JP2018184674A - Conjugated fiber, fabric, method for producing fiber structure, and clothing - Google Patents
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Abstract
Description
本発明は、複合繊維、布帛および繊維構造体の製造方法ならびに衣類に関する。 The present invention relates to a composite fiber, a method for producing a fabric and a fiber structure, and a garment.
従来、ポリエーテルアミドブロック樹脂を用いた繊維や複合繊維が各種提案されている。これらの繊維は、ポリエーテルアミドブロック樹脂の高い吸湿性を生かし、布帛に接触冷感性や帯電防止性を付与する目的で用いられている。
例えば、特許文献１は、ポリエーテルアミドブロック樹脂を含有する繊維とすることにより、優れた接触冷感を得ることが記載されている。
また特許文献２は、ポリエーテルアミドブロック樹脂からなる繊維を有する帯電性防止性繊維構造物とすることにより、繊維の物性や風合いを損なうことなく優れた帯電防止効果を得ることが記載されている。
Conventionally, various fibers and composite fibers using polyetheramide block resins have been proposed. These fibers are used for the purpose of imparting contact cooling sensation and antistatic properties to the fabric by taking advantage of the high hygroscopicity of the polyetheramide block resin.
For example,
しかしながら、特許文献１および特許文献２は、いずれも、ポリエーテルアミドブロック樹脂の樹脂ペレットを用い、溶融紡糸法にて製糸を行うと記載されているのみで、具体的な繊維化の方法は開示されていない。実際に、ポリエーテルアミドブロック樹脂を単独で溶融紡糸した場合、得られた繊維は、容易に膠着状態となるため、織物作製の整経の際や編立の際に、クリールからの解舒がスムーズにできず、衣類等に用いる布帛用の繊維としては、工業的に用いることができないものであった。
However,
したがって、本発明は上記の問題を解決し、衣類等に用いる布帛用の繊維として、実質的にポリエーテルアミドブロック樹脂単独からなる繊維を、工業的に用いることができるための繊維を得ることを目的とする。 Therefore, the present invention solves the above-mentioned problems, and obtains a fiber that can be used industrially as a fiber for fabrics and the like, which is substantially composed of a polyetheramide block resin alone. Objective.
上記目的を達成するため、本発明は、式（１）からなるポリエーテルブロックアミド共重合樹脂を芯成分とし、熱水可溶性樹脂を鞘成分とする複合繊維を第一の要旨とする。
また、熱水可溶性樹脂がテレフタル酸を主とする酸成分とエチレングリコールを主とするジオール成分からなる共重合ポリエステルであり、前記酸成分の８〜１５ｍｏｌ％がスルホイソフタル酸ナトリウム誘導体、前記酸成分の１０〜４０ｍｏｌ％がイソフタル酸またはその誘導体、前記ジオール成分の８〜２５ｍｏｌ％がジエチレングリコールである上記複合繊維を第二の要旨とする。 The hot water-soluble resin is a copolyester composed of an acid component mainly composed of terephthalic acid and a diol component mainly composed of ethylene glycol, and 8 to 15 mol% of the acid component is a sodium sulfoisophthalate derivative and the acid component. The above-mentioned composite fiber in which 10 to 40 mol% is isophthalic acid or a derivative thereof and 8 to 25 mol% of the diol component is diethylene glycol is a second gist.
更に、熱水可溶性樹脂がエチレンとビニルアルコールとの共重合樹脂である上記複合繊維を第三の要旨とする。 Furthermore, a third aspect is the above composite fiber in which the hot water soluble resin is a copolymer resin of ethylene and vinyl alcohol.
上記複合繊維を少なくとも２０質量％含む布帛であることを第四の要旨とする。 A fourth gist is a fabric containing at least 20% by mass of the composite fiber.
また上記複合繊維を含む布帛を６０℃以上の水で処理して熱水可溶性樹脂を溶解除去することを特徴とする、ポリエーテルブロックアミド共重合樹脂単独糸を含む繊維構造体の製造方法を第五の要旨とし、得られた繊維構造体を含む衣類を第六の要旨とする。 A method for producing a fiber structure comprising a polyether block amide copolymer resin single yarn is characterized in that the fabric containing the composite fiber is treated with water at 60 ° C. or higher to dissolve and remove the hot water-soluble resin. The fifth aspect is a garment including the obtained fiber structure.
本発明の複合繊維によれば、膠着なく、製編織時に解舒できるため、後工程で、熱水可溶性樹脂を除去することにより、実質的にポリエーテルアミドブロック樹脂単独糸を含む繊維構造体を工業的に製造することができる。 According to the conjugate fiber of the present invention, it can be unwound at the time of weaving and weaving without sticking. Therefore, by removing the hot water-soluble resin in a subsequent step, a fiber structure substantially containing a single polyetheramide block resin yarn is obtained. It can be manufactured industrially.
また、本発明の複合繊維を含む布帛を熱水で処理することにより得られた繊維構造物および繊維構造物を含む衣類は、優れた接触冷感性や帯電防止性を有する。 Moreover, the clothing containing the fiber structure obtained by processing the fabric containing the conjugate fiber of the present invention with hot water and the fiber structure has excellent contact cooling and antistatic properties.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明は、ポリエーテルブロックアミド共重合樹脂を芯成分とし、熱水可溶性樹脂を鞘成分とする複合繊維である。 The present invention is a composite fiber having a polyether block amide copolymer resin as a core component and a hot water-soluble resin as a sheath component.
まず、本発明におけるポリエーテルブロックアミド共重合樹脂は、ジカルボン酸末端を有するポリアミド単位とポリエーテルジオール単位との共重縮合で得られる共重合物であり、以下の式１で示される。
First, the polyether block amide copolymer resin in the present invention is a copolymer obtained by copolycondensation of a polyamide unit having a dicarboxylic acid terminal and a polyether diol unit, and is represented by the following
（式中、ＰＡはポリアミド単位（ハードセグメント）、ＰＥはポリエーテル単位（ソフトセグメント）、ｎは繰り返し単位を示す。)
(In the formula, PA represents a polyamide unit (hard segment), PE represents a polyether unit (soft segment), and n represents a repeating unit.)
ポリアミド単位としては、ポリアミド６、ポリアミド６，６、ポリアミド１２等が好適に用いられる。 As the polyamide unit, polyamide 6, polyamide 6, 6, polyamide 12 or the like is preferably used.
ポリエーテル単位としては、ポエチレングリコール、ポリテトラメチレングリコール等が好適に用いられる。 As the polyether unit, polyethylene glycol, polytetramethylene glycol and the like are preferably used.
また、「ポリアミド単位」と「ポリエーテル単位」の質量比は好ましくは９９：１〜５：９５、より好ましくは８０：２０〜１０：９０であり、この範囲であれば有効に用いることができる。 The mass ratio of “polyamide unit” and “polyether unit” is preferably 99: 1 to 5:95, more preferably 80:20 to 10:90, and can be effectively used within this range. .
市販されているものとしては、アルケマ社製のペバックス（Ｐｅｂａｘ（登録商標））等が挙げられ、中でも、ペバックス（Ｐｅｂａｘ（登録商標））ＭＶ１０７４（商品名）、ＭＨ１６５７（商品名）を用いると特に良好な制電性が得られる。 Examples of commercially available products include Pebax (Pebax (registered trademark)) manufactured by Arkema, Inc. Among them, Pebax (Pebax (registered trademark)) MV1074 (trade name) and MH1657 (trade name) are particularly used. Good antistatic properties can be obtained.
ポリエーテルブロックアミド共重合樹脂は、一般に耐衝撃性が強い樹脂として知られており、スポーツ用途の靴底等に使用されている。耐薬品性は、アルコールや一般的な有機溶媒に対しては耐性があるが、強酸および強アルカリに弱く、例えば濃硫酸や水酸化ナトリウム水溶液に溶解する。 The polyether block amide copolymer resin is generally known as a resin having high impact resistance, and is used for a shoe sole for sports use. The chemical resistance is resistant to alcohols and general organic solvents, but is weak against strong acids and strong alkalis, for example, dissolved in concentrated sulfuric acid or sodium hydroxide aqueous solution.
次に、熱水可溶性樹脂としては、共重合ポリエステル樹脂、エチレン−ビニルアルコール共重合樹脂が好適に挙げられる。 Next, preferred examples of the hot water-soluble resin include copolymer polyester resins and ethylene-vinyl alcohol copolymer resins.
本発明において、熱水可溶性樹脂は、熱水により溶解する樹脂であり、８０℃以上の水で溶解する樹脂が好ましく、より好ましくは、６０℃以上の水で溶解する樹脂である。 In the present invention, the hot water-soluble resin is a resin that dissolves in hot water, preferably a resin that dissolves in water at 80 ° C. or higher, and more preferably a resin that dissolves in water at 60 ° C. or higher.
本発明における共重合ポリエステル樹脂は、テレフタル酸を主とする酸成分とエチレングリコールを主とするジオール成分からなる。 The copolyester resin in the present invention comprises an acid component mainly composed of terephthalic acid and a diol component mainly composed of ethylene glycol.
本発明における共重合ポリエステル樹脂の酸成分は、８〜１５ｍｏｌ％がスルホイソフタル酸ナトリウム誘導体である。より好ましくは、９〜１２ｍｏｌ％である。
酸成分のスルホイソフタル酸ナトリウム誘導体の比率が８ｍｏｌ％未満であると、熱水可溶性が低下する傾向がある。１５ｍｏｌ％を超えると、反応性が低下するとともに重合度が上がらず、樹脂強度が著しく低下し、繊維として用いることが難しいおそれがある。
8-15 mol% of the acid component of the copolyester resin in the present invention is a sodium sulfoisophthalate derivative. More preferably, it is 9-12 mol%.
When the ratio of the sodium sulfoisophthalate derivative of the acid component is less than 8 mol%, the hot water solubility tends to decrease. When it exceeds 15 mol%, the reactivity is lowered and the degree of polymerization is not increased, the resin strength is significantly lowered, and it may be difficult to use as a fiber.
本発明における共重合ポリエステル樹脂の酸成分は、１０〜４０ｍｏｌ％がイソフタル酸またはイソフタル酸誘導体である。より好ましくは、２０〜３５ｍｏｌ％である。 10-40 mol% of the acid component of the copolyester resin in the present invention is isophthalic acid or an isophthalic acid derivative. More preferably, it is 20-35 mol%.
本発明における共重合ポリエステル樹脂のジオール成分は、８〜２５ｍｏｌ％がジエチレングリコールである。より好ましくは、１５〜２２ｍｏｌ％である。ジエチレングリコールの比率が８ｍｏｌ％未満であると、熱水可溶性が低下する傾向があり、２５ｍｏｌ％を超えると、衝撃強度が著しく低下するとともに、黄色に着色し、繊維として用いることが難しいおそれがある。 The diol component of the copolymerized polyester resin in the present invention is 8 to 25 mol% of diethylene glycol. More preferably, it is 15-22 mol%. When the ratio of diethylene glycol is less than 8 mol%, the hot water solubility tends to decrease, and when it exceeds 25 mol%, the impact strength is remarkably decreased, and it is colored yellow and may be difficult to use as a fiber.
本発明における共重合ポリエステル樹脂は、本発明の目的が損なわれない範囲であれば、更に他の成分が共重合されていてもよい。具体的な共重合成分としては、ジカルボン酸成分としては、ナフタレンジカルボン酸、４、４−ジフェニルジカルボン酸、アジピン酸、セバシン酸およびそのエステル形成性誘導体等の成分が挙げられる。また、ジオール成分としてはヘキサメチレングリコール、ネオペンチルグリコール、シクロヘキサンジメタノール、ビスフェノールＡ等が挙げられる。また、ポリエチレングリコール、ポリプロピレングリコール等のポリオキシアルキレングリコールも挙げられる。これら共重合成分の共重合量としては、構成する繰り返し単位当たり１０ｍｏｌ％以内が好ましく、５ｍｏｌ％以内がより好ましい。 The copolymer polyester resin in the present invention may be further copolymerized with other components as long as the object of the present invention is not impaired. Specific examples of the copolymer component include components such as naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, adipic acid, sebacic acid, and ester-forming derivatives thereof. Examples of the diol component include hexamethylene glycol, neopentyl glycol, cyclohexane dimethanol, and bisphenol A. Further, polyoxyalkylene glycols such as polyethylene glycol and polypropylene glycol are also included. The copolymerization amount of these copolymer components is preferably within 10 mol% per repeating unit constituting, and more preferably within 5 mol%.
本発明における共重合ポリエステルの製造方法としては、前述のジカルボン酸またはそのエステル形成性誘導体と、ジオールまたはそのエステル形成誘導体とを主たる出発原料として、常法に従い、エステル化またはエステル交換反応を行った後、さらに高温・減圧下で重縮合反応を行うことによって、製造する方法等が挙げられる。
また、重合触媒としては、一般にポリエステル重合に用いられている、三酸化アンチモンを代表とするアンチモン系触媒や酸化ゲルマニウムを代表とするゲルマニウム系触媒、更にはアルミニウム系触媒やチタン系触媒を用いることができる。
As a method for producing a copolyester in the present invention, esterification or transesterification was carried out according to a conventional method using the aforementioned dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as main starting materials. Thereafter, a method of producing the polycondensation reaction by performing a polycondensation reaction at a higher temperature and reduced pressure can be mentioned.
As the polymerization catalyst, an antimony catalyst represented by antimony trioxide, a germanium catalyst represented by germanium oxide, and an aluminum catalyst or titanium catalyst, which are generally used for polyester polymerization, may be used. it can.
本発明における共重合ポリエステル樹脂の粘度は、特に限定されるものではなく、通常のポリエステル繊維に利用されている固有粘度（以下ＩＶという）のポリエステルを使用することができる。重合性、紡糸性および繊維の力学的強度の点から、ＩＶは、０．３０〜０．６３のものを好適に用いることができる。より好ましくは、ＩＶが、０．３３〜０．４５である。 The viscosity of the copolyester resin in the present invention is not particularly limited, and a polyester having an intrinsic viscosity (hereinafter referred to as IV) used for ordinary polyester fibers can be used. In view of polymerizability, spinnability and mechanical strength of the fiber, IV of 0.30 to 0.63 can be preferably used. More preferably, IV is 0.33-0.45.
なお、本発明の目的を損なわない範囲において、この共重合ポリエステル樹脂の中には少量の他の重合体や酸化防止剤、熱安定剤、艶消し剤、顔料、染料、紫外線吸収剤、蛍光増白剤、可塑剤またはその他の添加剤等が含有されていてもよい。 As long as the object of the present invention is not impaired, the copolymer polyester resin includes a small amount of other polymers, antioxidants, heat stabilizers, matting agents, pigments, dyes, ultraviolet absorbers, fluorescent enhancers. Whitening agents, plasticizers or other additives may be contained.
本発明における共重合ポリエステル樹脂の水分率は、５０ｐｐｍ未満であることが好ましい。樹脂の乾燥方法としては、静置式真空乾燥機や撹拌翼付真空乾燥機を用いる方法が好適に挙げられる。本発明における共重合ポリエステル樹脂は、非晶性であり、ガラス転移温度（Ｔｇ）が、おおよそ６０〜７０℃となるため、静置式真空乾燥機での樹脂乾燥は、６０℃程度とし、数日間（例えば、１〜７日）の長時間をかけて５０ｐｐｍ未満とすることが好ましい。また撹拌翼付真空乾燥機（例えば、ホソカワミクロン株式会社製、ナウターミキサー（商品名））では、撹拌を続けながら８０〜１００℃で１２〜２４時間、さらに撹拌を続けたまま５５℃以下になるまで強制冷却することで５０ｐｐｍの水分率まで乾燥することができる。 The water content of the copolyester resin in the present invention is preferably less than 50 ppm. As a method for drying the resin, a method using a stationary vacuum dryer or a vacuum dryer equipped with a stirring blade is preferably exemplified. The copolymerized polyester resin in the present invention is amorphous and has a glass transition temperature (Tg) of about 60 to 70 ° C. Therefore, the resin drying in the stationary vacuum dryer is about 60 ° C. for several days. It is preferable to make it less than 50 ppm over a long time (for example, 1 to 7 days). Further, in a vacuum dryer with a stirring blade (for example, Nauter Mixer (trade name) manufactured by Hosokawa Micron Co., Ltd.), the temperature becomes 55 ° C. or lower while stirring is continued for 12 to 24 hours at 80 to 100 ° C. Can be dried to a moisture content of 50 ppm.
本発明における熱水可溶性樹脂に用いるエチレン−ビニルアルコール共重合樹脂について説明する。 The ethylene-vinyl alcohol copolymer resin used for the hot water-soluble resin in the present invention will be described.
エチレン−ビニルアルコール共重合樹脂は、エチレンと酢酸ビニルを重合して得たエチレン−酢酸ビニル共重合樹脂を更にケン化することで得られる樹脂で、以下の式（２）で示される。 The ethylene-vinyl alcohol copolymer resin is a resin obtained by further saponifying an ethylene-vinyl acetate copolymer resin obtained by polymerizing ethylene and vinyl acetate, and is represented by the following formula (2).
ここで、以下の式（３）で示されるエチレンコンテントは、１〜４５ｍｏｌ％であることが好ましく、より好ましくは、４〜４０ｍｏｌ％である。エチレンコンテントが１ｍｏｌ％未満では熱溶融しても、まだらとなり成形性が低下する傾向がある。４５ｍｏｌ％を超えると水溶性が低下し、熱水でも溶け残りが生じる傾向がある。エチレンコンテントが１５ｍｏｌ％以下であれば常温の水にも溶解するが、それ以上のコンテントの場合は６０℃から沸騰水で溶解することとなる。 Here, the ethylene content represented by the following formula (3) is preferably 1 to 45 mol%, and more preferably 4 to 40 mol%. If the ethylene content is less than 1 mol%, even if it is melted by heat, it tends to become mottled and the moldability tends to decrease. When it exceeds 45 mol%, the water solubility is lowered, and there is a tendency that undissolved residue is generated even with hot water. If the ethylene content is 15 mol% or less, it is dissolved in water at room temperature, but if it is more than that, it will be dissolved in boiling water from 60 ° C.
また以下の式（４）で示されるケン化度は、９０〜９９．７ｍｏｌ％が好ましく、９９．７ｍｏｌ％を超えると水溶性が低下する傾向があり、また安定的に生産することが難しいおそれがある。また、ケン化度が９０ｍｏｌ％未満の場合には、熱安定性が悪く熱分解やゲル発生によって満足な紡糸ができなくなるおそれがある。よって、より好ましいケン化度は、９５〜９９．５ｍｏｌ％である。 In addition, the saponification degree represented by the following formula (4) is preferably 90 to 99.7 mol%, and if it exceeds 99.7 mol%, the water solubility tends to decrease, and it may be difficult to produce stably. There is. On the other hand, if the degree of saponification is less than 90 mol%, the thermal stability is poor and there is a possibility that satisfactory spinning cannot be performed due to thermal decomposition or gel generation. Therefore, a more preferable degree of saponification is 95 to 99.5 mol%.
なお、エチレン、ビニルアルコール、酢酸ビニルの比率は、核磁気共鳴スペクトル（ＮＭＲ）を用いて測定することができる。 In addition, the ratio of ethylene, vinyl alcohol, and vinyl acetate can be measured using a nuclear magnetic resonance spectrum (NMR).
また、エチレン−ビニルアルコール共重合樹脂については、市販されている樹脂をそのまま利用してもよい。具体的には、日本合成化学株式会社製、「ソアノール（登録商標）」や株式会社クラレ製「エバール（登録商標）」や「エクセバール（登録商標）」の各種グレードの中より、適宜、選択することができる。 As the ethylene-vinyl alcohol copolymer resin, a commercially available resin may be used as it is. Specifically, select from various grades such as “Soarnol (registered trademark)” manufactured by Nippon Synthetic Chemical Co., Ltd. and “Eval (registered trademark)” or “Exval (registered trademark)” manufactured by Kuraray Co., Ltd. be able to.
次に、本発明の複合繊維の好ましい断面形状としては、図１、図２が例示される。図１は、ポリエーテルブロックアミド共重合樹脂を１つの芯成分とし、熱水可溶性樹脂を鞘成分とした芯鞘型形状の複合繊維である。この断面は、一つの芯成分を鞘成分が完全に囲んだ二重円の形状である。図２は、芯成分が２つ以上配置された複数の島成分からなり、鞘成分が複数の島成分を包含する形状である海島型形状である。
更に芯鞘型形状における芯成分や海島型形状における島成分の外形は、特に限定するものではないが、単純な丸型でもよいし、三角形であっても、Ｃ型や星形等の形であってもよい。また複合繊維の外周形状は、特に限定するものではなく、円形、三角形，四角形等多角形等の形状でもよい。
Next, FIG. 1 and FIG. 2 are illustrated as a preferable cross-sectional shape of the conjugate fiber of the present invention. FIG. 1 shows a core-sheath type composite fiber having a polyether block amide copolymer resin as one core component and a hot water-soluble resin as a sheath component. This cross section has a double circle shape in which a sheath component is completely surrounded by one core component. FIG. 2 shows a sea-island shape composed of a plurality of island components in which two or more core components are arranged, and the sheath component includes a plurality of island components.
Further, the outer shape of the core component in the core-sheath shape or the island component in the sea-island shape is not particularly limited, but may be a simple round shape, a triangle shape, a C shape, a star shape, or the like. There may be. The outer peripheral shape of the composite fiber is not particularly limited, and may be a shape such as a circle, a triangle, or a polygon such as a rectangle.
複合繊維を構成する繊維の本数は、１本の繊維から構成される、所謂モノフィラメントでも良いし、複数本の繊維から構成される、所謂マルチフィラメントでもよい。 The number of fibers constituting the composite fiber may be a so-called monofilament composed of one fiber or a so-called multifilament composed of a plurality of fibers.
また本発明の複合繊維における芯成分と鞘成分の質量比率（芯鞘比率、海島比率）は、特に限定されるものではないが、布帛または衣類等の衣料品として用いる際に、熱水で鞘成分または海成分を溶解して用い易い点、および安定して芯成分または島成分を鞘成分または海成分が完全に包み込む形状とし易い点から、芯（島）／鞘（海）が、２５／７５〜９０／１０の範囲が好ましく、より好ましくは、芯（島）／鞘（海）が５０／５０〜８５／１５の範囲であり、特に好ましくは、芯（島）／鞘（海）が、７０／３０〜８０／２０の範囲である。 The mass ratio of the core component to the sheath component (core-sheath ratio, sea-island ratio) in the conjugate fiber of the present invention is not particularly limited, but when used as clothing such as fabric or clothing, the sheath is heated with hot water. The core (island) / sheath (sea) is 25 / from the point that it is easy to dissolve and use the component or sea component, and that the core component or island component can be stably encapsulated by the sheath component or sea component. The range of 75 to 90/10 is preferred, more preferably the core (island) / sheath (sea) is in the range of 50/50 to 85/15, and particularly preferably the core (island) / sheath (sea). , 70/30 to 80/20.
更に海島型形状の場合、島数としてはノズルの吐出孔配置が一重円上にある３島、４島、二重円上に配置された５島、７島、三重円上に配置された１９島、３７島、四重円に配置された６１島等がバランスよく紡出し易く好ましい。 Further, in the case of the sea island shape, the number of islands is arranged on three islands, four islands, five islands, seven islands arranged on a double circle, seven islands arranged on a double circle, and 19 on a triple circle. Islands, 37 islands, 61 islands arranged in quadruple circles, and the like are preferred because they can be spun in a well-balanced manner.
本発明の複合繊維を含む布帛は、織物、編物、不織布等、いずれの形態の布帛としてもよい。 The fabric containing the conjugate fiber of the present invention may be any form of fabric such as a woven fabric, a knitted fabric, or a nonwoven fabric.
本発明の複合繊維を含む布帛は、接触冷感性、帯電防止性を得やすい点から、本発明の複合繊維を少なくとも２０質量％用いることが好ましい。より好ましくは、２５質量％以上である。 The fabric containing the conjugate fiber of the present invention preferably uses at least 20% by mass of the conjugate fiber of the present invention from the viewpoint of easy contact cooling and antistatic properties. More preferably, it is 25 mass% or more.
本発明の複合繊維を含む布帛は、熱水可溶性樹脂を溶解除去することにより、実質的にポリエーテルブロックアミド共重合樹脂単独糸を含む繊維構造体を製造することができる。 The fabric containing the conjugate fiber of the present invention can be produced by dissolving and removing the hot water-soluble resin to substantially produce a fiber structure containing a single polyether block amide copolymer resin yarn.
得られた実質的にポリエーテルブロックアミド共重合樹脂単独糸を含む繊維構造体は、好適に衣類に用いることができる。このような繊維構造体を含む衣類は、接触冷感性や帯電防止性に優れたものとなる。 The obtained fiber structure containing the polyether block amide copolymer resin single yarn can be suitably used for clothing. A garment including such a fiber structure has excellent contact cooling and antistatic properties.
次に、本発明の複合繊維、本発明の複合繊維を含む布帛、および衣類の製造方法の好適な例について説明する。
本発明の複合繊維の製造方法としては、例えば、芯成分を構成する樹脂と鞘成分を構成する樹脂を別々の押出機で加熱溶融し、ギヤポンプで計量押出ししてノズル内部で所望する形状に会合させ押出して繊維形状を得て巻き取って繊維化する、一般的な溶融複合押出法での紡糸方法が適応できる。
Next, the suitable example of the manufacturing method of the composite fiber of this invention, the fabric containing the composite fiber of this invention, and clothing is demonstrated.
As a method for producing the conjugate fiber of the present invention, for example, the resin constituting the core component and the resin constituting the sheath component are heated and melted with separate extruders, and are metered and extruded with a gear pump to associate with a desired shape inside the nozzle. The spinning method in a general melt composite extrusion method in which a fiber shape is obtained by extrusion and wound to be fiberized can be applied.
布帛の製造方法としては、例えば、織機を用い整経した経糸や緯糸として、織り込み製織して織物を製造してもよいし、丸編み機等を用いて製編して編物を製造してもよい。布帛として、接触冷感性および帯電防止性を得るためには、繊維の２０質量％以上を本発明の複合繊維を用いることが好ましい。より好ましくは、２５質量％以上である。 As a method for producing a fabric, for example, a woven fabric may be produced by weaving and weaving as warp or weft warped using a loom, or a knitted fabric may be produced by knitting using a circular knitting machine or the like. . In order to obtain contact cooling sensation and antistatic property as the fabric, it is preferable to use the composite fiber of the present invention for 20% by mass or more of the fiber. More preferably, it is 25 mass% or more.
また、芯成分と鞘成分を溶融し、溶融した樹脂を芯鞘形状で押出し、スパンレース法やスパンボンド法で不織布として、布帛を製造してもよい。 Alternatively, the core component and the sheath component may be melted, the melted resin may be extruded in a core-sheath shape, and a fabric may be produced as a nonwoven fabric by a spunlace method or a spunbond method.
本発明の複合繊維は、上記のような方法により、製編織時の糸の引き取り時等の工程でも、膠着することなく、容易に本発明の複合繊維を含む、織物、編物、不織布等の布帛を製造することができる。 The composite fiber of the present invention is a fabric such as a woven fabric, a knitted fabric, and a non-woven fabric, which easily contains the composite fiber of the present invention without sticking even in the process of taking up the yarn during knitting and weaving by the above method. Can be manufactured.
本発明の複合繊維を含む布帛は、熱可塑性樹脂を溶解除去することにより、実質的にポリエーテルブロックアミド共重合樹脂単独糸を含む繊維構造体を製造することができる。 The fabric containing the conjugate fiber of the present invention can be produced by dissolving and removing the thermoplastic resin to produce a fiber structure substantially containing a polyether block amide copolymer resin single yarn.
本発明の複合繊維を含む布帛において、熱水可溶性樹脂を溶解除去する方法としては、例えば、布帛の精練工程の前段階で６０℃以上の温度の水の中を潜らせることにより好適に溶解除去することができる。ここで、水の中で、水流や機械的な揉みを加えると溶解を効率的に行うことができる。また、液流染色機による染色前の工程として水のみを満たした状態で液流を加えることにより、熱水可溶性樹脂を溶解除去してもよい。本発明において、熱水可溶性樹脂の溶解除去する際の水の温度は、６０℃以上が好ましく、より好ましくは、８０℃以上である。 As a method for dissolving and removing the hot water-soluble resin in the fabric containing the conjugate fiber of the present invention, for example, it is preferably dissolved and removed by submerging in water at a temperature of 60 ° C. or more before the scouring step of the fabric. can do. Here, dissolution can be efficiently performed by adding water flow or mechanical stagnation in water. Further, the hot water-soluble resin may be dissolved and removed by adding a liquid flow in a state where only water is filled as a step before dyeing by a liquid dyeing machine. In the present invention, the temperature of water when dissolving and removing the hot water-soluble resin is preferably 60 ° C. or higher, and more preferably 80 ° C. or higher.
このようにして得られる、実質的にポリエーテルブロックアミド共重合樹脂単独糸を含む繊維構造体は、衣類に用いることによって、優れた接触冷感性や帯電防止性を有する衣類を得ることができる。 By using the fiber structure substantially including the polyether block amide copolymer resin single yarn thus obtained for clothing, it is possible to obtain clothing having excellent contact cooling and antistatic properties.
以下に実施例を挙げて本発明を具体的に説明する。尚、本発明は以下に述べる実施例に限定されるものではない。また、実施例および比較例での試作方法、測定方法および評価方法は以下の通りである。 The present invention will be specifically described below with reference to examples. In addition, this invention is not limited to the Example described below. The prototype method, measurement method, and evaluation method in Examples and Comparative Examples are as follows.
〔ポリエステル樹脂の作製〕
酸成分に対しグリコール成分のｍｏｌ比が１．２となるように、表１で示した共重合比率にてジオール成分をステンレス製オートクレーブに仕込み、２５０℃、２００ｋＰａの条件下でエステル化反応を行った。エステル化反応終了後、所定量の三酸化アンチモン触媒とリン酸トリメチルを加え、２８０℃、６６Ｐａの減圧下にて縮重合反応を行い、表１記載の組成の共重合ポリエステル樹脂を得た。得られた共重合ポリエステル樹脂は、ステンレスオートクレーブの底ノズルより窒素圧力下で水槽へ吐出冷却し固化させ、これをペレタイザーにてペレット化した。ここで特に熱水可溶性の高いもの（常温の水でも溶解するもの）は、共重合ポリエステル樹脂をストランドコンベア上の金属メッシュの上に吐出し、冷風を当てて固化させて索状とし、これをペレタイザーにてペレット化した。
[Production of polyester resin]
The diol component was charged into a stainless steel autoclave at the copolymerization ratio shown in Table 1 so that the molar ratio of the glycol component to the acid component was 1.2, and the esterification reaction was performed at 250 ° C. and 200 kPa. It was. After completion of the esterification reaction, a predetermined amount of antimony trioxide catalyst and trimethyl phosphate were added, and a condensation polymerization reaction was carried out under reduced pressure at 280 ° C. and 66 Pa to obtain a copolyester resin having the composition shown in Table 1. The obtained copolyester resin was discharged and cooled from a bottom nozzle of a stainless steel autoclave to a water tank under nitrogen pressure to be solidified, and pelletized with a pelletizer. Here, especially those that are highly soluble in hot water (those that can dissolve even at room temperature water), the copolyester resin is discharged onto a metal mesh on a strand conveyor and solidified by applying cold air to form a cord. Pelletized with a pelletizer.
〔ポリエステル樹脂の熱水可溶性評価〕
表１の各種樹脂ペレットについて、６０℃の水中で溶解したものを◎、８０℃の水中で溶解したものを○、８０℃の水中で溶解しなかったものを×とした。
[Evaluation of hot water solubility of polyester resin]
Regarding the various resin pellets in Table 1, those that were dissolved in 60 ° C. water were indicated as “◎”, those that were dissolved in 80 ° C. water were indicated as “◯”, and those that were not dissolved in 80 ° C. water were indicated as “X”.
〔筒編地作製方法〕
英光産業製試験筒編機ＮＣＲ−ＥＷ（釜径：３インチ半、２４ゲージ）を用いて、複合繊維を二本双糸にて、ウェール数：３０本／２５．４ｍｍ、コース数：６０本／２５．４ｍｍになるように編立て、筒編地を作製した。
[Cylinder knitted fabric production method]
Using Yoko Sangyo's test tube knitting machine NCR-EW (bottle diameter: 3 inches and a half, 24 gauge), composite fibers with two twin yarns, number of wales: 30 / 25.4 mm, number of courses: 60 A tubular knitted fabric was produced by knitting to 25.4 mm.
〔複合繊維の熱水可溶性評価〕
作製した筒編地を８０℃の水（イオン交換水、１：２０）に入れ、撹拌し１０分間処理した後、取り出し、更に水で洗浄した後、脱水し、風乾させた。処理前後の筒編地の質量を秤量し、質量減量率を求めた。筒編地に使用した複合繊維の組成より計算された鞘成分（海成分）の質量に対し、質量減量率が９５％以上のものを○と評価し、９５％未満のものを×と評価した。
[Hot water solubility evaluation of composite fibers]
The produced tubular knitted fabric was put in 80 ° C. water (ion exchange water, 1:20), stirred and treated for 10 minutes, then taken out, further washed with water, dehydrated and air dried. The mass of the tubular knitted fabric before and after the treatment was weighed to determine the mass loss rate. With respect to the mass of the sheath component (sea component) calculated from the composition of the composite fiber used for the tubular knitted fabric, a mass loss rate of 95% or more was evaluated as ○, and a mass less than 95% was evaluated as ×. .
〔接触冷感性評価〕
作製した筒編地を８０℃の水（イオン交換水、１：２０）に入れ、撹拌し１０分間処理した後、取り出し、更に水で洗浄した後、脱水し、風乾させた。処理前後の筒編地を、各々、左右の手で握り、冷感性に差があると判断したものには○、差が無いと判断したものには×と評価した。
[Contact Cool Sensitivity Evaluation]
The produced tubular knitted fabric was put in 80 ° C. water (ion exchange water, 1:20), stirred and treated for 10 minutes, then taken out, further washed with water, dehydrated and air dried. The tubular knitted fabrics before and after the treatment were each grasped with the left and right hands, and evaluated as ○ for those judged to have a difference in cold feeling, and evaluated as × for those judged to have no difference.
〔実施例１〕
表１に示す樹脂Ａ−１を鞘成分、アルケマ社製ペバックス（登録商標）ＭＨ１６５７（商品名）を芯成分として、芯／鞘比率が３／１（質量比率）となるように調整して、２７０℃にて、溶融紡糸し、１１０ｄｔｅｘ／２４ｆの複合繊維を得た。得られた複合繊維を用いて筒編地を作製した。
[Example 1]
Using resin A-1 shown in Table 1 as a sheath component, and Pekkas (registered trademark) MH1657 (trade name) manufactured by Arkema as a core component, the core / sheath ratio is adjusted to 3/1 (mass ratio), Melt spinning was performed at 270 ° C. to obtain a composite fiber of 110 dtex / 24f. A tubular knitted fabric was produced using the obtained conjugate fiber.
〔実施例２〕
繊維断面形状を、１９個の島成分を有する海島型形状とし、表１に示す樹脂Ｂ−１を海成分、アルケマ社製ペバックス（登録商標）ＭＨ１６５７（商品名）を島成分、海／島比率が４／６（質量比率）とする以外は、実施例１と同様に複合繊維を得た。得られた複合繊維を用いて筒編地を作製した。
[Example 2]
The cross-sectional shape of the fiber is a sea-island shape having 19 island components, the resin B-1 shown in Table 1 is the sea component, Pevacs (registered trademark) MH1657 (trade name) manufactured by Arkema is the island component, and the sea / island ratio The composite fiber was obtained in the same manner as in Example 1 except that the ratio was 4/6 (mass ratio). A tubular knitted fabric was produced using the obtained conjugate fiber.
〔実施例３〕
繊維断面形状を、１９個の島成分を有する海島型形状とし、表１に示す樹脂Ｂ−２を海成分、アルケマ社製ペバックス（登録商標）ＭＨ１６５７（商品名）を島成分、海／島比率が４／６（質量比率）とする以外は、実施例１と同様に複合繊維を得た。得られた複合繊維を用いて筒編地を作製した。
Example 3
The cross-sectional shape of the fiber is a sea-island shape having 19 island components, the resin B-2 shown in Table 1 is the sea component, Pebaks (registered trademark) MH1657 (trade name) manufactured by Arkema Co. is the island component, and the sea / island ratio The composite fiber was obtained in the same manner as in Example 1 except that the ratio was 4/6 (mass ratio). A tubular knitted fabric was produced using the obtained conjugate fiber.
〔実施例４〕
繊維断面形状を、３７個の島成分を有する海島型形状とし、表１に示す樹脂Ｃ−１を海成分、海／島比率が５／５（質量比率）とする以外は実施例２と同様に複合繊維を得た。得られた複合繊維を用いて筒編地を作製した。
Example 4
The cross-sectional shape of the fiber is a sea-island shape having 37 island components, and the resin C-1 shown in Table 1 is the sea component, and the sea / island ratio is 5/5 (mass ratio). A composite fiber was obtained. A tubular knitted fabric was produced using the obtained conjugate fiber.
〔実施例５〕
繊維断面形状を、３７個の島成分を有する海島型形状とし、表１に示す樹脂Ｃ−２を海成分、海／島比率が５／５（質量比率）とする以外は実施例２と同様に複合繊維を得た。得られた複合繊維を用いて筒編地を作製した。
Example 5
The cross-sectional shape of the fiber is a sea-island shape having 37 island components, and the resin C-2 shown in Table 1 is the sea component, and the sea / island ratio is 5/5 (mass ratio). A composite fiber was obtained. A tubular knitted fabric was produced using the obtained conjugate fiber.
〔実施例６〕
エチレンコンテントが３８ｍｏｌ％でケン化度が９８％の日本合成化学製ソアノール（登録商標）Ｅ３８０８（商品名）を鞘成分、アルケマ社製ペバックス（登録商標）ＭＶ１０７４（商品名）を芯成分、紡糸温度を２２０℃、とする以外は、実施例１と同様に、複合繊維を得た。得られた複合繊維を用いて筒編地を作製した。
Example 6
Soyanol (registered trademark) E3808 (trade name) made by Nippon Synthetic Chemical Co., Ltd. with 38 mol% ethylene content and 98% saponification degree is a sheath component, Pevacs (registered trademark) MV1074 (trade name) manufactured by Arkema Co., Ltd., core component, spinning temperature A composite fiber was obtained in the same manner as in Example 1 except that the temperature was 220 ° C. A tubular knitted fabric was produced using the obtained conjugate fiber.
〔実施例７〕
エチレンコンテントが６ｍｏｌ％でケン化度が９８．５％のクラレ製エクセバール（登録商標）ＲＳ−４１０４（商品名）を鞘成分、アルケマ社製ペバックス（登録商標）ＭＶ１０７４（商品名）を芯成分と、芯／鞘比率が３／１（質量比率）、紡糸温度が２４０℃、とする以外は、実施例２と同様に複合繊維を得た。得られた複合繊維を用いて筒編地を作製した。
Example 7
Exeval (registered trademark) RS-4104 (trade name) manufactured by Kuraray having an ethylene content of 6 mol% and a saponification degree of 98.5% is a sheath component, and Pevacs (registered trademark) MV1074 (trade name) manufactured by Arkema is used as a core component. A composite fiber was obtained in the same manner as in Example 2 except that the core / sheath ratio was 3/1 (mass ratio) and the spinning temperature was 240 ° C. A tubular knitted fabric was produced using the obtained conjugate fiber.
〔比較例１〕
表１に示した組成の樹脂Ｄを鞘成分、芯／鞘比率が３／１（質量比率）、紡糸温度２９０℃とする以外は、実施例１と同様に複合繊維を得た。得られた複合繊維を用いて筒編地を作製した。
[Comparative Example 1]
A composite fiber was obtained in the same manner as in Example 1 except that the resin D having the composition shown in Table 1 was a sheath component, the core / sheath ratio was 3/1 (mass ratio), and the spinning temperature was 290 ° C. A tubular knitted fabric was produced using the obtained conjugate fiber.
〔比較例２〕
表１に示した組成の樹脂Ｅを鞘成分とする以外は実施例１と同様に複合繊維を得た。得られた複合繊維を用いて筒編地を作製した。
[Comparative Example 2]
A composite fiber was obtained in the same manner as in Example 1 except that the resin E having the composition shown in Table 1 was used as the sheath component. A tubular knitted fabric was produced using the obtained conjugate fiber.
実施例および比較例の繊維断面形状、鞘（海）成分樹脂、鞘（海）成分の質量比率、芯（島）成分樹脂、島成分の質量比率、繊度、熱水可溶性評価、および接触冷感性評価を表２に示す。尚、表中、Ｅ３８０８は、日本合成化学製ソアノール（登録商標）Ｅ３８０８（商品名）、ＲＳ−４１０４は、クラレ製エクセバール（登録商標）ＲＳ−４１０４（商品名）、ＭＨ１６５７（商品名）は、アルケマ社製ペバックス（登録商標）ＭＨ１６５７（商品名）、ＭＶ１６５７（商品名）は、アルケマ社製ペバックス（登録商標）ＭＶ１６５７（商品名）を示す。 Fiber cross-sectional shapes of Examples and Comparative Examples, sheath (sea) component resin, mass ratio of sheath (sea) component, core (island) component resin, mass ratio of island component, fineness, hot water solubility evaluation, and contact cooling sensitivity The evaluation is shown in Table 2. In the table, E3808 is Soarnol (registered trademark) E3808 (trade name) manufactured by Nippon Synthetic Chemical Co., Ltd., RS-4104 is EXVAL (registered trademark) RS-4104 (trade name) manufactured by Kuraray, and MH1657 (trade name) is Pevacs (registered trademark) MH1657 (trade name) and MV1657 (trade name) manufactured by Arkema Co. indicate Pebax (registered trademark) MV1657 (trade name) manufactured by Arkema.
実施例１〜７から得られた複合繊維より作製した筒編地は、熱水可溶性であり、熱水処理した後の筒編地は、実質的にポリエーテルブロック共重合樹脂単独の繊維からなり、接触冷感性および帯電防止性に優れたものであった。
比較例１から得られた複合繊維より作製した筒編地は、熱水可溶性評価の際、全く減量せず、接触冷感性もなかった。
比較例２から得られた複合繊維より得られた筒編地は、熱水可溶性評価の際、全く減量しなかった。その後、筒編地に対し、８０℃の熱水に代えて、２％水酸化ナトリウム水溶
液を用いて、９０℃、３０分間にて減量処理したところ、芯成分を含めすべてが溶解した。得られた筒編地は接触冷感性がなかった。
また、実施例１〜７より得られた複合繊維を５０質量％用いて製編し、液流染色機に、８０℃の水により液流させた後、染色した繊維構造物を、シャツに用いたところ、洗濯を繰り返しても、接触冷感性に優れ、帯電防止性に優れていた。同様に比較例１および比較例２の複合繊維からシャツを作製したところ、接触冷感性は全く感じられなかった。また洗濯を繰り返すと静電気により、肌にまとわりつくものとなった。
The tubular knitted fabrics made from the composite fibers obtained from Examples 1 to 7 are soluble in hot water, and the tubular knitted fabric after the hot water treatment is substantially composed of fibers of a polyether block copolymer resin alone. It was excellent in contact cooling sensitivity and antistatic property.
The tubular knitted fabric produced from the composite fiber obtained from Comparative Example 1 did not lose weight at the time of hot water solubility evaluation, and did not have contact cooling sensation.
The tubular knitted fabric obtained from the composite fiber obtained from Comparative Example 2 did not lose weight at the time of hot water solubility evaluation. Thereafter, the tubular knitted fabric was subjected to a weight reduction treatment at 90 ° C. for 30 minutes using a 2% sodium hydroxide aqueous solution instead of 80 ° C. hot water, and everything including the core component was dissolved. The obtained tubular knitted fabric did not have contact cooling sensation.
Further, the composite fiber obtained from Examples 1 to 7 was knitted using 50% by mass, and the dyed fiber structure was used for a shirt after being made to flow in a liquid dyeing machine with water at 80 ° C. However, even after repeated washing, it was excellent in contact cooling and antistatic properties. Similarly, when a shirt was produced from the composite fibers of Comparative Example 1 and Comparative Example 2, no contact cooling sensation was felt. Moreover, when washing was repeated, it became clinging to the skin due to static electricity.
本発明の複合繊維は、布帛化した後、熱水で処理することにより、実質的にポリエーテルブロックアミド共重合樹脂からなる単独糸を含む繊維構造物を工業的に得ることができるため、得られた繊維構造物は、接触冷感性、帯電防止性に優れ、衣類等の衣料用途に好適に用いることができる。 The composite fiber of the present invention can be obtained industrially by producing a fiber structure containing a single yarn substantially made of a polyether block amide copolymer resin by treating with hot water after forming into a fabric. The obtained fiber structure is excellent in contact cooling sensation and antistatic property, and can be suitably used for apparel applications such as clothing.
１ 熱水可溶性樹脂
２ ポリエーテルブロックアミド共重合樹脂
1 Hot water
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