JP7195592B2 - Composite fiber with latent crimpability - Google Patents
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Description
本発明は、優れた潜在捲縮性を有し、かつ顔料を含有する原着複合繊維に関する。 TECHNICAL FIELD The present invention relates to a spun-dyed conjugate fiber having excellent latent crimpability and containing a pigment.
従来から、ポリエステル繊維は、衣料用、産業資材用等種々の用途に使用されているが、中でも立体捲縮を有するポリエステル繊維は、その伸縮性を生かし、貼付剤やサポーター等の医療衛生材の基布に適した不織布の構成繊維として広く用いられている。このような伸縮性に富んだ立体捲縮を有するポリエステル繊維として、熱収縮特性の異なるポリマーをサイドバイサイドまたは偏心芯鞘構造に複合した潜在捲縮性能を有する複合繊維が数多く提案されている。
例えば、特許文献１、２には、５－ナトリウムスルホイソフタル酸成分を共重合したポリエチレンテレフタレート系共重合ポリエステルとポリエチレンテレフタレートとの複合繊維が開示されている。また、特許文献３にはイソフタル酸とビスフェノールＡのエチレンオキシド付加体（ＢＡＥＯ）とを共重合したポリエステルとポリエチレンテレフタレートとの複合繊維が開示されている。
Conventionally, polyester fibers have been used in various applications such as clothing and industrial materials. Among them, polyester fibers with three-dimensional crimps are used for medical sanitary materials such as patches and supporters, taking advantage of their stretchability. It is widely used as a constituent fiber of nonwoven fabric suitable for base fabric. As such highly stretchable and three-dimensionally crimped polyester fibers, there have been proposed many conjugated fibers having latent crimp performance in which polymers having different heat shrinkage properties are conjugated in a side-by-side or eccentric core-sheath structure.
For example, Patent Documents 1 and 2 disclose a composite fiber of polyethylene terephthalate and polyethylene terephthalate-based copolymer polyester obtained by copolymerizing a 5-sodium sulfoisophthalic acid component. Further, Patent Document 3 discloses a composite fiber of polyester and polyethylene terephthalate obtained by copolymerizing isophthalic acid and an ethylene oxide adduct of bisphenol A (BAEO).
特許文献１～３に開示される潜在捲縮性複合繊維はいずれも白色繊維であり、着色された複合繊維が要求される場合、得られた繊維に色付けのための染色加工が必要になる。染色工程を要する場合、コストアップや工程が長くなることによる納期の長期化、また、染色工程にて発生する排水による環境汚染などの問題を有している。
これらの問題を解決する手段として有色顔料を含有させる原着繊維が広く用いられている。例えば、特許文献４、５には、特定の共重合ポリエステルとポリエチレンテレフタレートからなるサイドバイサイド型潜在捲縮性複合繊維であって、ポリエステルに有色顔料を含有させた原着繊維およびこの繊維を用いた不織布が開示されている。有色顔料としては、コストが安く扱いやすいことから無機系顔料が用いられることが多いが、繊維製造における延伸工程および不織布加工工程において、繊維表面が摩擦抵抗を受けた際に、一部の無機系顔料が脱落するという問題があり、特に２．６デシテックス以下の細い繊度の繊維の場合は、その問題がより顕著に発生しやすい。工程中に、顔料が脱落すると、機械設備の汚染が生じることや、機械設備に脱落した顔料が堆積し、その顔料の堆積物が原料繊維表面に付着してしまい、そのような堆積物が付着した原料繊維が製品に混入すれば、得られる繊維製品における品質面における問題が生じる恐れがあった。
All of the latently crimpable conjugate fibers disclosed in Patent Documents 1 to 3 are white fibers, and when colored conjugate fibers are required, the obtained fibers need to be dyed for coloring. When a dyeing process is required, there are problems such as an increase in cost and a long delivery time due to the lengthening of the process, and environmental pollution due to wastewater generated in the dyeing process.
As a means of solving these problems, dope-dyed fibers containing colored pigments are widely used. For example, Patent Documents 4 and 5 disclose a side-by-side latent crimpable conjugate fiber composed of a specific copolyester and polyethylene terephthalate, which is a dope-dyed fiber in which polyester contains a colored pigment, and a nonwoven fabric using this fiber. is disclosed. Inorganic pigments are often used as colored pigments because they are inexpensive and easy to handle. There is a problem that the pigment falls off, and this problem is more likely to occur particularly in the case of fine fineness fibers of 2.6 decitex or less. If the pigment falls off during the process, it may cause contamination of the machinery and equipment, or the fallen pigment will accumulate on the machinery and equipment, and the deposit of the pigment will adhere to the surface of the raw material fiber, and such deposits will adhere. If the raw material fibers that have been treated are mixed into the product, there is a possibility that the obtained fiber product will have quality problems.
本発明は上記のような問題点を解決し、染色加工を必要としないで使用することができる原着複合繊維であって、細い繊度の原着複合繊維であっても、優れた品質と伸縮性を有する繊維製品を得ることができる潜在捲縮能を有する原着複合繊維を提供しようとするものである。 The present invention solves the above-mentioned problems, and is a spun-dyed conjugated fiber that can be used without the need for dyeing, and even if it is spun-dyed conjugated fiber with a fine fineness, it has excellent quality and elasticity. Disclosed is a solution-dyed conjugated fiber having latent crimpability from which a textile product having elasticity can be obtained.
本発明者らは、上記の課題を解決するために鋭意検討した結果、有色顔料を含む原着複合繊維であっても、無機系顔料と有機系顔料の両者を含み、かつ無機系顔料と有機系顔料との色調を特定したものをポリエステルに含有させることにより、紡糸操業性を悪化させることなく、機械設備や不織布の汚染の少ない優れた品質と伸縮性を有する不織布を得ることが可能な原着複合繊維を得ることを見出し、本発明に到達した。 The inventors of the present invention have made intensive studies to solve the above problems, and found that even a solution-dyed composite fiber containing a colored pigment contains both an inorganic pigment and an organic pigment, and It is possible to obtain a nonwoven fabric with excellent quality and elasticity with less contamination of machinery and nonwoven fabric without deteriorating spinning operability by including in polyester a color tone that is specified with the system pigment. The present inventors have found that it is possible to obtain a conjugated fiber, and arrived at the present invention.
すなわち、本発明は、粘度の異なる２種のポリエステルがサイドバイサイドに接合して複合され、単繊維繊度が２．６デシテックス以下である潜在捲縮性を有する複合繊維であり、
粘度の異なる２種のポリエステルが、ポリエチレンテレフタレート同士の組合せであるか、ポリエチレンテレフタレートとエチレンテレフタレートを主たる繰り返し単位とする共重合ポリエステルとの組合せであるか、エチレンテレフタレートを主たる繰り返し単位とする共重合ポリエステル同士の組合せのいずれかであり、
粘度の異なる２種のポリエステルは、いずれにも白色顔料を含有し、
かつ粘度の異なる２種のポリエステルのいずれか一方あるいは両方に有色顔料を含有し、有色顔料が、無機系顔料と有機系顔料のいずれも含み、無機系顔料が赤色以外の顔料を含み、有機系顔料が少なくとも赤色顔料を含むことを特徴とする潜在捲縮性を有する複合繊維を要旨とするものである。
That is, the present invention relates to a conjugated fiber having a single fiber fineness of 2.6 decitex or less and having latent crimpability, wherein two kinds of polyesters having different viscosities are bonded side-by-side to form a conjugated fiber.
The two types of polyester having different viscosities are a combination of polyethylene terephthalates, a combination of polyethylene terephthalate and a copolymerized polyester having ethylene terephthalate as a main repeating unit, or a copolymerized polyester having ethylene terephthalate as a main repeating unit. is any combination of
Two types of polyesters with different viscosities both contain a white pigment,
And one or both of the two polyesters with different viscosities contains a colored pigment, the colored pigment contains both an inorganic pigment and an organic pigment, the inorganic pigment contains a pigment other than red, and the organic The gist of the present invention is a conjugate fiber having latent crimpability, wherein the pigment contains at least a red pigment.
以下、本発明について詳細に説明する。 The present invention will be described in detail below.
本発明の潜在捲縮性を有する複合繊維は、有色顔料を含み着色されてなる原着繊維であり、粘度の異なる２種のポリエステルがサイドバイサイド型あるいは偏心芯鞘型に接合して複合されている。その断面形状は、円形断面であっても、偏平や六葉、三角等の異形であっても、あるいは中空部を有するものであってもよい。 The latent crimpable conjugate fiber of the present invention is a dyed fiber that contains a color pigment and is colored, and two types of polyesters with different viscosities are bonded side-by-side or eccentric core-sheath type. . Its cross-sectional shape may be a circular cross-section, an irregular shape such as a flattened shape, a hexalobed shape, or a triangular shape, or it may have a hollow portion.
本発明の複合繊維は、単繊維繊度が２．６ｄｔｅｘ以下である。２．６ｄｔｅｘ以下とすることにより、この複合繊維からなる繊維製品は、柔軟性に優れたものとなる。なお、単繊維繊度の下限は、０．４ｄｔｅｘ程度とする。０．４ｄｔｅｘを下回ると紡糸操業性が悪化し、均質な繊維を得にくくなるためである。 The composite fiber of the present invention has a single fiber fineness of 2.6 dtex or less. By setting the density to 2.6 dtex or less, the fiber product made of this composite fiber has excellent flexibility. The lower limit of the single fiber fineness is about 0.4 dtex. This is because if it is less than 0.4 dtex, the spinning operability deteriorates, making it difficult to obtain homogeneous fibers.
本発明の複合繊維を構成する２種のポリエステルは、粘度が異なるものであるが、その極限粘度差は、０．０３以上が好ましい。粘度差が小さい場合は、良好に捲縮が顕在化しにくいためである。紡糸安定性を考慮すると、高粘度のポリエステルの極限粘度は０．６０～０．８０、低粘度ポリエステルの極限粘度は０．５２～０．７２の範囲とし、その範囲において少なくとも粘度差０．０３以上のものを選択するとよい。なお、極限粘度差の上限は０．２０以下であることが好ましい。極限粘度差が０．２０を超えると、紡糸口金直下の糸条の曲がりが大きくなり、紡糸が不安定になりやすいためである。 The two polyesters constituting the conjugate fiber of the present invention have different viscosities, and the difference in intrinsic viscosity is preferably 0.03 or more. This is because when the difference in viscosity is small, crimps are less likely to manifest well. Considering the spinning stability, the intrinsic viscosity of the high-viscosity polyester should be in the range of 0.60 to 0.80, and the intrinsic viscosity of the low-viscosity polyester should be in the range of 0.52 to 0.72, with a viscosity difference of at least 0.03 in that range. Choose any of the above. In addition, the upper limit of the intrinsic viscosity difference is preferably 0.20 or less. This is because if the intrinsic viscosity difference exceeds 0.20, the bending of the yarn immediately below the spinneret becomes large, and the spinning tends to become unstable.
２種のポリエステルの組合せとしては、高粘度ポリエチレンテレフタレート／低粘度ポリエチレンテレフタレート等のホモボリエステル同士の組合せであっても、高粘度共重合ポリエステル／低粘度共重合ポリエステル等の共重合ポリエステル同士の組合せであっても、ポリエチレンテレフタレート／共重合ポリエステル等のホモポリエステルと共重合ポリエステルの組合せであってもよい。ポリエチレンテレフタレートと共重合ポリエステルとの組合せの場合は、共重合ポリエステルを高粘度とする。 As a combination of two kinds of polyesters, a combination of homopolyesters such as high-viscosity polyethylene terephthalate/low-viscosity polyethylene terephthalate, and a combination of co-polyesters such as high-viscosity copolymer polyester/low-viscosity copolymer polyester. or a combination of a homopolyester such as polyethylene terephthalate/copolyester and a copolyester. In the case of a combination of polyethylene terephthalate and copolyester, the copolyester is made highly viscous.
具体的な組合せとしては、低粘度ポリエステル（Ａ）として、ポリエチレンテレフタレートまたはこれを主体とするポリエステル、高粘度ポリエステル（Ｂ）として、エチレンテレフタレートを主たる繰り返し単位とし、イソフタル酸とビスフェノールＡのエチレンオキシド付加物（ＢＡＥＯ）を共重合してなる共重合ポリエステルが挙げられる。 Specific combinations include, as the low-viscosity polyester (A), polyethylene terephthalate or a polyester mainly composed of this, and as the high-viscosity polyester (B), an ethylene oxide adduct of isophthalic acid and bisphenol A containing ethylene terephthalate as a main repeating unit. A copolymer polyester obtained by copolymerizing (BAEO) can be mentioned.
上記した組合せの低粘度ポリエステル（Ａ）は、ホモポリマーであるポリエチレンテレフタレート（ＰＥＴ）が好ましく用いられるが、本発明の効果を損なわない範囲であれば、イソフタル酸、アジピン酸、セバシン酸などのジカルボン酸成分、１，４－ブタンジオール、１，６－ヘキサンジオールなどのジオール成分を共重合したものでもよい。また、安定剤、蛍光剤、強化剤、難燃剤、酸化防止剤、分散剤等の改質剤が添加されたものを用いてもよい。 Polyethylene terephthalate (PET), which is a homopolymer, is preferably used as the low-viscosity polyester (A) in the combination described above. A copolymer of an acid component and a diol component such as 1,4-butanediol and 1,6-hexanediol may also be used. In addition, those to which modifiers such as stabilizers, fluorescent agents, reinforcing agents, flame retardants, antioxidants and dispersants are added may be used.
高粘度ポリエステル（Ｂ）は、エチレンテレフタレートを主たる繰り返し単位とし、イソフタル酸を０～９ｍｏｌ％、ビスフェノールＡのエチレンオキシド付加物（ＢＡＥＯ）を５～１１ｍｏｌ％共重合し、さらにイソフタル酸とＢＡＥＯの合計量が１０～１８ｍｏｌ％とした共重合ポリエステルであることが好ましい。イソフタル酸の共重合割合が９ｍｏｌ％を超えるとポリマーの融点が低下し、得られる繊維の強度が低下する傾向となり、また、ＢＡＥＯの共重合割合が５ｍｏｌ％未満であると、得られる複合繊維は十分な潜在捲縮性能を有しにくく、このような複合繊維を不織布とした場合、伸長率や伸長回復率が小さく、伸縮性能が劣るものとなる。一方、ＢＡＥＯの共重合割合が１１ｍｏｌ％を超えるとポリマーの融点が低下し、得られる繊維の強度が低下する傾向となる。ＢＡＥＯはビスフェノールＡ１ｍｏｌに対して、エチレンオキシドを２～１０ｍｏｌ付加したものが好ましく、さらには２～５ｍｏｌ付加したものが好ましい。また、イソフタル酸とＢＡＥＯの合計量が１０ｍｏｌ％未満であると、繊度が小さく細い複合繊維は潜在捲縮性能が不十分となりやすく、１８ｍｏｌ％を超えるとポリマーの融点が低下し、得られる繊維の強度が低下する傾向となる。 The high-viscosity polyester (B) has ethylene terephthalate as a main repeating unit, is copolymerized with 0 to 9 mol% of isophthalic acid, and 5 to 11 mol% of ethylene oxide adduct of bisphenol A (BAEO), and the total amount of isophthalic acid and BAEO. is preferably a copolyester having a content of 10 to 18 mol %. When the copolymerization ratio of isophthalic acid exceeds 9 mol%, the melting point of the polymer tends to decrease, and the strength of the resulting fiber tends to decrease. It is difficult to have sufficient latent crimp performance, and when such a conjugate fiber is made into a nonwoven fabric, the elongation rate and elongation recovery rate are small, and the stretchability is inferior. On the other hand, when the copolymerization ratio of BAEO exceeds 11 mol %, the melting point of the polymer tends to decrease and the strength of the resulting fiber tends to decrease. BAEO is preferably obtained by adding 2 to 10 mol, more preferably 2 to 5 mol, of ethylene oxide to 1 mol of bisphenol A. If the total amount of isophthalic acid and BAEO is less than 10 mol%, fine conjugate fibers with small fineness tend to have insufficient latent crimp performance. The strength tends to decrease.
本発明において、２種のポリエステルは、いずれも白色顔料を含む。白色顔料を含むことにより、繊維の透明感がなくなり、隠蔽性が向上し、また有色顔料のマット調に発色する傾向となる。また、繊維の重量感が増し、さらに、繊維表面に白色顔料である微粒子が部分的に露出することにもなり、表面摩擦抵抗を下げる効果も発揮し、これらの相乗効果により、この複合繊維を用いて不織布としたときに良好なドレープ感や高級感を発現することも可能となる。 In the present invention, both of the two polyesters contain a white pigment. By containing a white pigment, the transparency of the fiber is lost, the concealability is improved, and the color tends to develop in a matte tone of the colored pigment. In addition, the weight of the fiber increases, and the fine particles of the white pigment are partially exposed on the fiber surface, which also exerts the effect of lowering the surface friction resistance. It also becomes possible to develop a good drape feeling and a high-class feeling when it is used to form a nonwoven fabric.
本発明の複合繊維を構成する２種のポリエステルとして、上記した低粘度ポリエステル（Ａ）として、ポリエチレンテレフタレートまたはこれを主体とするポリエステル、高粘度ポリエステル（Ｂ）として、エチレンテレフタレートを主たる繰り返し単位とし、イソフタル酸とビスフェノールＡのエチレンオキシド付加物（ＢＡＥＯ）を共重合してなる共重合ポリエステルの組合せを採用する場合、それぞれのポリエステルが含む白色顔料は、高粘度ポリエステル（Ｂ）が含む白色顔料の比率が、低粘度ポリエステル（Ａ）が含む白色顔料の比率よりも多く含むものとする。高粘度ポリエステルに、より多くの白色顔料を含有させることによって、複合繊維の製造工程において、紡糸時の冷却固化を遅らせ、得られる未延伸糸における伸度を高くすることができ、これによって、延伸工程にて高倍率で延伸することが可能となり、より細い繊維径の繊維を安定的に生産することができる。
白色顔料の顔料は、高粘度ポリエステルである共重合ポリエステルの総質量に対する白色顔料の含有量が０．３～６質量％であることが好ましく、より好ましくは０．４～５質量％である。含有量が０．３質量％未満であると、白色顔料を含有させる効果を奏しにくく、含有量が６質量％を超えると、紡糸、延伸時に糸切れや毛羽等が発生しやすくなる。また、低粘度ポリエステルの総質量に対する白色顔料の含有量は、高粘度ポリエステルよりも少なく設定するが、多くとも０．４質量％がよい。
As the two types of polyesters constituting the composite fiber of the present invention, the low-viscosity polyester (A) is polyethylene terephthalate or a polyester mainly composed of this, and the high-viscosity polyester (B) is ethylene terephthalate as a main repeating unit, When adopting a combination of copolyesters obtained by copolymerizing ethylene oxide adducts (BAEO) of isophthalic acid and bisphenol A, the white pigment contained in each polyester has a ratio of the white pigment contained in the high-viscosity polyester (B). , the ratio of the white pigment contained in the low-viscosity polyester (A). By including a larger amount of white pigment in the high-viscosity polyester, it is possible to delay cooling and solidification during spinning in the manufacturing process of the composite fiber, and to increase the elongation of the obtained undrawn yarn. It is possible to draw at a high draw ratio in the process, and fibers with a smaller fiber diameter can be stably produced.
The content of the white pigment is preferably 0.3 to 6% by mass, more preferably 0.4 to 5% by mass, based on the total mass of the copolyester, which is a high-viscosity polyester. If the content is less than 0.3% by mass, it is difficult to obtain the effect of including the white pigment. Also, the content of the white pigment with respect to the total mass of the low-viscosity polyester is set to be less than that of the high-viscosity polyester, but is preferably 0.4% by mass at most.
本発明で使用する白色顔料は、成形、焼成等の工程を経て得られる無機材料を微粒化したものを用いるとよく、酸化チタン、酸化珪素、酸化亜鉛等の無機酸化物微粒子が代表的であり、ポリエステルとの界面における表面張力が小さく、溶融時に凝集し難いものが操業上及び品位上から好ましい。なかでも酸化チタンを用いることが好ましい。 As the white pigment used in the present invention, fine particles of an inorganic material obtained through processes such as molding and firing are preferably used, and inorganic oxide fine particles such as titanium oxide, silicon oxide, and zinc oxide are typical examples. , the surface tension at the interface with the polyester is small, and it is preferable from the point of view of operation and quality that it is difficult to agglomerate when melted. Among them, it is preferable to use titanium oxide.
白色顔料は、平均粒径が０．２～２μｍの範囲にあるものを用いるとよい。なお、平均粒径とは、セラミック微粒子をエチレングリコール溶液に微分散させた後、島津製作所社製のレーザー回折式粒度分布測定装置ＳＡＬＤ―２０００Ｊを用い、体積分布基準換算、屈折率１．７０―０．２０ｉの条件で測定するものである。平均粒径がこの範囲にある白色顔料が繊維表面に部分的に露出することにより、繊維表面の滑りがよくなる。平均粒径がこの範囲より小さいと繊維表面を改質する効果が乏しい。一方、この範囲より大きいと粒子が局部的に大きく露出してしまうため摩擦抵抗が大きくなり、さらには、粒子が局在するために、紡糸時に応力の偏りによる糸切れが発生したり、延伸時に毛羽が発生する等、操業的な問題が発生する場合がある。 A white pigment having an average particle size in the range of 0.2 to 2 μm is preferably used. In addition, the average particle size is obtained by finely dispersing the ceramic fine particles in an ethylene glycol solution, using a laser diffraction particle size distribution analyzer SALD-2000J manufactured by Shimadzu Corporation, converted to volume distribution, and having a refractive index of 1.70-. It is measured under the condition of 0.20i. By partially exposing the white pigment having an average particle size within this range on the fiber surface, the fiber surface becomes smoother. If the average particle size is smaller than this range, the effect of modifying the fiber surface is poor. On the other hand, if it is larger than this range, the particles are locally exposed to a large extent, resulting in increased frictional resistance. Furthermore, since the particles are localized, yarn breakage may occur due to uneven stress during spinning, or during drawing. Operational problems such as fluffing may occur.
白色顔料の密度は３．５ｇ／ｃｍ３以上のものを用いるとよい。密度が３．５ｇ／ｃｍ３より小さいと、繊維の密度を増す効果が乏しく、不織布としたときに良好なドレープ性や高級感を発現しにくい傾向となり、一方、密度を増すために多量に含有させ過ぎた場合は紡糸時に糸切れが発生したり、延伸、加工時に毛羽が発生する等、操業性に問題があり、好ましくない。白色顔料の密度の上限は特に限定されるものではないが、凝集によるトラブルや操業性を考慮すると、５ｇ／ｃｍ３程度がよい。 A white pigment having a density of 3.5 g/cm 3 or more is preferably used. If the density is less than 3.5 g/cm 3 , the effect of increasing the density of the fibers is poor, and it tends to be difficult to develop a good drape property and a luxurious feeling when made into a nonwoven fabric. If it is excessively applied, it is not preferable because it causes a problem in workability such as yarn breakage during spinning or generation of fluff during drawing and processing. Although the upper limit of the density of the white pigment is not particularly limited, it is preferably about 5 g/cm 3 in consideration of problems due to aggregation and workability.
白色顔料は、ポリエステルの重合時あるいは紡糸時の溶融段階で添加することが可能であるが、凝集を防ぎ、より均一に分散させることを考慮すると、重合時に添加することが好ましい。 The white pigment can be added at the time of polymerizing the polyester or at the melting stage during spinning, but is preferably added at the time of polymerization in order to prevent agglomeration and more uniformly disperse the polyester.
本発明の複合繊維は、所望の色を付与するために有色顔料を含有する。本発明において有色顔料とは、白色顔料以外の色を呈する顔料をいう。有色顔料は、粘度の異なるポリエステルのいずれか一方、あるいは両方に含有する場合のいずれでもよいが、低粘度ポリエステルのみに有色顔料を添加することが好ましい。これは有色顔料を低粘度ポリエステルに添加することにより見かけの溶融粘度が高くなり、低粘度ポリエステルと高粘度ポリエステルとの見かけの溶融粘度差が小さくなることにより、紡糸性が向上するためである。
潜在捲縮性を有する複合繊維の性質上、一方が有色顔料を含有するだけでも着色の効果が十分に得られるため、両方に有色顔料を含有させずともよい。
The bicomponent fibers of the present invention contain colored pigments to impart the desired color. In the present invention, the colored pigment refers to a pigment exhibiting a color other than a white pigment. The colored pigment may be contained in one or both of the polyesters having different viscosities, but it is preferable to add the colored pigment only to the low-viscosity polyester. This is because the addition of the colored pigment to the low-viscosity polyester increases the apparent melt viscosity and reduces the apparent melt-viscosity difference between the low-viscosity polyester and the high-viscosity polyester, thereby improving spinnability.
Due to the property of conjugate fibers having latent crimpability, a sufficient coloring effect can be obtained even if only one of them contains a colored pigment.
本発明においては、有色顔料として、無機系顔料と有機系顔料のいずれも含まれている必要があり、無機系顔料としては赤色以外の色を呈する顔料を含み、有機系顔料としては少なくとも赤色を呈する顔料を含む。有機系顔料は一般的に、無機系顔料よりも含有させるポリマーであるポリエステルとの馴染みがよいため、有色顔料の粒子がポリエステルから脱落し難くなる。そのため、機械設備の汚染や、機械設備に脱落し堆積した有色顔料が、原料繊維や、これを用いた不織布などの製品に混入してしまうなどの、品質面での問題を解決することができる。また、有機系顔料は、調色能力が高く、発色が良好であるため、ポリエステルへの含有量を少なくすることができ、さらには、ポリエステルとのなじみが良く、柔軟性に優れるため、繊維製造時に、良好に延伸が可能となり、延伸時に脱落が生じにくい。脱落や、脱落した顔料が混入した場合に、顔料の色が赤色の場合、特に目立つため、品質面での問題が生じやすいため、少なくとも赤色顔料は、無機系顔料ではなく、有機系顔料として含有させる。なお、赤色以外の顔料としても、当然ながら有機系顔料を用いることは好ましい。 In the present invention, the colored pigments must contain both inorganic pigments and organic pigments. The inorganic pigments include pigments exhibiting colors other than red, and the organic pigments include at least red pigments. Contains pigments that give Since organic pigments generally have better compatibility with polyester, which is a polymer to be contained, than inorganic pigments, particles of colored pigments are less likely to come off from polyester. Therefore, it is possible to solve quality problems such as contamination of machinery and equipment, and colored pigments that fall off and accumulate on machinery and equipment are mixed into raw fibers and products such as nonwoven fabrics using this. . In addition, organic pigments have high toning ability and good color development, so the content in polyester can be reduced. In some cases, the film can be stretched satisfactorily and is less likely to come off during stretching. If the color of the pigment falls off or is mixed with the red pigment, it is particularly conspicuous, and quality problems are likely to occur. Therefore, at least the red pigment is included as an organic pigment, not an inorganic pigment. Let As a pigment other than red, naturally, it is preferable to use an organic pigment.
有機系顔料の種類としては、フタロシアニン系、ペリレン系、イソインドリノン系、アゾ系、アンスラキノン系等が挙げられる。 Types of organic pigments include phthalocyanine-based, perylene-based, isoindolinone-based, azo-based, and anthraquinone-based pigments.
有機系顔料は繊維全体に対して０．００１５～０．３０質量％含まれていることが好ましく、さらには０．００２０～０．２５質量％含まれていることが好ましい。含有量が０．００１５質量％未満であると、所望する十分な発色が得られにくくなる。一方、含有量が０．３０質量％を超えるとコスト的に不利になるため好ましくない。 The organic pigment is preferably contained in an amount of 0.0015 to 0.30% by mass, more preferably 0.0020 to 0.25% by mass, based on the entire fiber. If the content is less than 0.0015% by mass, it becomes difficult to obtain the desired and sufficient color development. On the other hand, if the content exceeds 0.30% by mass, it is disadvantageous in terms of cost, which is not preferable.
また有色顔料として、赤以外の色を呈する顔料は、本発明の効果を損なわない範囲で無機系顔料を含有させる。有機系顔料は耐熱性に劣るため色調が安定しにくいため、特に色合いの調整に用いられるカーボンブラックは、取扱い性が良好であるため、無機系顔料として好ましく用いる。無機系の有色顔料としては、カーボンブラック以外として、酸化鉄、酸化鉄亜鉛、群青等が挙げられる。目的とする発色を得るためには、色調の安定性という観点からも、これらの無機系顔料である有色顔料を適宜選定し、ブレンドして使用する。なお、無機系顔料は、上記したようにポリエステルとの馴染が有機系顔料と比較して劣るため、凝集しやすい傾向にあるが、有機系顔料と無機系顔料とを併用して用いることにより顔料同士の凝集を抑制することもできる。 In addition, as colored pigments, pigments exhibiting colors other than red contain inorganic pigments within a range that does not impair the effects of the present invention. Since organic pigments are inferior in heat resistance and color tone is difficult to stabilize, carbon black, which is particularly used for color adjustment, is preferably used as an inorganic pigment because it is easy to handle. Inorganic colored pigments other than carbon black include iron oxide, zinc iron oxide, ultramarine blue, and the like. In order to obtain the desired color development, from the viewpoint of color tone stability, these inorganic colored pigments are appropriately selected and blended for use. As described above, inorganic pigments are less compatible with polyester than organic pigments, so they tend to aggregate easily. Aggregation between them can also be suppressed.
有色顔料の添加方法については、ポリエステルの重合段階あるいは複合繊維の製糸段階のいずれかの過程で添加すればよく、特に限定はしないが、設備の汚染、制御等取扱性から製糸段階に添加するのが好ましい。添加方法としては、マスターバッチ方式、リキッドカラー方式等が挙げられるが、溶融紡糸時の安定性、有色顔料の取扱性等より、マスターバッチ方式が好ましい。なお、マスターバッチ方式を採用する場合、原料ペレットの段階で計量混合して溶融紡糸する方法、別々に溶融させたポリマーを計量混合して紡糸する方法等が挙げられるが、いずれの方法で行ってもよい。 Regarding the method of adding the colored pigment, it may be added in either the polymerization stage of the polyester or the spinning stage of the composite fiber, and is not particularly limited. is preferred. Examples of the method of addition include a masterbatch system and a liquid color system, but the masterbatch system is preferred in terms of stability during melt spinning and handleability of colored pigments. In the case of adopting the masterbatch method, there are a method of weighing and mixing at the stage of raw material pellets and melt spinning, and a method of weighing and mixing separately melted polymers and spinning. good too.
次に、本発明の複合繊維の製造方法について説明する。まず、所定の白色顔料あるいは有色顔料を含んでなる高粘度ポリエステルおよび低粘度ポリエステルを準備し、通常の複合紡糸装置により複合紡糸し、得られた未延伸糸に延伸、熱処理を施す。本発明においては、未延伸糸の繊度は特に限定されるものではなく、長繊維を得る場合には、３０～２００ｄｔｅｘの糸条とし、紡績糸用や不織布用の短繊維を得る場合には、５０～１００万デニールの糸束に集束してから延伸を行うことが好ましい。このとき、熱処理時の条件としては、潜在捲縮を後工程の熱処理で顕在化させるため、高温で熱処理を行うことは好ましくなく、１００～１６０℃で熱処理することが好ましい。また、長繊維を得る場合は、延伸、熱処理後巻き取り機で巻き取る。紡績糸用や不織布用の短繊維を得る場合には、延伸、熱処理後、８～１８個／２５ｍｍ程度の機械捲縮を付与し、仕上げ油剤を付与した後、糸条束を切断して短繊維とする。 Next, the method for producing the composite fiber of the present invention will be described. First, high-viscosity polyester and low-viscosity polyester containing a predetermined white pigment or colored pigment are prepared, conjugate-spun by a normal conjugate-spinning apparatus, and the resulting undrawn yarn is drawn and heat-treated. In the present invention, the fineness of the undrawn yarn is not particularly limited. It is preferable to draw the yarn after bundling it into a yarn bundle of 500,000 to 1,000,000 denier. At this time, as a condition for the heat treatment, it is not preferable to perform the heat treatment at a high temperature, and it is preferable to perform the heat treatment at 100 to 160° C. because the latent crimps are revealed by the heat treatment in the subsequent step. Further, when obtaining a long fiber, it is wound with a winder after drawing and heat treatment. When obtaining staple fibers for spun yarn or non-woven fabric, after drawing and heat treatment, mechanical crimps of about 8 to 18 crimps/25 mm are applied, a finishing oil is applied, and the yarn bundle is cut and shortened. fiber.
本発明の複合繊維は、熱処理によって潜在捲縮性能を顕在化してスパイラル状の立体捲縮を発現する。潜在捲縮性能を良好に顕在化させるためには、弛緩状態で熱処理することが好ましい。熱処理条件としては、例えば、１６０～１９０℃に設定した熱風乾燥機中にて３０秒～２分間程度処理することにより良好に立体捲縮を発現させることができる。 The conjugate fiber of the present invention reveals the latent crimping performance by heat treatment and develops a spiral three-dimensional crimp. In order to satisfactorily reveal the latent crimp performance, the heat treatment is preferably performed in a relaxed state. As for the heat treatment conditions, for example, three-dimensional crimps can be satisfactorily developed by treating for about 30 seconds to 2 minutes in a hot air dryer set at 160 to 190°C.
本発明の不織布は、上記した本発明の複合繊維により構成されるものであり、本発明の複合繊維が有する特徴が活かされ、伸縮性、嵩高性により優れた不織布である。本発明の不織布は、本発明の複合繊維のみからなるものとすることが好ましいが、他の繊維を含有してもよく、この場合は、本発明の複合繊維の割合を７０質量％以上とすることが好ましい。 The nonwoven fabric of the present invention is composed of the above-described conjugate fiber of the present invention, and is a nonwoven fabric that is excellent in stretchability and bulkiness by making use of the characteristics of the conjugate fiber of the present invention. The nonwoven fabric of the present invention preferably consists of only the conjugate fiber of the present invention, but may contain other fibers. In this case, the ratio of the conjugate fiber of the present invention is 70% by mass or more. is preferred.
本発明の不織布は、構成繊維同士が三次元的に交絡することにより不織布としての形状を保持しているものが好ましい。この構成繊維同士が三次元的に交絡してなる不織布は、多数の繊維が堆積してなる不織ウエブに高圧液体流を噴射することによって構成繊維同士を三次元的に交絡させることにより得られる。この構成繊維同士の三次元的な交絡により、形態保持性と実用上十分な強力そして柔軟性が不織布に具備される。不織布の目付は、用途に応じて適宜選択すればよいが、２０～２００ｇ／ｍ２程度がよい。 The nonwoven fabric of the present invention preferably retains its shape as a nonwoven fabric by three-dimensionally entangling the constituent fibers. The nonwoven fabric in which the constituent fibers are three-dimensionally entangled is obtained by three-dimensionally entangling the constituent fibers by injecting a high-pressure liquid flow onto a nonwoven web formed by stacking a large number of fibers. . Due to the three-dimensional entanglement of the constituent fibers, the nonwoven fabric is endowed with shape retention, practically sufficient strength and flexibility. The basis weight of the non-woven fabric may be appropriately selected depending on the application, and is preferably about 20 to 200 g/m 2 .
次に、本発明の不織布の製造方法の一例を挙げる。不織布の構成繊維となる繊維（本発明の複合繊維）を、カード機等を用いてカーディングしてカードウエブを作製し、得られたカードウエブに高圧液体流処理を施して構成繊維同士を三次元的に交絡させて一体化し、不織布を得る。本発明の複合繊維の潜在捲縮性能を発現させるには、高圧液体流処理により不織布に含まれる液体を除去するための乾燥工程において、乾燥熱処理を施し、液体除去と同時に潜在捲縮性能を発現させてスパイラル状の立体捲縮を顕在化させるとよい。 Next, an example of the manufacturing method of the nonwoven fabric of this invention is given. A carded web is produced by carding the fibers that will be the constituent fibers of the nonwoven fabric (composite fibers of the present invention) using a carding machine or the like, and the resulting carded web is subjected to a high-pressure liquid flow treatment to tertiary separate the constituent fibers. They are originally entangled and integrated to obtain a nonwoven fabric. In order to develop the latent crimp performance of the conjugate fiber of the present invention, dry heat treatment is performed in the drying process for removing the liquid contained in the nonwoven fabric by high-pressure liquid flow treatment, and the latent crimp performance is developed at the same time as the liquid is removed. It is preferable to make the spiral three-dimensional crimp visible.
本発明の複合繊維は、優れた潜在捲縮能を有しており、製糸性よく得ることができ、品質、伸縮性に優れた不織布を得ることが可能である。 The conjugate fiber of the present invention has excellent latent crimpability, can be obtained with good spinnability, and can be used to obtain a nonwoven fabric with excellent quality and stretchability.
本発明によれば、繊維製造における延伸工程および不織布加工工程において、白色顔料以外の有色顔料に由来した機台汚れが生じにくく、優れた潜在捲縮性を発揮し、品位の高い伸縮性に優れた繊維製品を得ることができる。 According to the present invention, in the stretching process and the non-woven fabric processing process in the production of fibers, it is difficult for machine base stains due to colored pigments other than white pigments to occur, exhibits excellent latent crimpability, and has excellent stretchability with high quality. It is possible to obtain a textile product.
（１）極限粘度〔η〕
フェノールとテトラクロロエタンとの等重量混合物を溶媒とし、２０℃で測定した。
（２）製糸性
孔数１０３８孔の丸断面複合紡糸ノズルを用い、８錘で７日間紡糸し、１日当たりの糸切れ回数が５回以下を合格（○）とし、糸切れ回数が５回を越えるものを不合格（×）とした。
（３）不織布の品位
目付８０ｇ／ｍ２、幅２ｍ、長さ３０００ｍの不織布を製造し、１ｍｍ２以上の、脱落した有色顔料に由来する濃色異物欠点と、繊維膠着による欠点を目視で確認した。欠点数が５ケ／１００ｍ以下を合格（○）、５ケ／１００ｍを超えるものを不合格（×）とした。
（４）不織布の伸縮性（伸長回復率）
２５ｍｍ（機械方向と直交する方向）×１５０ｍｍ（機械方向）の試料片を５枚作製し、定速伸長形引張試験機を用い、つかみ間隔１００ｍｍとして、機械方向に１００ｍｍ／分の速度でつかみ間隔が１５０ｍｍとなるまで伸ばし、この状態で１分間保持した後、１００ｍｍ／分の速度で元に戻し、３分間放置後、再び１００ｍｍ／分の速度で伸ばし、荷重がかかるまでの伸びＡを測定し、下記式により、それぞれの伸長回復率を算出し、その平均値を求めた。
伸長回復率％＝〔（５０－Ａ）／５０〕×１００
なお、伸長回復率が６０％以上のものを合格とした。
(1) Intrinsic viscosity [η]
A mixture of equal weights of phenol and tetrachloroethane was used as a solvent and measured at 20°C.
(2) Spinning performance Using a round cross-section composite spinning nozzle with 1038 holes, spinning for 7 days with 8 spindles, the number of yarn breakages per day of 5 times or less was evaluated as a pass (○), and the number of yarn breakages was 5 times. Those exceeding the value were regarded as disqualified (x).
(3) Quality of non-woven fabric A non-woven fabric having a basis weight of 80 g/m 2 , a width of 2 m and a length of 3000 m is produced, and a dark-colored foreign matter defect of 1 mm 2 or more derived from the fallen colored pigment and a defect due to fiber adhesion are visually confirmed. did. A defect number of 5/100 m or less was evaluated as a pass (○), and a defect number exceeding 5/100 m was evaluated as a failure (x).
(4) Elasticity of nonwoven fabric (elongation recovery rate)
Five specimens of 25 mm (direction perpendicular to the machine direction) x 150 mm (machine direction) are prepared, and a constant-speed elongation type tensile tester is used, with a grip interval of 100 mm and a speed of 100 mm / min in the machine direction. After holding this state for 1 minute, it was returned to its original state at a speed of 100 mm/min, left for 3 minutes, stretched again at a speed of 100 mm/min, and the elongation A until a load was applied was measured. , the elongation recovery rate of each was calculated by the following formula, and the average value was obtained.
Elongation recovery rate % = [(50-A) / 50] × 100
In addition, the thing with the elongation recovery rate of 60% or more was made into the pass.
実施例１
低粘度ポリエステルとして、白色顔料である密度３．９ｇ／ｃｍ３、平均粒径０．７μｍの二酸化チタン微粒子を重合時に添加し、二酸化チタン微粒子の含有量が０．３質量％である〔η〕０．６９のポリエチレンテレフタレートを用い、そして、〔η〕０．７４のポリエチレンテレフタレートをベースポリマーとし、有色顔料として、有機系顔料（赤色、黄色）、無機系顔料（カーボンブラック）を練り込んだマスターバッチをポリエステル（Ａ）中の有色顔料濃度が０．１質量％となるように混合した。
Example 1
As the low-viscosity polyester, fine particles of titanium dioxide, which is a white pigment and has a density of 3.9 g/cm 3 and an average particle diameter of 0.7 μm, are added during polymerization, and the content of the fine particles of titanium dioxide is 0.3% by mass [η]. Using polyethylene terephthalate of 0.69 and using polyethylene terephthalate of [η] 0.74 as a base polymer, a master kneaded with organic pigments (red, yellow) and inorganic pigments (carbon black) as colored pigments. The batch was mixed so that the colored pigment concentration in polyester (A) was 0.1% by weight.
高粘度ポリエステルとして、エチレンテレフタレート単位を主たる繰り返し単位とし、イソフタル酸４ｍｏｌ％、ＢＡＥＯ７ｍｏｌ％共重合した共重合ポリエステルであって、白色顔料である密度３．９ｇ／ｃｍ３、平均粒径０．７μｍの二酸化チタン微粒子を２．０質量％含有する〔η〕０．７８の共重合ポリエステルを用いた。 The high-viscosity polyester is a copolyester obtained by copolymerizing 4 mol % isophthalic acid and 7 mol % BAEO with ethylene terephthalate units as main repeating units, and is a white pigment having a density of 3.9 g/cm 3 and an average particle diameter of 0.7 μm. Copolyester [η] 0.78 containing 2.0% by mass of titanium dioxide fine particles was used.
低粘度ポリエステルと高粘度ポリエステルとを、複合質量比を１：１として複合溶融紡糸装置を用いて、孔数１０３８孔の丸断面口金孔から、紡糸温度３００℃、引取速度９００ｍ／分、吐出量３８６ｇ／分でサイドバイサイド型複合繊維を紡糸した。得られた未延伸糸を、延伸温度７３℃、延伸倍率３．６０倍に延伸し、次いで１４０℃で緊張熱処理を行い、スタッフィングボックスで機械捲縮（捲縮数１２個／２５ｍｍ）を付与した後、仕上げ油剤を付与し、繊維長４４ｍｍに切断し、単糸繊度１．３ｄｔｅｘの複合繊維を得た。複合繊維中の有色顔料の含有量は０．０５質量％であり、複合繊維中の有機系顔料の含有量は０．０４８質量％であった。得られた複合繊維のみを用い、カード機にて開繊し、不織ウェブを作製した。この不織ウェブをネットコンベアー上に供給し、孔径０．１２ｍｍ、孔間隔１．０ｍｍの噴射孔を複数個有する噴射ノズルを３段階に設け、前段２０ｋｇ／ｃｍ２、中段４０ｋｇ／ｃｍ２、後段１００ｋｇ／ｃｍ２の水圧で不織ウェブに高圧液体流処理を施しウェブの交絡化を行った。次いで１８０℃×１分の乾熱処理を行って潜在捲縮性能を顕在化させ、スパイラル状の立体捲縮を発現させ、目付８０ｇ／ｍ２の不織布を得た。 A low-viscosity polyester and a high-viscosity polyester are mixed at a composite mass ratio of 1:1, and are spun at a spinning temperature of 300° C., a take-up speed of 900 m/min, and a discharge rate from a round-section spinneret with 1,038 holes using a composite melt spinning apparatus. A side-by-side bicomponent fiber was spun at 386 g/min. The obtained undrawn yarn was drawn at a draw temperature of 73° C. and a draw ratio of 3.60 times, then subjected to tension heat treatment at 140° C., and mechanically crimped in a stuffing box (12 crimps/25 mm). After that, a finishing oil was applied, and the fibers were cut into fibers of 44 mm in length to obtain composite fibers with a single filament fineness of 1.3 dtex. The content of the colored pigment in the composite fiber was 0.05% by mass, and the content of the organic pigment in the composite fiber was 0.048% by mass. Using only the obtained conjugate fiber, it was opened by a carding machine to prepare a nonwoven web. This nonwoven web is supplied onto a net conveyor, and injection nozzles having a plurality of injection holes with a hole diameter of 0.12 mm and a hole interval of 1.0 mm are provided in three stages: front stage 20 kg/cm 2 , middle stage 40 kg/cm 2 , rear stage. The nonwoven web was subjected to high pressure liquid flow treatment at a water pressure of 100 kg/cm 2 to entangle the web. Next, a dry heat treatment was performed at 180° C. for 1 minute to reveal the latent crimp performance and develop spiral three-dimensional crimps, thereby obtaining a nonwoven fabric having a basis weight of 80 g/m 2 .
実施例２～５
有色顔料濃度が表１に示す値となるようにマスターバッチを添加した以外は、実施例１と同様に行った。
Examples 2-5
The procedure of Example 1 was repeated except that the masterbatch was added so that the concentration of the colored pigment would be the value shown in Table 1.
実施例６～７
高粘度ポリエステルである共重合ポリエステルの共重合量が表１に示す値となるように変更した以外は、実施例１と同様に行った。
Examples 6-7
The procedure was carried out in the same manner as in Example 1, except that the copolymerization amount of the copolyester, which is a high-viscosity polyester, was changed to the value shown in Table 1.
実施例８～９、比較例１
複合繊維の単糸繊度を表１に示す値となるように変更した以外は、実施例１と同様に行った。
Examples 8-9, Comparative Example 1
The same procedure as in Example 1 was carried out, except that the single filament fineness of the composite fiber was changed to the value shown in Table 1.
比較例２～３
低粘度ポリエステルに添加する有色顔料の種類を無機系（赤色、黄色、カーボンブラック）に変更し、有色顔料濃度を表１に示す値となるようにマスターバッチを添加した以外は、実施例１と同様に行った。
Comparative Examples 2-3
Example 1 except that the type of colored pigment added to the low-viscosity polyester was changed to inorganic (red, yellow, carbon black), and the masterbatch was added so that the colored pigment concentration was the value shown in Table 1. did the same.
上記の実施例１～９、比較例１～３で得られた複合繊維の製糸性と、該複合繊維を不織布としたときの品位、伸縮性の評価結果を表１に示す。
表１から明らかなように、実施例１～９では製糸性よく複合繊維を得ることができ、得られた複合繊維から作製した不織布は、品位、伸縮性のいずれにおいても優れるものであった。
Table 1 shows the spinnability of the composite fibers obtained in Examples 1 to 9 and Comparative Examples 1 to 3, and the evaluation results of the quality and stretchability when the composite fibers were made into nonwoven fabrics.
As is clear from Table 1, in Examples 1 to 9, conjugated fibers could be obtained with good spinnability, and the nonwoven fabrics produced from the obtained conjugated fibers were excellent in both quality and stretchability.
比較例１は、単糸繊度が太すぎたため、風合いに劣るものとなった。 In Comparative Example 1, the single filament fineness was too thick, so the texture was poor.
比較例２～３は、ポリエステル（Ａ）中の有色顔料を無機系のみに変更したため、不織布に多くの濃色異物欠点が発生し、品位に劣るものとなった。 In Comparative Examples 2 and 3, since the colored pigment in the polyester (A) was changed to only an inorganic pigment, many dark-colored foreign matter defects occurred in the nonwoven fabric, resulting in inferior quality.
Claims (6)
粘度の異なる２種のポリエステルが、ポリエチレンテレフタレート同士の組合せであるか、ポリエチレンテレフタレートとエチレンテレフタレートを主たる繰り返し単位とする共重合ポリエステルとの組合せであるか、エチレンテレフタレートを主たる繰り返し単位とする共重合ポリエステル同士の組合せのいずれかであり、
粘度の異なる２種のポリエステルは、いずれにも白色顔料を含有し、
かつ粘度の異なる２種のポリエステルのいずれか一方あるいは両方に有色顔料を含有し、
有色顔料が、無機系顔料と有機系顔料のいずれも含み、無機系顔料が赤色以外の顔料を含み、有機系顔料が少なくとも赤色顔料を含むことを特徴とする潜在捲縮性を有する複合繊維。 A conjugated fiber having a single fiber fineness of 2.6 decitex or less and having latent crimpability, wherein two types of polyesters having different viscosities are bonded and combined in a side-by-side type or eccentric sheath-core type,
The two types of polyester having different viscosities are a combination of polyethylene terephthalates, a combination of polyethylene terephthalate and a copolymerized polyester having ethylene terephthalate as a main repeating unit, or a copolymerized polyester having ethylene terephthalate as a main repeating unit. is any combination of
Two types of polyesters with different viscosities both contain a white pigment,
and containing a colored pigment in either one or both of two polyesters with different viscosities,
A latent crimpable conjugate fiber, wherein the colored pigment contains both an inorganic pigment and an organic pigment, the inorganic pigment contains a pigment other than red, and the organic pigment contains at least a red pigment.
A nonwoven fabric comprising the latent crimpable conjugate fiber according to any one of claims 1 to 5.
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