon 6, nylon 66, nylon elastomer, and the like.
[0024]
Usually, in the process of being used as a charging brush for OA equipment for a long period of time, severe bending, pulling, bending, wear, etc. are repeated, the performance of the conductive polymer deteriorates, and the static elimination performance has to be reduced. It was. Usually, once the continuity is lost due to a strain such as a crack, the portion constituting the conductive polymer is difficult to be repaired and must be replaced in a short period of time.
The present inventors studied by dispersing conductive carbon black in various polymers, and because polyamide has an appropriate polar group, it has good compatibility and adhesiveness with conductive carbon black and is highly conductive. Even if carbon black is blended, the fluidity does not decrease so much that it has both high electrical conductivity and good fluidity. In addition, the conductive carbon black and polyamide are mechanically bonded to each other. Was also found to be very good.
[0025]
In contrast, when conductive carbon black is kneaded and blended with a polyester polymer, the reason is not clear, but even at a low blending ratio, the viscosity of the polymer suddenly increases, the fluidity is lost, and the desired conductivity and fiber are obtained. It is difficult to become a conductive polymer that can be made into a polymer, and it cannot be opposed to a polyamide polymer at all.
[0026]
In addition, it is easy to obtain a conductive polymer having a certain degree of fluidity and good conductivity by kneading and blending conductive carbon black as compared with a polyester polymer. However, polyolefin-based polymers have poor adhesion to conductive carbon black, and the mechanical properties of the resulting polymers are considerably fragile compared to those of polyamide-based polymers. Careful attention must be paid when making composite fibers. Problems such as cutting of the conductive polymer layer are likely to occur.
From the above, thermoplastic polyamide is most suitable as the polymer containing conductive carbon black.
[0027]
On the other hand, the polymer layer (B) plays an important role in maintaining good processability during fiberization and maintaining consumption performance and long-term durability performance. The polymer component constituting the polymer layer (B) is not particularly limited as long as it is a fiber-forming thermoplastic polymer having a melting point of 170 ° C. or higher, and specifically includes polyester, polyamide, polyolefin and the like. Preferably a thermoplastic polyamide, more preferably a dicarboxylic acid component and a diamine component, wherein 60 mol% or more of the dicarboxylic acid component is an aromatic dicarboxylic acid, and 60 mol% or more of the diamine component. It is important to use a thermoplastic polyamide which is an aliphatic alkylene diamine having 6 to 12 carbon atoms. Such a polyamide is characterized by excellent heat resistance, particularly heat resistance under wet heat, and stringiness, and excellent strength of the resulting fiber.
[0028]
As the aromatic dicarboxylic acid, terephthalic acid is preferable from the viewpoint of heat resistance, and is isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,4-phenic acid. Rangeoxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, dibenzoic acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic One kind or two or more kinds of aromatic dicarboxylic acids such as acid and 4,4′-biphenyldicarboxylic acid can be used in combination. The content of the aromatic dicarboxylic acid is 60 mol% or more of the dicarboxylic acid component, and preferably 75 mol% or more.
[0029]
Examples of dicarboxylic acids other than the aromatic dicarboxylic acids include malonic acid, dimethylmalonic acid, succinic acid, 3,3-diethylsuccinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, and trimethyl. Aliphatic dicarboxylic acids such as adipic acid, pimelic acid, azelaic acid, sebacic acid and suberic acid; and alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, These acids can be used alone or in combination of two or more.
Furthermore, a polyvalent carboxylic acid such as trimellitic acid, trimesic acid, pyromellitic acid or the like can be contained within a range where fiberization is easy.
In the present invention, the dicarboxylic acid component is preferably 100% aromatic dicarboxylic acid in terms of fiber properties, heat resistance, and the like.
[0030]
Further, 60 mol% or more of the diamine component is preferably composed of an aliphatic alkylene diamine having 6 to 12 carbon atoms. Examples of the aliphatic alkylene diamine include 1,6-hexanediamine and 1,8-octanediamine. 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine, 5-methyl-1,9-nonanediamine And the like. Of these, 1,9-nonanediamine alone or a combination of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is preferable from the viewpoint of fiber properties and heat resistance.
The content of the aliphatic alkylene diamine is preferably 60 mol% or more of the diamine component, more preferably 75 mol% or more, and particularly preferably 90 mol% or more.
[0031]
Examples of diamines other than the above aliphatic alkylene diamines include aliphatic diamines such as ethylene diamine, propylene diamine, and 1,4-butane diamine; fats such as cyclohexane diamine, methyl cyclohexane diamine, isophorone diamine, norbornane dimethyl diamine, and tricyclodecane dimethyl diamine. Cyclic diamines; aromatic diamines such as p-phenylenediamine, m-phenylenediamine, xylylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylether, or the like The mixture of these can be mentioned, These can use not only one type but 2 or more types.
[0032]
When 1,9-nonanediamine and 2-methyl-1,8-octanediamine are used in combination as the aliphatic alkylenediamine, 60 to 100 mol% of the diamine component is 1,9-nonanediamine and 2-methyl-1,8. It consists of octanediamine, and the molar ratio is preferably the former: the latter = 30: 70 to 99: 1, particularly the former: the latter = 40: 60 to 95: 5.
[0033]
The polyamide used in the present invention is [CONH / CH in its molecular chain. ₂ ] Is preferably 1/2 to 1/8, particularly preferably 1/3 to 1/5.
[0034]
The intrinsic viscosity (value measured at 30 ° C. in concentrated sulfuric acid) of the above polyamide is preferably 0.6 to 2.0 dl / g, particularly 0.6 to 1.8 dl / g, 0.7 to 1. 6 dl / g is preferred. The polyamide within the range of the intrinsic viscosity has good melt viscosity characteristics when fiberized, and further has excellent fiber properties and heat resistance.
[0035]
Furthermore, in the above-mentioned polyamide, it is preferable that 10% or more of the terminal groups of the molecular chain are sealed with an end-capping agent, 40% or more of the terminals, and 70% or more of the terminals are sealed. Is preferred.
[0036]
The method for producing the above polyamide is not particularly limited, and any known method can be used as a method for producing the crystalline polyamide. For example, it can be produced by a solution polymerization method or an interfacial polymerization method using acid chloride and diamine as raw materials, a melt polymerization method using dicarboxylic acid or an alkyl ester of dicarboxylic acid and diamine as raw materials, or a solid phase polymerization method.
[0037]
The above-mentioned polyamide has good adhesion to the conductive polymer layer (A) of the present invention, is less likely to cause interface peeling, and is suitable from the viewpoint of heat resistance and fiber properties.
[0038]
Next, the electrical resistance value R (Ω / cm · f) of the conductive fiber used in the present invention can be appropriately set depending on the application, but a charging brush or the like incorporated in an OA device such as a copying machine or a printer is used. In the case of a target, it is preferable that the electric resistance value R (Ω / cm · f) when 100 V is applied satisfies the following formula.
logR = 7.0-10.9
As a more preferable electric resistance value R (Ω / cm · f),
logR = 7.5-10.5
It is.
[0039]
In order to realize such electric resistance characteristics, in the present invention, it is preferable to use two kinds of conductive carbon blacks having different oil absorption amounts, for example, conductive carbon having an oil absorption amount of 130 to 350 cc / 100 g. It is preferable to use black in combination with conductive carbon black having an oil absorption of 15 to 130 cc / 100 g. When the former is called α type and the latter is called β type, the oil absorption ratio of α type and β type is preferably α / β = 1.2-25. In the present invention, the oil absorption is determined by the following method.
<Oil absorption amount>
Using linseed oil, the saturation amount (cc) at 100 g of each carbon was measured (cc / 100 g).
[0040]
As a combination of such conductive carbon blacks, in the present invention, the specific electric resistance value is 10 ^-3 -10 ² Carbon black having a resistance value of Ω · cm, 10 ⁰ -10 ⁶ It is preferable to use carbon black having a resistance value of Ω · cm in combination.
Further, the mixing ratio of the conductive carbon blacks is preferably α type: β type = 10: 1 to 1:10 from the viewpoint of obtaining good conductive performance.
[0041]
The method for producing the conductive conjugate fiber of the present invention is not particularly limited. For example, a method in which a composite spinning is performed using a melt spinning apparatus used for producing a multi-core core-sheath type conjugate fiber, and then drawn. Or may be manufactured by a method in which high-speed spinning is performed and the drawing step is omitted. However, in order to expose the conductive polymer layer (A) to the fiber surface in a desired state, the introduction hole for the conductive polymer (A) and the polymer (B) for the distribution plate in the spinning device It is preferable to adjust the positional relationship of the introduction holes and to adjust the composite ratio of both polymers.
[0042]
The single fiber fineness of the conductive fiber used in the present invention can be about 1 to 15 dtex depending on the application. Less than 1 dtex is not preferable because the spinning processability is unstable. If it is larger than 15 dtex, it is not preferable because the texture is poor and the charge removal performance is inferior.
[0043]
Moreover, the cross-sectional form of the conjugate fiber of the present invention is not particularly limited as long as the above-described conditions are satisfied. For example, cross-sectional forms as seen in FIGS. 1 to 10 can be exemplified.
[0044]
Such a conductive conjugate fiber of the present invention has a neutralizing performance excellent in fiber physical properties and durability in actual use, as well as clothing such as a uniform, OA such as a wiping cloth, a copying machine and a printer. It can be suitably used as a charging brush, a static elimination brush, or a cleaning brush incorporated in an apparatus.
[0045]
Next, the ultrafine fiber will be described. The ultrafine fiber used in the present invention has a single fiber fineness of 0.01 to 1 dtex. Yes When such fine fibers are used as a raw fiber for the fiber mixing process with conductive fibers, it is easy to cause inconveniences such as poor unraveling of fine fibers, yarn breakage, and deterioration of the quality of mixed fibers. Type composite fibers are used, and the desired extra fine fibers are formed by dividing the composite fibers by external force during mixing while avoiding such inconvenience. . like that fiber As , A split type composite fiber having a cross section in which both components are joined is used as a raw material fiber, comprising a polyamide component and a polyester component containing inorganic fine particles, and one component is not completely surrounded by the other component. . When the single fiber fineness of the ultrafine fiber is greater than 1 dtex, excellent wiping performance cannot be obtained in wiping applications. On the other hand, the case of less than 0.01 dtex is not preferable because the fiber itself is easily damaged and there are problems such as fibrillation.
[0046]
Moreover, the primary average particle diameter (μm) of the inorganic fine particles and the content (mass%) of the inorganic fine particles in the polyester satisfy the following formulas (1) to (3) as the ultrafine fibers, and the reduced viscosity (ηsp / C) of the polyester is A split type composite fiber having a reduced viscosity (ηsp / C) of polyamide of 1.6 to 2.2 is preferably 0.65 to 0.95.
0.01 ≦ Primary average particle size (μm) ≦ 5.0 (1)
0.05 ≦ Inorganic fine particle content (mass%) ≦ 10.0 (2)
0.01 ≦ X ≦ 3.0 (3)
X = primary average particle diameter (μm) × inorganic fine particle content (mass%)
[0047]
As the kind of inorganic fine particles, any inorganic fine particles can be used as long as they have no deterioration effect on the polyester forming the fiber and are excellent in stability by themselves. Typical examples of the inorganic fine particles include silica, alumina, calcium carbonate, titanium oxide, barium sulfate and the like, and these inorganic fine particles may be used alone or in combination of two or more. When two or more kinds are used in combination, the sum of the products of the particle diameters (a1, a2,...) And the contents (b1, b2,. That is, X = a1 × b1 + a2 × b2 +... An × bn X satisfies the above range.
[0048]
The primary average particle diameter of the inorganic fine particles is preferably 0.01 to 5.0 μm, and more preferably 0.03 to 3.0 μm. If the primary average particle size of the inorganic fine particles is less than 0.01 μm, even if slight fluctuations occur in the temperature of the heating zone for drawing, the running speed of the yarn, the tension applied to the running yarn, etc., the composite fiber Loops, fluff, fineness spots, etc. are likely to occur. On the other hand, when the primary average particle diameter of the inorganic fine particles exceeds 3.0 μm, the stretchability of the fibers is lowered and the yarn-making property becomes poor, and the yarn is likely to be broken during the production of the composite fiber. Here, the primary average particle diameter of the inorganic fine particles refers to a value when measured using a centrifugal sedimentation method.
[0049]
Furthermore, the content of the inorganic fine particles is preferably 0.05% by mass to 10.0% by mass based on the mass of the polyester. More preferably, it is 0.3 mass%-5.0 mass%. When the content of the inorganic fine particles is less than 0.1% by mass based on the mass of the polyester, slight changes are caused in the temperature of the heating zone for drawing, the running speed of the yarn, the tension applied to the running yarn, and the like. Even if it occurs, loops, fluff, fineness spots and the like are generated in the resulting composite fiber. On the other hand, when the content of the inorganic fine particles exceeds 10.0% by mass, the inorganic fine particles are run in the fiber drawing process. The resistance between the strip and air becomes excessive, leading to the generation of fluff and the occurrence of yarn breakage, and the process becomes unstable.
Furthermore, in the present invention, it is desirable that the product X of the primary average particle diameter and the content of the inorganic fine particles be within a specific range. If the product X is less than 0.01, the composite fiber may have loops, fluff, fineness spots, and the like. Not only is the process unsatisfactory due to poor processability, but unstretched parts frequently occur in the obtained fiber, which makes it difficult to use for clothing, and the splitting property is deteriorated.
[0050]
The polyester component constituting the ultrafine fiber is not particularly limited as long as it is a melt-spinnable polyester, but a polyethylene terephthalate, polybutylene terephthalate, or ethylene terephthalate unit and / or butylene terephthalate unit is a main repeating structural unit, and a small amount is added thereto. Copolyesters containing other copolymerized units are preferred, and polyethylene terephthalate is more preferred.
[0051]
In the case of using a copolyester having an ethylene terephthalate unit and / or a butylene terephthalate unit as a main repeating unit as the polyester, the proportion of the copolymerized unit in the copolyester is preferably 10 mol% or less, and other copolymer in that case Examples of polymerized units include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, and 5-alkali metal sulfoisophthalic acid: oxalic acid, adipic acid, azelaic acid, sebacic acid, and the like. Aliphatic dicarboxylic acids; multifunctional carboxylic acids such as trimellitic acid and pyromellitic acid: or carboxylic acid units derived from their ester-forming components: diethylene glycol, propylene glycol, butanediol or ethylene glycol, polyethylene glycol Can be exemplified Le, glycerin, units derived from pentaerythritol. And the copolyester may contain the 1 type (s) or 2 or more types of an above described copolymer unit.
[0052]
The method for adding the inorganic fine particles to the polymer is not particularly limited, and it may be added and mixed so that the inorganic fine particles are uniformly mixed in the polymer at an arbitrary stage until immediately before melt spinning the polymer. For example, the inorganic fine particles may be added at any time during the polymerization of the polymer, may be added later to the polymer after the polymerization, such as during the production of pellets, or before the polymer is spun from the spinneret. In the stage, the inorganic fine particles may be uniformly melt-mixed in the polymer.
[0053]
In the polymer forming the ultrafine fiber used in the present invention, in addition to the above-described inorganic fine particles, if necessary, a fluorescent brightener, a stabilizer, an antioxidant, an ultraviolet absorber, a hydrolysis inhibitor, You may contain the 1 type (s) or 2 or more types of an antistatic agent, a flame retardant, a coloring agent, and another additive.
[0054]
In the case where a split composite fiber of polyester and polyamide is used as the raw fiber for the ultrafine fiber used in the present invention, the polyester preferably has a specific range of reduced viscosity. Viscosity was measured using an Ubbelohde viscometer in an o-chlorophenol solution at a concentration of 1 g / 100 cc and 30 ° C., and the reduced viscosity (ηsp / C) at that time was 0.65 to 0.95 dl / g. From the viewpoints of spinnability and splitting property of the resulting composite fiber. When the reduced viscosity is lower than 0.65, fuzz and yarn breakage are generated in the fiberizing process, resulting in poor processability. On the other hand, if it is higher than 0.95, the fiber forming processability is similarly unfavorable.
[0055]
For example, nylon 4, nylon 6, nylon 7, nylon 11, nylon 12, nylon 66, nylon 6, 10, polymetaxylene Examples thereof include diadipamide, polyparaxylene decanamide, polybiscyclohexylmethane decanamide, and copolyamides containing them as components. Nylon 6 and polyamide mainly composed of nylon 6 are preferable.
[0056]
The reduced viscosity of the polyamide preferably satisfies a certain range, and the reduced viscosity ηsp / C when measured at 30 ° C. in an O-chlorophenol solution at a concentration of 1 g / 100 cc using an Ubbelohde viscometer is 1.6 to It is important to enter the range of 2.2. When the reduced viscosity is less than 1.6 or exceeds 2.2, fluff and yarn breakage occur in the fiberizing process, resulting in not only poor processability but also poor splitting property of the composite fiber. As described above, the combination of the preferred viscosity range of polyester and the preferred viscosity range of polyamide provides high speed spinnability and maximizes the difference in strain on the molecular structure of the composite bicomponent interface of the resulting composite fiber. It is considered that good splitting properties in the post-processing steps are expressed.
[0057]
Further, the presence of inorganic fine particles having a specific primary average particle size and a specific content in the polyester exerts a synergistic effect suitable for easy splitting when subjected to chemical and physical treatments.
[0058]
As the split type composite fiber, the polyamide component and the polyester component (which has a low affinity with the polyamide component) are in a single filament form in a composite form in which one component does not completely surround the other component in the cross section of the single filament. The side-by-side type composite fiber as shown in FIG. 11, the side-by-side repetitive type composite fiber as shown in FIG. 12, and the radial type as shown in FIGS. A composite fiber composed of a component having a shape and another component having a shape that complements the radiating portion, and a V-shape that complements the component having the radial shape and the radiating portion as shown in FIG. A composite fiber composed of the same component as the component having the radial shape and the other component having a concave shape and the V-shaped shape complementing the concave portion as shown in FIG. A sky portion can be given a side-by-side repeating type composite fibers.
[0059]
The polyester component and the polyamide component constituting the composite fiber can be easily divided by performing chemical treatment such as treatment with an alkaline aqueous solution, treatment with a polyamide swelling agent and / or physical treatment such as false twisting. It is.
[0060]
In the divided fiber, “divided” means, for example, when the composite fiber has a cross section as shown in FIG. 12, the joint portion of each component is divided, for example, five segment yarns of polyamide component and polyester component This refers to the state of 11 fine fibers consisting of 6 segment yarns. For example, when the composite fiber has a cross section as shown in FIG. 15, it is divided in the same manner and has a cross-shaped cross section. It means a state in which five fine fibers are formed by one segment yarn of a component and four segment yarns of a polyester component having a sector cross section. Furthermore, even if the composite fiber has any other cross-sectional shape, the divided state can be easily inferred from the above description.
[0061]
The degree of division of the composite fiber of the present invention after the division treatment is preferably 80% or more. Here, the degree of division refers to a value measured by the following method. That is, observe any 100 cross-sections of the composite fibers in the area to be measured (including those that are split into fiber bundles and those that are not partly split), and are actually split and present After splitting, the fine fibers (N) are counted. In this case, the number of composite fibers that are not divided at all is one, and the one that is partially divided is the total number of semi-divided composite fibers and the number of divided fine fibers that are divided therefrom. Next, a post-division fine fiber (Np) obtained when the 100 composite fibers are assumed to be completely divided is calculated, and the value of N / Np × 100 is set as the division degree. In addition, the said division | segmentation degree is calculated | required about the thing which carried out the immersion stirring process for 5 to 20 minutes at 98 degreeC in alkaline aqueous solution (concentration 4g / l) as a division | segmentation process conditions, and dried.
[0062]
Next, the method for producing the ultrafine fiber of the present invention will be described. As described above, the ultrafine fiber of the present invention is not particularly limited as long as it is a production method capable of obtaining a single fiber fineness of 1 dtex or less, but it is desirable to form the ultrafine fiber by dividing the split type composite fiber. An example of a method for producing such split-type composite fibers is as follows: first, polyester and polyamide are melt-extruded by individual extruders, introduced into a spinning head, and passed through a spinneret that forms the desired individual composite shape. And melt spinning. In this case, the melt spinning temperature, melt spinning speed, etc. are not particularly limited and can be carried out under the same conditions as those usually used for producing polyester fibers. When the melting point of the polyester is high, generally the melt spinning temperature is set to a temperature in the range of (melting point of polyester + 20 ° C.) to (melting point of polyester + 40 ° C.) (for example, generally about 280 to 300 ° C. when the polyester used is polyethylene terephthalate). , And the melt spinning speed (melt spinning amount) is about 20 to 50 g / spindle hole 1 mm. ² -About a minute is preferable because a composite fiber with good quality can be obtained with good spinning processability.
Further, the size and number of the spinning holes in the spinneret, the shape of the spinning holes, etc. are not particularly limited, and can be adjusted according to the single fiber fineness, the total denier number, the cross-sectional shape, etc. of the target composite fiber. Generally, the size of the spinning hole (single hole) is about 0.018 to 0.07 mm. ² It is desirable to keep the degree. When nozzle dirt accumulates around the hole of the spinneret and thread breakage occurs, a method of blocking the oxygen by forming the nozzle hole outlet in a tapered shape or steam-sealing the atmosphere under the nozzle is preferable.
[0063]
The composite fiber melt-spun by the above is once cooled to a temperature not higher than the glass transition temperature of the lower one of the composite two-component polymers, preferably 10 ° C. or lower than the glass transition temperature. . The cooling method or cooling device in this case is not particularly limited as long as it is a method or device that can cool the spun composite fiber below its glass transition temperature, but a cooling air blowing tube or the like under the spinneret. It is preferable to provide a cooling air blowing device and to cool the glass fiber below the glass transition temperature by blowing cooling air to the spun composite fiber. At that time, the cooling conditions such as the temperature and humidity of the cooling air, the blowing speed of the cooling air, and the cooling air blowing angle with respect to the spun fiber are not particularly limited, and the composite fiber spun from the base is swayed in the fiber. Any conditions may be used as long as they can be promptly and uniformly cooled to the glass transition temperature or less while preventing them from occurring. Among them, the cooling air temperature is about 20-30 ° C., the cooling air humidity is 20-60%, and the cooling air blowing speed is about 0.4-1.0 m / sec. It is preferable to cool the conjugate fiber spun with the direction perpendicular to the spinning direction because a high-quality conjugate fiber can be obtained smoothly. In addition, when cooling is performed under the above-described conditions using a cooling air blowing cylinder, a cooling air blowing cylinder having a length of about 80 to 160 cm with a slight gap or no gap immediately below the spinneret. Is preferably arranged.
[0064]
Next, the composite fiber cooled to below the glass transition temperature is subsequently introduced directly into the heating zone and drawn. Although the temperature of the heating zone may vary depending on the type of polyester, etc., in general, if the temperature is 40 ° C. or higher than the glass transition temperature of polyester and polyamide, the physical properties of the resulting composite fiber will be satisfactory in practice. For example, in the case of a composite fiber of polyethylene terephthalate and nylon 6, the temperature of the heating zone is preferably about 100 ° C. or higher. The upper limit temperature of the heating zone may be a temperature at which fusion between fibers, yarn breakage, single yarn breakage or the like does not occur in the heating zone. The type and structure of the heating zone can heat the composite fiber running in the heating zone without contacting the heating means in the heating zone, and the yarn running in the heating zone and the air surrounding it. Any structure may be used as long as it can cause resistance between them and increase the yarn tension to cause the fibers to stretch. Among them, as the heating zone, a cylindrical heating zone is preferably used, and a tube heater having an inner diameter of about 20 to 50 mm, in which the tube wall itself is a heater, is particularly preferable. The installation position of the heating zone from the spinneret, the length of the heating zone, etc. are the type of composite fiber, the amount of composite bicomponent polymer spun, the cooling temperature of the composite fiber, the traveling speed of the composite fiber, the temperature of the heating zone, the heating It can be adjusted according to the inner diameter of the zone, but generally the distance from the bottom of the spinneret to the inlet of the heating zone is about 0.5 to 3.0 m, and the length of the heating zone is about 1.0 to 2.0 m. It is desirable that the composite fiber can be heated and uniformly stretched smoothly in the heating zone.
[0065]
Then, if necessary, an oil agent is applied to the composite fiber drawn in the heating zone, and then the composite fiber is taken up at a high speed. The production process of the stretched conjugate fiber comprising the series of steps described above is preferably performed at a take-up speed of the conjugate fiber of 3500 m / min or more, and more preferably at a take-up speed of 4000 m / min or more. When the take-up speed of the composite fiber is less than 3500 m / min, the fiber is not sufficiently drawn in the heating zone, the mechanical properties of the resulting composite fiber are lowered, and the process of the present invention comprising the series of steps described above. The method is not carried out smoothly, and in particular, the yarn tension fluctuation in the heating zone, overheating, etc. occur, and uniform stretching is difficult to perform. Further, in carrying out the method of the present invention, the {drawing speed (m / min)} of the conjugate fiber ÷ {the amount of spinning of the conjugate fiber (25 g / spinning hole 1 mm) ² The value of min)} is preferably in the range of about 140-200.
In the present invention, split-type composite fibers such as those obtained by the above-described manufacturing method are used and physically split in a fiber mixing step to form ultrafine fibers.
[0066]
About the manufacturing method of the blended yarn of this invention, it is the method of sending to a separate supply roller so that it may become an ultrafine fiber (split type composite fiber) on a core, and a conductive fiber on the side, and uniting both. The supply roller speed of the conductive fiber is set to be equal to or higher than the other roller supply speed.
Furthermore, it is necessary to integrate so that a conductive fiber and an ultrafine fiber may not isolate | separate. For this purpose, there are methods such as twisting and winding, but it is preferable to integrate by air entanglement method in terms of tension applied to the conductive fiber, and 2.0 kg / cm ² The above-mentioned air entangled nozzle is used for entanglement and mixing, and the number of entanglement at that time is 10 pieces / m or more, more preferably 15 pieces / m or more. If the number of entanglements is less than 10, it is not preferable because the effect of suppressing static electricity is reduced and the conductive fiber is easily affected by physical breakage.
[0067]
In the present invention, preferably, at least two kinds of conductive carbon blacks having different oil absorption amounts are contained, and the electrical resistance value R (Ω / cm · f) when 100 V is applied satisfies the following formula: Conductive fiber, more preferably, the above-mentioned conductive fiber containing two types of conductive carbon black having an oil absorption ratio of 1.2 to 25, and is flat and has a temperature of 20 degrees or more and 120 degrees or less. It consists of a cross section with at least two angles and has a specific surface area of 4000 cm. ² It is preferable to use a blended yarn composed of ultrafine fibers of at least / g because when used in various brushes for copying machines, a clear and uniform printed image can be maintained over a long period of time.
[0068]
logR = 7.0-10.9
As a more preferable electric resistance value R (Ω / cm · f),
logR = 7.5-10.5
It is.
[0069]
The mixed yarn of the present invention has a neutralizing performance excellent in fiber physical properties and durability in actual use, and can be suitably used as a charging brush or a neutralizing brush incorporated in an OA device such as a copying machine or a printer. it can. In addition, taking advantage of the excellent fastness to dyeing, it can also be used in work clothes such as work clothes and uniforms in an environment that dislikes static electricity, and in wiping cloths.
[0070]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In addition, the measurement of the electrical resistance value of the conductive fiber, the measurement of the charge amount, the dyeing fastness of the fabric, the wiping performance, the image evaluation when using a charging brush, and the like were performed by the following methods.
[0071]
<Electric resistance value R>
A direct current voltage of 25 to 500 V was applied to the conductive fiber (single fiber) sample set on the parallel clip electrode by the voltage ammeter method, and the voltage and current value flowing through the sample at that time were determined according to Ohm's law. Moreover, the electrical resistance value prescribed | regulated by this invention is calculated | required at the time of 100V application.
[0072]
<Charged charge amount>
Using a simple Faraday gauge according to JIS L-1094, the charged charge amount was measured using an acrylic fiber cloth as a friction cloth in an atmosphere of 20 ° C. and 40% RH.
[0073]
<Dyeing fastness to washing>
A sample dyed according to the dyeing conditions shown in Example 1 was cut out to 100 × 40 mm, and two 50 × 40 mm nylon attached cloths were sewn side by side on the surface of the sample piece. -0844: 1997 Washing was performed according to the A-2 method, and the determination was performed based on the following.
(1) Liquid contamination
The remaining liquid after the washing test is put into a 2 × 4 × 1 cm magnetic beaker, and JIS L-0801 9. Judgment was carried out.
(2) Contamination of attached cloth
Regarding the contamination of the nylon-attached cloth, see JIS L-0801, 9. Judgment was carried out.
[0074]
<Image evaluation method>
In the brush charging method, a charged image output test was performed by applying a DC bias voltage with the brush rotating direction opposite to the photoconductor, and image evaluation after initial and 10,000 copies was performed according to the following criteria.
(1) Initial performance evaluation
○: A clear and uniform image is obtained.
Δ: Slightly abnormal discharge traces are observed.
X: The image is unclear and streaks are conspicuous.
(2) Repeated (10,000 sheets) image evaluation
A: A clear and uniform image similar to the initial one can be obtained.
Δ: Slightly abnormal discharge traces are observed.
X: The image is unclear and streaks are conspicuous.
[0075]
<Wipeability evaluation method>
1) Wiping performance evaluation
The slide glass on which the contaminants were adhered was temporarily bonded to a flat test table of a friction tester (testing machine conforming to JIS L 0823), and was wiped off with a friction piece equipped with a test cloth. The wiping load was 200 g, the wiping width was 20 mm, and the wiping stress was 100 g / mm. Wiping was performed several times, the transmitted light rate before and after wiping was measured, and calculated as follows.
Wiping rate (%) = [(Wn−W0) / (Wb−W0)] × 100
Wb: Transmittance of the slide glass at 380 nm or 580 nm
Wn: transmittance after wiping off
W0: Transmittance before wiping
[0076]
[Pollutants]
a. Cleaning power against nicotine
A slide glass (20 sheets) was placed horizontally in the fumigation box, fumigated with about 20 cigarettes (pieces), and pollutants were adhered mainly with nicotine. The visible light transmittance was adjusted to 20% or less.
b. Cleaning power against lubricating oil
A frame was placed on the slide glass, and a commercially available lubricant was sprayed from a distance of 30 cm for 3 seconds to prepare a sample.
c. Cleaning power against glue
Glue consisting of 10 g / l corn starch on a slide glass (0.5 g / cm ² ) Was applied.
[0077]
Reference Example 1 (Production of thermoplastic polyamide)
The amounts of terephthalic acid, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, benzoic acid, sodium hypophosphite-hydrate (0.1% by mass relative to the raw materials) shown in Table 1 and Distilled water (2.2 liters) was added to an autoclave with an internal volume of 20 liters to perform nitrogen substitution. Subsequently, the mixture was stirred at 100 ° C. for 30 minutes, and the internal temperature was raised to 210 ° C. over 2 hours. At this time, the autoclave is 22 kg / cm ² (2.16 × 10 ⁶ The pressure was increased to Pa). The reaction was continued for 1 hour, and then the temperature was raised to 230 ° C., and then maintained at 230 ° C. for 2 hours. ² (2.16 × 10 ⁶ The reaction was continued while maintaining at Pa). Next, the pressure is 10 kg / cm over 30 minutes. ² (9.81 × 10 ⁵ Pa) and the reaction was continued for another hour to obtain a prepolymer. The prepolymer was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less.
The pulverized product was subjected to solid phase polymerization at 230 ° C. and 0.1 mmHg (13.3 Pa) for 10 hours to obtain polyamide. Intrinsic viscosity of the obtained polyamide and CONH / CH ₂ Is shown in Table 1.
[Table 1]

[0078]
Example 1
Nylon 6 containing 35% by mass of conductive carbon black (oil absorption amount: 115 cc / 100 g) was used as the conductive polymer component (A), and the thermoplastic polyamide (PA9MT) shown in Reference Example 1 in Table 1 was used as the polymer component (B). ), A: B composite ratio 13/87 mass%, composite spinning with a four-core core-sheath exposed cross section as shown in FIG. 3, followed by stretching, 25 denier / 4f (27.8 dtex / 4f) ) Conductive composite fiber (L ₂ : Filament cross-sectional length of 1 filament = 88 μm). The fiberization processability was good and no problem. In the obtained conductive conjugate fiber, the conductive polymer layer (A) was continuously continuous in the fiber axis direction. Further, the number of exposed portions on the fiber surface of the conductive polymer layer (A) is 4, and the exposed distance L in the fiber cross-section circumferential direction of the conductive polymer layer, respectively. ₁ (Μm) is 0.6 μm in the circumferential direction, and 0.1 ≦ L ₁ (Μm) ≦ L ₂ / 10 conditions were satisfied. Furthermore, the electric resistance value when 100 V is applied is 2 × 10. ⁸ It was very stable at Ω / cm · f (that is, logR = 8.3), and had excellent conductive performance even under a low applied voltage.
The split type composite fiber for mixing with the obtained conductive fiber had a reduced viscosity of 0.85 (concentration in orthochlorophenol 1 g / dl, 30) containing 1.0% by mass of silica having a primary average particle size of 0.04 μm. ° C) polyethylene terephthalate (hereinafter abbreviated as PET) and nylon 6 having a reduced viscosity of 1.80 (concentration in orthochlorophenol of 1 g / dl, 30 ° C), and each was melt-extruded separately, and then each polymer part 2 is supplied to a spinning head that forms a multi-layered composite shape with 6 layers of PET and 5 layers of nylon as shown in FIG. 2, and the diameter of the metering portion is 0.25 mmφ, the land length is 0.5 mm, and the nozzle Melt spinning was carried out at a spinning temperature of 285 ° C. from a 24-hole round hole nozzle in which the hole outlet was in a trumpet shape and the outlet diameter was 0.5 mmφ (see Table 2).
[0079]
A horizontal blowing type cooling air spraying device having a length of 1.0 m is installed directly under the spinneret, and the composite fiber spun from the base is immediately introduced into the cooling air spraying device, at a temperature of 25 ° C. and a humidity of 65 RH%. The cooled air adjusted to was blown onto the spun fiber at a speed of 0.5 m / second, and the fiber was cooled to 50 ° C. or lower (fiber temperature at the outlet of the cooling air spray device = 40 ° C.).
[0080]
The composite fiber cooled to 50 ° C. or lower is introduced into a tube heater (inner wall temperature 180 ° C.) having a length of 1.0 m and an inner diameter of 30 mm installed at a position 1.6 m from directly below the spinneret, and drawn in the tube heater. After that, an oil agent was applied to the fiber coming out of the tube heater by a guide oiling method, and subsequently wound up at a take-up speed of 4300 m / min via a pair of (two) take-up rollers, and the stretched 75 denier 24 A filament (82.5 dtex / 24f) composite fiber was produced (see Table 3). Air entanglement was performed at a ratio of the obtained conductive fibers (25% by mass) and split ultrafine fibers (75% by mass), false twisting was performed at 3390 T / M, and a temperature was 170 ° C. to perform split processing. A cylindrical knitted fabric was prepared using the obtained crimped yarn made of polyester and polyamide, and subjected to relaxation, water washing, drying, presetting, alkali weight loss, water washing treatment and drying, and each performance was evaluated. The results are shown in Table 1. A product having cleaning ability against nicotine, lubricating oil and glue was obtained. Furthermore, when the cross section of the fiber was observed, it showed a good splitting property of 95% splitting.
Subsequently, the polyester was dyed under the following conditions.
[0081]

After the reduction cleaning, cold water washing was performed.
[0082]
The charged amount of woven fabric is 3.5μ coulomb / m ² Met. The actual amount of charge after wearing for 2 years and repeated washing about 250 times during that period is 4.8μcoulomb / m ² Excellent static neutralization performance, that is, the standard value (hereinafter simply abbreviated as the standard value) of the ESD Safety Guidelines published by the Ministry of Labor, Industrial Safety Research Institute 7μ coulomb / m ² It cleared the following, was very excellent in durability, and excellent in cleaning power against nicotine, lubricating oil and glue.
[0083]
[Table 2]

[Table 3]

[Table 4]

[0084]
Examples 2-4
Using the same conductive fibers as in Example 1, Example 2 has the cross-sectional shape of the ultrafine fiber as shown in FIG. 16, Example 3 has the cross-sectional shape as shown in FIG. 18, and Example 4 is made of PET and nylon 6. The same operation as in Example 1 was performed except that the composite ratio was 3/1. Both the fiber forming processability and the splitting property are good, and the initial charged charge amount of the fabric and the charged charge amount after 250 washings both clear the reference value and have excellent actual durability. Nicotine, lubricating oil The cleaning power against glue was also excellent.
[0085]
Examples 5-6
The same conductive fibers as in Example 1 were used, and in Example 5, titanium oxide having a primary average particle diameter of 0.4 μm was used in place of the silica used in Example 1, and the titanium oxide content in PET was 0.5. Example 6 was carried out in the same manner as in Example 1 except that barium sulfate having a primary average particle size of 0.6 μm was used instead of silica and the barium sulfate content in PET was 1.0% by mass. did. Both the fiber forming processability and the splitting property are good, and the initial charged charge amount of the fabric and the charged charge amount after 250 washings both clear the reference value and have excellent actual durability. Nicotine, lubricating oil The cleaning power against glue was also excellent.
[0086]
Examples 7-10
Example 7 uses the same ultrafine fibers as in Example 1, Example 7 shows the composite cross-sectional shape of the conductive fiber in FIG. 1, Example 8 shows the composite cross-sectional shape in FIG. 6, Example 9 shows the composite cross-sectional shape in FIG. 10 was carried out in the same manner as in Example 1 except that nylon 12 was used as the conductive carbon matrix polymer. Both the fiber forming processability and the splitting property are good, and the initial charged charge amount of the fabric and the charged charge amount after 250 washings both clear the reference value and have excellent actual durability. Nicotine, lubricating oil The cleaning power against glue was also excellent.
[0087]
Example 11
Nylon 6 containing 35% by mass of two types of conductive carbon blacks (α type oil absorption: 180 cc / 100 g, β type oil absorption: 80 cc / 100 g, mixing ratio α / β = 2/1) with different conductivity performance Except for the use of the conductive polymer component (A), fiberization was carried out in the same manner as in Example 1, and 25 denier / 4f (27.8 dtex / 4f) conductive composite fiber (L ₂ : Filament cross-sectional length of 1 filament = 88 μm). The fiberization processability was good and no problem. In the obtained conductive conjugate fiber, the conductive polymer layer (A) was continuously continuous in the fiber axis direction. Further, the number of exposed portions on the fiber surface of the conductive polymer layer (A) is 4, and the exposed distance L in the fiber cross-section circumferential direction of the conductive polymer layer, respectively. ₁ (Μm) is 0.6 μm in the circumferential direction, and 0.1 ≦ L ₁ (Μm) ≦ L ₂ / 10 conditions were satisfied. Furthermore, the electric resistance value when 100 V is applied is 1 × 10 ⁹ It was very stable at Ω / cm · f (that is, logR = 9.0), and had excellent conductive performance even under a low applied voltage.
Air entanglement was performed at a ratio of the obtained conductive fiber (25% by mass) and the same split-type ultrafine fiber (75% by mass) as in Example 1, and false twist was applied at a temperature of 3390 T / M and a temperature of 170 ° C.
About the resulting blended yarn, 50,000 piles / (2.54 cm) ² A conductive brush of density was created. As a result of image evaluation with a copying machine, it was very excellent with no abnormal discharge. The image evaluation was good for 10,000 copies and the durability was very good. Table 2 shows the composite composition, fiber form, fiberization processability, electrical resistance value, and image evaluation result of the conductive conjugate fiber.
[0088]
Examples 12-14
Fiberization was carried out in the same manner as in Example 11 except that the type of carbon black, the mixing ratio thereof, and the addition amount to the matrix polymer were changed as shown in Table 2. All were excellent in fiberization process property and image characteristics (see Tables 2 to 4).
[0089]
Comparative Examples 1-4
Although it implemented similarly to Example 1 except manufacturing a fiber as shown in Table 2 as an electroconductive composite fiber, the static elimination performance or the fiberization process property was unsatisfactory.
[0090]
Comparative Examples 5-6
Fibers as shown in Tables 2 and 3 were produced as split-type ultrafine fibers and mixed fibers, and image evaluation was performed in the same manner as in Example 11. However, all of them were defective. (See Tables 2-4)
[0091]
【The invention's effect】
In the present invention, conductive composite fibers obtained by composite spinning a thermoplastic polymer containing a specific amount of conductive carbon black by a method satisfying predetermined conditions, and excellent mechanical properties such as strength and elongation. By using mixed yarn of split-type composite fibers made of high-quality polyester and polyamide, it has excellent static elimination performance even after long-term actual use as a charging brush for clothing or copying machines, etc., and used as a wiping cloth It is possible to provide a mixed fiber having an amazing wiping power sometimes. In addition, when the conductive conjugate fiber of the present invention is mixed with other fibers to obtain a fiber product, even if a dyeing process is performed, the other fibers are excellent in dyeing fastness.
[Brief description of the drawings]
FIG. 1 is a schematic view showing an example of a cross-sectional form of a conductive conjugate fiber used in the present invention.
FIG. 2 is a schematic view showing another example of the cross-sectional form of the conductive conjugate fiber used in the present invention.
FIG. 3 is a schematic view showing another example of the cross-sectional form of the conductive conjugate fiber used in the present invention.
FIG. 4 is a schematic view showing another example of the cross-sectional form of the conductive conjugate fiber used in the present invention.
FIG. 5 is a schematic view showing another example of the cross-sectional form of the conductive conjugate fiber used in the present invention.
FIG. 6 is a schematic view showing another example of the cross-sectional form of the conductive conjugate fiber used in the present invention.
FIG. 7 is a schematic view showing another example of the cross-sectional form of the conductive conjugate fiber used in the present invention.
FIG. 8 is a schematic view showing another example of the cross-sectional form of the conductive conjugate fiber used in the present invention.
FIG. 9 is a schematic view showing an example of a cross-sectional form of a conductive conjugate fiber outside the present invention.
FIG. 10 is a schematic view showing another example of the cross-sectional form of the conductive conjugate fiber outside the present invention.
FIG. 11 is a schematic view showing an example of a cross-sectional form of a split type composite fiber used in the present invention.
FIG. 12 is a schematic view showing another example of the cross-sectional form of the split-type conjugate fiber used in the present invention.
FIG. 13 is a schematic view showing another example of the cross-sectional form of the split-type conjugate fiber used in the present invention.
FIG. 14 is a schematic view showing another example of the cross-sectional shape of the split-type conjugate fiber used in the present invention.
FIG. 15 is a schematic view showing another example of the cross-sectional form of the split-type conjugate fiber used in the present invention.
FIG. 16 is a schematic view showing another example of the cross-sectional shape of the split-type conjugate fiber used in the present invention.
FIG. 17 is a schematic diagram showing another example of the cross-sectional shape of the split-type conjugate fiber used in the present invention.
FIG. 18 is a schematic view showing another example of the cross-sectional shape of the split-type conjugate fiber used in the present invention.
[Explanation of symbols]
A: Conductive polymer layer (A)
B: Polymer layer (B)

Claims (5)

It consists of a conductive fiber having a single fiber fineness of 1 dtex to 15 dtex containing a thermoplastic polymer containing 15% by mass to 50% by mass of conductive carbon black, a polyester component containing a polyamide component and inorganic fine particles. It is composed of ultrafine fibers having a single fiber fineness of 0.01 to 1 dtex obtained by dividing a split type composite fiber having a cross section in which both components are joined without completely surrounding the other component, and the number of entanglements is A blended yarn of 10 / m or more. The mixed fiber according to claim 1, wherein the conductive fiber has a fiber mixing ratio of 0.05 mass% to 50 mass%. A conductive composite comprising a conductive polymer layer (A) made of a thermoplastic polyamide containing 15 to 50% by weight of conductive carbon black and a polymer layer (B) made of a thermoplastic polyamide having a melting point of 170 ° C. or higher. It is a fiber, and the conductive polymer layer (A) is exposed at one or more locations on the fiber surface when viewed in an arbitrary fiber cross section, and the exposure distance L ₁ (μm) per exposed location is expressed by the following formula: The polymer layer (B) satisfying and is a conductive composite fiber that occupies 60% or more of the fiber cross-sectional circumference and occupies 50% to 97% by mass of the total mass of the fiber. The blended yarn described.
_{0.1 ≦ L 1 ≦ L 2/} 10
L ₂ : Fiber cross-sectional circumference of a filament (μm) The thermoplastic polyamide constituting the polymer layer (B) of the conductive fiber is a dicarboxylic acid component in which 60 mol% or more of the dicarboxylic acid component is an aromatic dicarboxylic acid and 60 mol% or more of the diamine component has 6 to 12 carbon atoms. 4. The blended yarn according to claim 3, which is a conductive conjugate fiber, which is a thermoplastic polyamide polymerized from a diamine component which is an aliphatic alkylene diamine. The ultrafine fibers are polyester ultrafine fibers containing polyamide ultrafine fibers and inorganic fine particles, and the primary average particle diameter (μm) of the inorganic fine particles and the content of inorganic fine particles (% by mass) in the polyester are represented by the following formulas (1) to ( 5), the reduced viscosity (ηsp / C) of the polyester is 0.65 to 0.95, and the reduced viscosity (ηsp / C) of the polyamide is 1.6 to 2.2. Yarn.
0.01 ≦ Primary average particle size (μm) ≦ 5.0 (1)
0.05 ≦ Inorganic fine particle content (mass%) ≦ 10.0 (2)
0.01 ≦ X ≦ 3.0 (3)
X = primary average particle diameter (μm) × inorganic fine particle content (mass%)

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