JPWO2020250994A1 - Polyurethane elastic fiber and products containing it, and surface treatment agent for polyurethane elastic fiber - Google Patents

Polyurethane elastic fiber and products containing it, and surface treatment agent for polyurethane elastic fiber Download PDF

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JPWO2020250994A1
JPWO2020250994A1 JP2021526140A JP2021526140A JPWO2020250994A1 JP WO2020250994 A1 JPWO2020250994 A1 JP WO2020250994A1 JP 2021526140 A JP2021526140 A JP 2021526140A JP 2021526140 A JP2021526140 A JP 2021526140A JP WO2020250994 A1 JPWO2020250994 A1 JP WO2020250994A1
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polyurethane elastic
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hydrocarbon compound
elastic fiber
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JP7065259B2 (en
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均 佐藤
英之 後藤
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Asahi Kasei Corp
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Abstract

シリコーンオイルの含有量が少なくても、解舒性が良好であり、マルチフィラメントの単糸のバラけが少ないポリウレタン弾性繊維及びそれを含む製品、並びに、該ポリウレタン弾性繊維の製造に好適なポリウレタン弾性繊維用表面処理剤を提供する。本発明のポリウレタン弾性繊維用表面処理剤は、下記式（１）：｛式中、ｎは２〜５の整数である。｝で表される炭化水素化合物を、ポリウレタン弾性繊維重量に対して１０ｐｐｍ以上１００００ｐｐｍ以下で含有することを特徴とするポリウレタン弾性繊維、該ポリウレタン弾性繊維を含む布帛、衛生材料製品、並びに該炭化水素化合物を、０．１０重量％以上２５重量％以下で含有することを特徴とする。Polyurethane elastic fibers and products containing them, which have good unfoldability even when the content of silicone oil is low and the variation of single yarns of multifilaments is small, and polyurethane elastic fibers suitable for producing the polyurethane elastic fibers. Provides a surface treatment agent for use. The surface treatment agent for polyurethane elastic fibers of the present invention has the following formula (1): {in the formula, n is an integer of 2 to 5. } Is contained in a polyurethane elastic fiber of 10 ppm or more and 10000 ppm or less with respect to the weight of the polyurethane elastic fiber, a fabric containing the polyurethane elastic fiber, a sanitary material product, and the hydrocarbon compound. Is contained in an amount of 0.10% by weight or more and 25% by weight or less.

Description

本発明は、ポリウレタン弾性繊維及びそれを含有する製品、並びにポリウレタン弾性繊維用表面処理剤に関する。 The present invention relates to polyurethane elastic fibers, products containing them, and surface treatment agents for polyurethane elastic fibers.

ポリウレタン弾性繊維は、高伸度で優れた弾性特性を有する。しかしながら、ポリウレタン重合体は柔軟かつ粘着性のある素材であるために、ポリウレタン弾性繊維を使用した製品の製造工程において、ポリウレタン弾性繊維の巻糸体からの糸の解舒時や糸の走行時のガイド、ローラーでの摩擦抵抗による糸切れ、生産ばらつき等の問題が発生しやすく、特に巻糸体の長期の保管後の使用でそれらの問題が非常に顕著である。
それらの問題を解決するために、シリコーンオイルからなる処理剤を糸に付与する方法が知られており、シリコーンオイルは高価であるため一般に安価な鉱物油を用いてシリコーンオイルを希釈して処理剤を調製して糸に付与される。しかし、シリコーンオイルを鉱物油等で希釈した処理剤では、コストダウンはできるものの、該処理剤を付与されたポリウレタン弾性繊維の巻糸体からの解舒性や摩擦性が低下してしまい、十分な解舒性、摩擦性が得られない。Polyurethane elastic fibers have high elongation and excellent elastic properties. However, since the polyurethane polymer is a flexible and adhesive material, in the manufacturing process of a product using the polyurethane elastic fiber, when the yarn is unwound from the winding body of the polyurethane elastic fiber or when the yarn is run. Problems such as yarn breakage due to frictional resistance between guides and rollers, production variation, etc. are likely to occur, and these problems are particularly remarkable when the wound yarn is used after long-term storage.
In order to solve these problems, a method of applying a treatment agent consisting of silicone oil to the thread is known, and since silicone oil is expensive, the treatment agent is generally obtained by diluting the silicone oil with an inexpensive mineral oil. Is prepared and applied to the thread. However, although the cost can be reduced by using a treatment agent obtained by diluting silicone oil with mineral oil or the like, the unwinding property and frictional property of the polyurethane elastic fiber to which the treatment agent is applied are lowered, which is sufficient. It is not possible to obtain good elasticity and friction.

以下の特許文献１では、シリコーンオイルを鉱物油で希釈したポリウレタン弾性繊維用表面処理剤中に特定のアミンや有機酸を添加する方法が報告されているが、鉱物油中に塩基性又は酸性化合物を添加する方法は処理剤の保管安定性に不安があり、また、調合の工数増やコストアップの問題がある。 In the following Patent Document 1, a method of adding a specific amine or organic acid to a surface treatment agent for polyurethane elastic fibers obtained by diluting silicone oil with mineral oil is reported, but a basic or acidic compound is reported in the mineral oil. The method of adding the above has concerns about the storage stability of the treatment agent, and also has the problems of increasing the number of preparation steps and increasing the cost.

以下の特許文献２では、シリコーンオイルを鉱物油で希釈したポリウレタン弾性繊維用表面処理剤で解舒性を向上する手段として特定の粘度範囲からなる炭化水素油（鉱物油）を特定量以上使用した処理剤を糸に付与する手法が報告されている。しかし、粘度の高い炭化水素油を使用すると、処理剤自体の粘度が高くなってしまい安定した糸への塗布が難しく、また、処理剤自体の高粘度化による混合不良や保管安定性の問題がある。 In the following Patent Document 2, a hydrocarbon oil (mineral oil) having a specific viscosity range is used in a specific amount or more as a means for improving the solubilization property with a surface treatment agent for polyurethane elastic fibers obtained by diluting silicone oil with mineral oil. A method of applying a treatment agent to a thread has been reported. However, when a highly viscous hydrocarbon oil is used, the viscosity of the treatment agent itself becomes high, making it difficult to apply it to a stable yarn, and there are problems of mixing failure and storage stability due to the high viscosity of the treatment agent itself. be.

以下の特許文献３では、シリコーンオイルと高級脂肪酸金属塩からなる改質剤を練りこんだ紡糸原液を乾式紡糸して、解舒性の良いポリウレタン弾性繊維を得る方法が報告されている。しかし、一定の技術的な改善はあるものの、改質剤の練りこみによってマルチフィラメントの単糸間合着性が弱くなり、マルチフィラメントから単糸が剥離してしまう現象（以下、単糸バラけという。）が発生しやすくなり、その単糸バラけが編立等のポリウレタン弾性繊維の使用時に糸切れの原因となってしまうという問題がある。 The following Patent Document 3 reports a method of dry-spinning a spinning stock solution kneaded with a modifier composed of a silicone oil and a higher fatty acid metal salt to obtain polyurethane elastic fibers having good unfoldability. However, although there are some technical improvements, the kneading of the modifier weakens the bondability between the single yarns of the multifilament, and the single yarn is peeled off from the multifilament (hereinafter, single yarn disintegration). ) Is likely to occur, and there is a problem that the single yarn loosening causes yarn breakage when using polyurethane elastic fibers such as knitting.

このように、シリコーンオイルの少ない含有量で解舒性が改善され、マルチフィラメントの単糸バラけが少ないポリウレタン弾性繊維は未だ得られてない。 As described above, a polyurethane elastic fiber in which the unfoldability is improved with a small content of silicone oil and the single yarn variation of the multifilament is small has not yet been obtained.

特開２００７-２７０４１４号公報Japanese Unexamined Patent Publication No. 2007-270414 特開２０１７-１１０３１９号公報Japanese Unexamined Patent Publication No. 2017-110319 特開２００９-２８７１２６号公報Japanese Unexamined Patent Publication No. 2009-287126

前記した従来技術の問題点に鑑み、本発明が解決しようとする課題は、シリコーンオイルの含有量が少なくても、解舒性が良好であり、マルチフィラメントの単糸バラけが少ないポリウレタン弾性繊維及びそれを含む製品、並びに、前記ポリウレタン弾性繊維の製造に好適なポリウレタン弾性繊維用表面処理剤を提供することである。 In view of the above-mentioned problems of the prior art, the problems to be solved by the present invention are polyurethane elastic fibers having good unwinding property even if the content of silicone oil is small and having less variation in single yarn of multifilament. It is an object of the present invention to provide a product containing the same, and a surface treatment agent for polyurethane elastic fiber suitable for producing the polyurethane elastic fiber.

本願発明者らは、前記課題を解決すべく、鋭意検討し実験を重ねた結果、特定の分岐炭化水素化合物を特定量、ポリウレタン弾性繊維に含有させることで上記問題を解決できることを予想外に発見し、本発明を完成するに至ったものである。 As a result of diligent studies and experiments in order to solve the above problems, the inventors of the present application unexpectedly discovered that the above problems can be solved by containing a specific amount of a specific branched hydrocarbon compound in the polyurethane elastic fiber. However, the present invention has been completed.

すなわち、本発明は以下の通りのものである。
［１］下記式（１）：

Figure 2020250994
｛式中、ｎは２〜５の整数である。｝で表される炭化水素化合物を、ポリウレタン弾性繊維重量に対して１０ｐｐｍ以上１００００ｐｐｍ以下で含有することを特徴とするポリウレタン弾性繊維。
［２］式中、ｎ＝３である前記式（１）で表される炭化水素化合物をポリウレタン弾性繊維重量に対して１０ｐｐｍ以上８０００ｐｐｍ以下で含有する、前記［１］に記載のポリウレタン弾性繊維。
［３］式中、ｎが２〜５の整数である前記式（１）で表される炭化水素化合物以外の炭化水素化合物をさらに含有する、前記［１］又は［２］に記載のポリウレタン弾性繊維。
［４］ヘキサンによる抽出液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうち、トリアコンタンの保持時間より長い保持時間を占める成分の面積が５％未満である、前記［１］〜［３］のいずれかに記載のポリウレタン弾性繊維。
［５］ヘキサンによる抽出液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうち、オクトコサンの保持時間より長い保持時間を占める成分の面積が５％未満である、前記［１］〜［４］のいずれかに記載のポリウレタン弾性繊維。
［６］ヘキサンによる抽出液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうち、ヘキサデカンの保持時間よりも短い保持時間を占める成分の面積が５％未満である、前記［１］〜［５］のいずれかに記載のポリウレタン弾性繊維。
［７］ヘキサンによる抽出液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうち、オクタデカンの保持時間よりも短い保持時間を占める面積が２０％未満である、前記［１］〜［６］のいずれかに記載のポリウレタン弾性繊維。
［８］ヘキサンによる抽出液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうち、オクタデカンとオクトコサンの保持時間の間を占める成分の面積が８０％以上である、前記［１］〜［７］のいずれかに記載のポリウレタン弾性繊維。
［９］前記［１］〜［８］のいずれかに記載のポリウレタン弾性繊維を含む布帛。
［１０］前記［１］〜［８］のいずれかに記載のポリウレタン弾性繊維を含む衛生材料製品。
［１１］下記式（１）：
Figure 2020250994
 ｛式中、ｎは２〜５の整数である。｝で表される炭化水素化合物を、０．１０重量％以上２５重量％以下で含有することを特徴とするポリウレタン弾性繊維用表面処理剤。
［１２］式中、ｎ＝３である前記式（１）で表される炭化水素化合物を、０．１０重量％以上２０重量％以下で含有する、前記［１１］に記載のポリウレタン弾性繊維用表面処理剤。
［１３］式中、ｎが２〜５の整数である前記式（１）で表される炭化水素化合物以外の炭化水素化合物をさらに含有する、前記［１１］又は［１２］に記載のポリウレタン弾性繊維。
［１４］ヘキサンに溶解した溶液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうちトリアコンタンの保持時間より長い保持時間を占める成分の面積が５％未満である、前記［１１］〜［１３］に記載のポリウレタン弾性繊維用表面処理剤。
［１５］ヘキサンに溶解した溶液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうち、オクトコサンの保持時間より長い保持時間を占める成分の面積が５％未満である、前記［１１］〜［１４］のいずれかに記載のポリウレタン弾性繊維用表面処理剤。
［１６］ヘキサンに溶解した溶液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうちヘキサデカンの保持時間よりも短い保持時間を占める面積が５％未満である、前記［１１］〜［１５］のいずれかに記載のポリウレタン弾性繊維用表面処理剤。
［１７］ヘキサンに溶解した溶液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうち、オクタデカンの保持時間よりも短い保持時間を占める面積が２０％未満である、前記［１１］〜［１６］のいずれかに記載のポリウレタン弾性繊維用表面処理剤。
［１８］ヘキサンに溶解した溶液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうち、オクタデカンとオクトコサンの保持時間の間に占める成分の面積が８０％以上である、前記［１１］〜［１７］のいずれかに記載のポリウレタン弾性繊維用表面処理剤。
［１９］シリコーンオイルを２０重量％以上７０重量％以下でさらに含有する、前記［１１］〜［１８］のいずれかに記載のポリウレタン弾性繊維用表面処理剤。That is, the present invention is as follows.
[1] The following formula (1):
Figure 2020250994
 {In the formula, n is an integer of 2-5. }, The polyurethane elastic fiber is characterized by containing the hydrocarbon compound represented by} in an amount of 10 ppm or more and 10000 ppm or less with respect to the weight of the polyurethane elastic fiber.
[2] The polyurethane elastic fiber according to the above [1], which contains the hydrocarbon compound represented by the formula (1) having n = 3 in an amount of 10 ppm or more and 8000 ppm or less with respect to the weight of the polyurethane elastic fiber.
[3] The polyurethane elasticity according to the above [1] or [2], further containing a hydrocarbon compound other than the hydrocarbon compound represented by the formula (1) in which n is an integer of 2 to 5. fiber.
[4] In the GC / MS measurement of the extract with hexane, the area of the component occupying the retention time longer than the retention time of triacontane is less than 5% of the total area of the peak derived from the hydrocarbon compound. ] To [3]. The polyurethane elastic fiber according to any one of.
[5] In the GC / MS measurement of the extract with hexane, the area of the component occupying the retention time longer than the retention time of octocosan is less than 5% of the total area of the peak derived from the hydrocarbon compound. The polyurethane elastic fiber according to any one of [4].
[6] In the GC / MS measurement of the extract with hexane, the area of the component occupying the retention time shorter than the retention time of hexadecane is less than 5% of the total area of the peak derived from the hydrocarbon compound. ] To [5]. The polyurethane elastic fiber according to any one of.
[7] In the GC / MS measurement of the extract with hexane, less than 20% of the total area of the peak derived from the hydrocarbon compound occupies a holding time shorter than the holding time of octadecane. The polyurethane elastic fiber according to any one of [6].
[8] In the GC / MS measurement of the extract with hexane, the area of the component that occupies between the retention time of octadecane and octocosan is 80% or more of the total area of the peak derived from the hydrocarbon compound. The polyurethane elastic fiber according to any one of [7].
[9] A fabric containing the polyurethane elastic fiber according to any one of the above [1] to [8].
[10] A sanitary material product containing the polyurethane elastic fiber according to any one of the above [1] to [8].
[11] The following formula (1):
Figure 2020250994
 {In the formula, n is an integer of 2-5. } Is contained in an amount of 0.10% by weight or more and 25% by weight or less of the hydrocarbon compound, which is a surface treatment agent for polyurethane elastic fibers.
[12] The polyurethane elastic fiber according to the above [11], which contains the hydrocarbon compound represented by the formula (1) having n = 3 in an amount of 0.10% by weight or more and 20% by weight or less. Surface treatment agent.
[13] The polyurethane elasticity according to the above [11] or [12], further containing a hydrocarbon compound other than the hydrocarbon compound represented by the formula (1) in which n is an integer of 2 to 5. fiber.
[14] In the GC / MS measurement of the solution dissolved in hexane, the area of the component occupying the retention time longer than the retention time of triacontane in the total area of the peak derived from the hydrocarbon compound is less than 5%. ] To [13]. The surface treatment agent for polyurethane elastic fibers.
[15] In the GC / MS measurement of the solution dissolved in hexane, the area of the component occupying the retention time longer than the retention time of octocosan is less than 5% in the total area of the peak derived from the hydrocarbon compound. ] To [14]. The surface treatment agent for polyurethane elastic fibers according to any one of [14].
[16] In the GC / MS measurement of the solution dissolved in hexane, less than 5% of the total area of the peak derived from the hydrocarbon compound occupies the holding time shorter than the holding time of hexadecane. The surface treatment agent for polyurethane elastic fibers according to any one of [15].
[17] In the GC / MS measurement of the solution dissolved in hexane, less than 20% of the total area of the peak derived from the hydrocarbon compound occupies the holding time shorter than the holding time of octadecane. [11] The surface treatment agent for polyurethane elastic fibers according to any one of [16].
[18] In the GC / MS measurement of the solution dissolved in hexane, the area of the component occupied during the retention time of octadecane and octocosan is 80% or more of the total area of the peak derived from the hydrocarbon compound. ] To [17]. The surface treatment agent for polyurethane elastic fibers according to any one of [17].
[19] The surface treatment agent for polyurethane elastic fibers according to any one of [11] to [18] above, further containing 20% by weight or more and 70% by weight or less of silicone oil.

本発明に係る特定の分岐炭化水素化合物を特定量含有したポリウレタン弾性繊維は、シリコーンオイルの含有量が少なくても、解舒性が良好であり、マルチフィラメントの単糸バラけが少ないポリウレタン弾性繊維である。それゆえ、本発明に係るポリウレタン弾性繊維は、布帛、衛生材料製品等に好適に利用可能である。 The polyurethane elastic fiber containing a specific amount of a specific branched hydrocarbon compound according to the present invention is a polyurethane elastic fiber having good detonability even if the content of silicone oil is small and having little variation in single yarn of a multifilament. be. Therefore, the polyurethane elastic fiber according to the present invention can be suitably used for fabrics, sanitary material products and the like.

炭化水素化合物のＧＣ／ＭＳ測定における全ピーク面積の算出例を示すグラフである。It is a graph which shows the calculation example of the total peak area in the GC / MS measurement of a hydrocarbon compound. 炭化水素化合物の全ピーク面積のうちオクタデカンよりも保持時間の短い成分の面積の算出例を示すグラフである。It is a graph which shows the calculation example of the area of the component which has a shorter retention time than octadecane among the total peak area of a hydrocarbon compound. 炭化水素化合物の全ピーク面積のうちオクタデカンとオクトコサンの間の保持時間の成分の面積の算出例ヘキサンによる抽出液のＧＣ／ＭＳ測定。Calculation example of the area of the retention time component between octadecane and octocosan in the total peak area of the hydrocarbon compound GC / MS measurement of the extract with hexane. 単糸バラけ状態を示す説明図である。It is explanatory drawing which shows the single yarn loosening state.

以下、本発明を実施するための形態（以下「本実施形態」という）について詳細に説明する。尚、本発明は、以下の実施形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。 Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

本発明の１の実施形態は、下記式（１）：

Figure 2020250994
｛式中、ｎは２〜５の整数である。｝で表される炭化水素化合物（以下、特定化合物ともいう。）を、ポリウレタン弾性繊維重量に対して１０ｐｐｍ以上１００００ｐｐｍ以下で含有することを特徴とするポリウレタン弾性繊維である。One embodiment of the present invention has the following formula (1):
Figure 2020250994
 {In the formula, n is an integer of 2-5. }, The polyurethane elastic fiber is characterized by containing a hydrocarbon compound (hereinafter, also referred to as a specific compound) in an amount of 10 ppm or more and 10000 ppm or less with respect to the weight of the polyurethane elastic fiber.

また、本発明の他の実施形態は、下記式（１）：

Figure 2020250994
｛式中、ｎは２〜５の整数である。｝で表される炭化水素化合物を、０．１０重量％以上２５重量％以下で含有することを特徴とするポリウレタン弾性繊維用表面処理剤である。Further, another embodiment of the present invention has the following formula (1):
Figure 2020250994
 {In the formula, n is an integer of 2-5. } Is a surface treatment agent for polyurethane elastic fibers, which comprises 0.10% by weight or more and 25% by weight or less of the hydrocarbon compound represented by.

本実施形態のポリウレタン弾性繊維において、前記特定化合物の含有量を前記特定範囲内にすることで解舒性が向上する理由は定かではないが、そうすることで、前記化合物がポリウレタン弾性繊維の表面上に局在化しやすくなり、表面での前記化合物の流動性の高さから解舒性を向上させることができると考えられる。
前記特定化合物の含有量が１０ｐｐｍ未満であると、十分な解舒性向上効果を発揮することが難しく、より高い解舒性が得られるという観点からは３０ｐｐｍ以上であることが好ましい。他方、含有量が１００００ｐｐｍを超えると、単糸バラけが発生しやすくなり、また、経時での解舒性が悪化する傾向がある。前記特定化合物の含有量の好ましい上限としては９０００ｐｐｍ以下であり、さらに好ましくは５０００ｐｐｍ以下である。
前記特定化合物のポリウレタン弾性繊維への含有の状態としては、前記特定化合物はポリウレタン弾性繊維の内部に含有していても、表面に付着していてもよい。また、前記特定化合物のポリウレタン弾性繊維への含有のさせ方としては、前記特定化合物又は前記特定化合物とそれ以外の炭化水素化合物からなる混合物を紡糸原液に直接練りこんでもよいし、前記特定化合物又は前記特定化合物とそれ以外の炭化水素化合物からなる混合物を表面処理剤に添加し糸表面に塗布する方法のいずれでも構わない。In the polyurethane elastic fiber of the present embodiment, the reason why the solubilization property is improved by keeping the content of the specific compound within the specific range is not clear, but by doing so, the compound is the surface of the polyurethane elastic fiber. It is considered that the compound is easily localized on the surface, and the elasticity of the compound can be improved due to the high fluidity of the compound on the surface.
When the content of the specific compound is less than 10 ppm, it is difficult to exert a sufficient effect of improving the solvability, and it is preferable that the content is 30 ppm or more from the viewpoint of obtaining higher solvability. On the other hand, when the content exceeds 10000 ppm, single yarn disintegration tends to occur, and the unfoldability with time tends to deteriorate. The upper limit of the content of the specific compound is preferably 9000 ppm or less, more preferably 5000 ppm or less.
As for the state of the specific compound contained in the polyurethane elastic fiber, the specific compound may be contained inside the polyurethane elastic fiber or may be attached to the surface thereof. Further, as a method of incorporating the specific compound into the polyurethane elastic fiber, the specific compound or a mixture of the specific compound and a hydrocarbon compound other than the specific compound may be directly kneaded into the spinning stock solution, or the specific compound or Any method may be used in which a mixture of the specific compound and other hydrocarbon compounds is added to the surface treatment agent and applied to the thread surface.

前記表面処理剤中の前記特定化合物の含有量は、０．１０重量％以上２５重量％以下であることが好ましく、また、前記炭化水素混合物の含有量としては、単糸バラけを抑制する観点から２０重量％以下が好ましく、より好ましくは１７重量％以下である。 The content of the specific compound in the surface treatment agent is preferably 0.10% by weight or more and 25% by weight or less, and the content of the hydrocarbon mixture is from the viewpoint of suppressing single yarn dispersal. It is preferably 20% by weight or less, and more preferably 17% by weight or less.

単糸バラけ抑制と平滑性の観点から、前記化合物は、式中、ｎ＝２〜３である前記式（１）で表される炭化水素化合物が好ましく、より好ましくは式中、ｎ＝３である化合物、すなわち、フィタンである。
尚、１の実施形態のポリウレタン弾性繊維では、式中、ｎ＝３である前記式（１）で表される炭化水素化合物をポリウレタン弾性繊維重量に対して１０ｐｐｍ以上８０００ｐｐｍ以下で含有することが好ましい。
また、他の実施形態であるポリウレタン弾性繊維用表面処理剤では、式中、ｎ＝３である前記式（１）で表される炭化水素化合物を、０．１０重量％以上２０重量％以下で含有することが好ましい。From the viewpoint of suppressing single yarn dispersal and smoothness, the compound is preferably a hydrocarbon compound represented by the above formula (1) in which n = 2 to 3 in the formula, and more preferably n = 3 in the formula. Is a compound, i.e., phytane.
The polyurethane elastic fiber of the first embodiment preferably contains the hydrocarbon compound represented by the formula (1) having n = 3 in the formula at 10 ppm or more and 8000 ppm or less with respect to the weight of the polyurethane elastic fiber. ..
Further, in the surface treatment agent for polyurethane elastic fibers according to another embodiment, the hydrocarbon compound represented by the above formula (1) having n = 3 in the formula is contained in an amount of 0.10% by weight or more and 20% by weight or less. It is preferable to contain it.

本実施形態のポリウレタン弾性繊維は、ポリウレタン重合体を紡糸することにより得られる繊維である。前記ポリウレタン重合体を製造する方法に関しては、公知のポリウレタン化反応の技術を用いることができる。高分子ポリオール、例えば、ポリアルキレンエーテルグリコールと、ジイソシアネートとをジイソシアネート過剰の条件下で反応させ、末端にイソシアネート基を有するウレタンプレポリマーを合成し、次いで、このウレタンプレポリマーを２官能性アミン等の活性水素含有化合物で鎖伸張反応を行い、ポリウレタン重合体を得ることができる。この際、必要に応じて末端停止剤として単官能性活性水素原子を２官能性アミンに混合して用いてもよい。ゲルが少なく、均一なポリマーが得られるという観点からは、ジイソシアネートと高分子ポリオールのモル比は１．７０以下であることが好ましく、より好ましくは１．６５以下、さらに好ましくは１．６０以下である。 The polyurethane elastic fiber of the present embodiment is a fiber obtained by spinning a polyurethane polymer. As for the method for producing the polyurethane polymer, a known polyurethane reaction technique can be used. A high molecular weight polyol, for example, polyalkylene ether glycol and diisocyanate are reacted under the condition of excess diisocyanate to synthesize a urethane prepolymer having an isocyanate group at the terminal, and then this urethane prepolymer is used as a bifunctional amine or the like. A polyurethane polymer can be obtained by carrying out a chain extension reaction with an active hydrogen-containing compound. At this time, if necessary, a monofunctional active hydrogen atom may be mixed with the bifunctional amine and used as a terminal terminator. From the viewpoint of obtaining a uniform polymer with less gel, the molar ratio of the diisocyanate to the polymer polyol is preferably 1.70 or less, more preferably 1.65 or less, still more preferably 1.60 or less. be.

高分子ポリオールとしては、実質的に線状のホモ又は共重合体からなる各種ジオール、例えば、ポリエステルジオール、ポリエーテルジオール、ポリエステルアミドジオール、ポリアクリルジオール、ポリチオエステルジオール、ポリチオエーテルジオール、ポリカーボネートジオール、これらの混合物、及びこれらの共重合物等が挙げられ、好ましくは、ポリアルキレンエーテルグリコールであり、例えば、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリテトラメチレンエーテルグリコール、ポリオキシペンタメチレングリコール、テトラメチレン基と２，２−ジメチルプロピレン基から成る共重合ポリエーテルグリコール、テトラメチレン基と３−メチルテトラメチレン基から成る共重合ポリエーテルグリコール、及びこれらの混合物等である。これらの中でも、優れた弾性機能を示すという観点からは、高分子ポリオールとしては、ポリテトラメチレンエーテルグリコール、テトラメチレン基と２，２−ジメチルプロピレン基から成る共重合ポリエーテルグリコールがより好適である。 Examples of the high-polymer polyol include various diols consisting of substantially linear homo or copolymers, for example, polyester diols, polyether diols, polyester amide diols, polyacrylic diols, polythioester diols, polythio ether diols, and polycarbonate diols. Examples thereof include a mixture thereof and a copolymer thereof, and preferred are polyalkylene ether glycols, for example, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, polyoxypentamethylene glycol, and tetra. A copolymerized polyether glycol composed of a methylene group and a 2,2-dimethylpropylene group, a copolymerized polyether glycol composed of a tetramethylene group and a 3-methyltetramethylene group, and a mixture thereof. Among these, from the viewpoint of exhibiting excellent elastic function, as the polymer polyol, polytetramethylene ether glycol and a copolymerized polyether glycol composed of a tetramethylene group and a 2,2-dimethylpropylene group are more preferable. ..

高分子ポリオールの水酸基価から算出される数平均分子量は、優れた弾性性能を得るためには、５００以上であることが好ましく、より好ましくは１０００以上、さらにより好ましくは１５００以上である。また、高い耐熱性の糸が得られるという観点からは、５０００以下であることが好ましく、より優れた耐熱性を得るためには３０００以下が好ましく、より好ましくは２５００以下である。 The number average molecular weight calculated from the hydroxyl value of the polymer polyol is preferably 500 or more, more preferably 1000 or more, and even more preferably 1500 or more in order to obtain excellent elastic performance. Further, from the viewpoint of obtaining a yarn having high heat resistance, it is preferably 5000 or less, and in order to obtain more excellent heat resistance, it is preferably 3000 or less, more preferably 2500 or less.

ジイソシアネートとしては、脂肪族、脂環族、芳香族のジイソシアネート等が挙げられる。例えば、４，４’−ジフェニルメタンジイソシアネート、２，４’−ジフェニルメタンジイソシアネート、２，４−又は２，６−トリレンジイソシアネート、ｍ−又はｐ−キシリレンジイシシアネート、α，α，α’，α’−テトラメチル−キシリレンジイソシアネート、４，４’−ジフェニルエーテルジイソシアネート、４，４’−ジシクロヘキシルジイソシアネート、１，３−又は１，４−シクロヘキシレンジイソシアネート、３−（α−イソシアナートエチル）フェニルイソシアネート、１，６−ヘキサメチレンジイソシアネート、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、イソホロンジイソシアネート、これらの混合物、及びこれらの共重合物等が挙げられ、これらの中でもより好ましくは、４，４’−ジフェニルメタンジイソシアネートである。 Examples of the diisocyanate include aliphatic, alicyclic, and aromatic diisocyanates. For example, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, m- or p-xylylene diisocyanate, α, α, α', α'. -Tetramethyl-xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-dicyclohexyl diisocyanate, 1,3- or 1,4-cyclohexamethylene diisocyanate, 3- (α-isocyanatoethyl) phenyl isocyanate, 1 , 6-Hexamethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, mixtures thereof, copolymers thereof and the like, and among these, 4,4'-diphenylmethane diisocyanate is more preferable.

活性水素含有化合物、すなわち、多官能性活性水素原子を有する鎖延長剤としては、例えば、ヒドラジン、ポリヒドラジン、エチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、２，２−ジメチル−１，３−プロパンジオール、ジエチレングリコール、ジプロピレングリコール、１，４−シクロヘキサンジメタノール、フェニルジエタノールアミン等の低分子ジオールや、エチレンジアミン、１，２−プロピレンジアミン、１，３−プロピレンジアミン、２−メチル−１，５−ペンタンジアミン、トリエチレンジアミン、ｍ−キシリレンジアミン、ピペラジン、ｏ−、ｍ−又はｐ−フェニレンジアミン、１，３−ジアミノシクロヘキサン、１，４−ジアミノシクロヘキサン、１，６−ヘキサメチレンジアミン、Ｎ，Ｎ’−（メチレンジ−４，１−フェニレン）ビス［２−（エチルアミノ）−ウレア］等の２官能性アミンが挙げられる。 Examples of the chain extender having an active hydrogen-containing compound, that is, a polyfunctional active hydrogen atom, include hydrazine, polyhydrazine, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, and 1,3-butane. Diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, Low molecular weight diols such as phenyldiethanolamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 2-methyl-1,5-pentanediamine, triethylenediamine, m-xylylenediamine, piperazine, o-, m- or p-phenylenediamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,6-hexamethylenediamine, N, N'-(methylenedi-4,1-phenylene) bis [2- (ethyl) Bifunctional amines such as amino) -urea] can be mentioned.

これらは単独で、又は混合して用いることができる。低分子ジオールより２官能性アミンが好ましく、エチレンジアミン、１，２−プロピレンジアミン、１，３−ジアミノシクロヘキサン、及び２−メチル−１，５−ペンタジアミンの群から選ばれる少なくとも１種が５〜４０モル％含まれるエチレンジアミン混合物が好ましいものとして挙げられ、より好ましくは、エチレンジアミン単独である。 These can be used alone or in combination. Bifunctional amines are preferred over low molecular weight diols, with at least one selected from the group ethylenediamine, 1,2-propylenediamine, 1,3-diaminocyclohexane, and 2-methyl-1,5-pentadiamine being 5-40. Ethylenediamine mixture containing mol% is mentioned as preferable, and ethylenediamine alone is more preferable.

単官能性活性水素原子を有する末端停止剤としては、例えば、メタノール、エタノール、２−プロパノール、２−メチル−２−プロパノール、１−ブタノール、２−エチル−１−ヘキサノール、３−メチル−１−ブタノール等のモノアルコールや、イソプロピルアミン、ｎ−ブチルアミン、ｔ−ブチルアミン、２−エチルヘキシルアミン等のモノアルキルアミンや、ジエチルアミン、ジメチルアミン、ジ−ｎ−ブチルアミン、ジ−ｔ−ブチルアミン、ジイソブチルアミン、ジ−２−エチルヘキシルアミン、及びジイソプロピルアミン等のジアルキルアミンが挙げられる。これらは単独で、又は混合して用いることができる。モノアルコールより、１官能性アミンであるモノアルキルアミンまたはジアルキルアミンが好ましい。 Examples of the terminal terminator having a monofunctional active hydrogen atom include methanol, ethanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-ethyl-1-hexanol, and 3-methyl-1-. Monoalcohols such as butanol, monoalkylamines such as isopropylamine, n-butylamine, t-butylamine, 2-ethylhexylamine, diethylamine, dimethylamine, di-n-butylamine, di-t-butylamine, diisobutylamine, di Examples thereof include -2-ethylhexylamine and dialkylamines such as diisopropylamine. These can be used alone or in combination. Monoalkylamines or dialkylamines, which are monofunctional amines, are preferable to monoalcohols.

ポリウレタン化反応の操作に関しては、ウレタンプレポリマー合成時やウレタンプレポリマーと活性水素含有化合物との反応時に、ジメチルホルムアミド、ジメチルスルホキシド、及びジメチルアセトアミド等のアミド系極性溶媒を用いることができ、好ましくはジメチルアセトアミドである。 Regarding the operation of the polyurethaneization reaction, an amide-based polar solvent such as dimethylformamide, dimethylsulfoxide, and dimethylacetamide can be used during the synthesis of the urethane prepolymer or the reaction between the urethane prepolymer and the active hydrogen-containing compound, and is preferable. It is dimethylacetamide.

ポリウレタン重合体組成物には、各種安定剤や顔料などが含有されていてもよい。例えば、ヒンダードフェノール系、ベンゾトリアゾール系、ベンゾフェノン系、リン系、各種ヒンダードアミン系の酸化防止剤、ステアリン酸マグネシウムで代表されるような金属石鹸、酸化チタン、酸化鉄、酸化亜鉛、酸化セリウム、酸化マグネシウム等の無機物、カーボンブラック、各種顔料、銀、亜鉛、これらの化合物などを含む抗菌剤、消臭剤、帯電防止剤、酸化窒素捕捉剤、熱酸化安定剤、光安定剤等を併用して含有してもよい。
また、単糸のバラけを抑制するためにアルコールとカルボン酸又はリン酸の縮合物からなるエステル化合物やリン酸エステル化合物を含有してもよい。エステル化合物やリン酸エステル化合物の好適な例としては、クエン酸トリメチルやアジピン酸ビス（２−エチルヘキシル）、安息香酸メチル、安息香酸ベンジル、ジ安息香酸ジエチレングリコール、ジ安息香酸ジプロピレングリコール、トリメット酸トリメチル、フタル酸ジブチル、リン酸トリクレジル、リン酸ジフェニル２−エチルヘキシル等が挙げられ、また、上記化合物のいずれか２つ以上を組み合わせて使用してもよい。The polyurethane polymer composition may contain various stabilizers, pigments and the like. For example, hindered phenol-based, benzotriazole-based, benzophenone-based, phosphorus-based, various hindered amine-based antioxidants, metal soaps such as magnesium stearate, titanium oxide, iron oxide, zinc oxide, cerium oxide, oxidation. Inorganic substances such as magnesium, carbon black, various pigments, silver, zinc, antibacterial agents containing these compounds, deodorants, antistatic agents, nitrogen oxide trapping agents, thermal oxidation stabilizers, light stabilizers, etc. It may be contained.
Further, an ester compound or a phosphoric acid ester compound composed of a condensate of alcohol and a carboxylic acid or a phosphoric acid may be contained in order to suppress the disintegration of the single yarn. Suitable examples of ester compounds and phosphate ester compounds are trimethyl citrate, bis (2-ethylhexyl) adipate, methyl benzoate, benzyl benzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, trimethyl trimetate. , Dibutyl phthalate, tricresyl phosphate, diphenyl 2-ethylhexyl phosphate and the like, and any two or more of the above compounds may be used in combination.

このようにして得られたポリウレタン重合体は、公知の乾式紡糸、溶融紡糸又は湿式紡糸法等で繊維状に成形し、ポリウレタン弾性繊維を得ることができる。また、異なる原料を用いて重合したポリウレタン重合体を紡糸の前段階で混合して紡糸してもよい。好ましい紡糸方法としては、ポリウレタン重合体をアミド系極性溶媒に溶解して得られたポリウレタン紡糸原液を乾式紡糸である。乾式紡糸は、溶融紡糸や湿式紡糸に比べて、ハードセグメント間の水素結合による物理架橋を最も強固に形成させることができる。 The polyurethane polymer thus obtained can be formed into fibers by a known dry spinning, melt spinning, wet spinning method or the like to obtain polyurethane elastic fibers. Further, polyurethane polymers polymerized using different raw materials may be mixed and spun at the pre-spinning stage. As a preferred spinning method, a polyurethane spinning stock solution obtained by dissolving a polyurethane polymer in an amide-based polar solvent is used for dry spinning. Compared with melt spinning and wet spinning, dry spinning can form the strongest physical cross-linking due to hydrogen bonds between hard segments.

本実施形態のポリウレタン弾性繊維は、解舒時の抵抗や使用時の摩擦を低減するために表面処理剤を含有させて使用することができる。表面処理剤は、紡糸原液にあらかじめ練りこんでおいてもよいし、紡糸時に紙管に巻き取る前にロールオイリングや、ガイドオイリング等の公知の方法によって付与してもよい。あるいは表面処理剤を付与せずに巻き取った後に巻き返して別の巻糸体を作る工程で表面処理剤を付与しても構わない。ポリウレタン弾性繊維へ表面処理剤を含有させる際、コスト及び品質の観点からは、ポリウレタン弾性繊維重量に対する表面処理剤の含有量は１．０重量％以上４．０重量％以下が好ましく、表面処理剤としては前記含有率の全範囲において所望の効果が奏されることが好ましい。 The polyurethane elastic fiber of the present embodiment can be used by containing a surface treatment agent in order to reduce resistance during unwinding and friction during use. The surface treatment agent may be kneaded into the undiluted spinning solution in advance, or may be applied by a known method such as roll oiling or guide oiling before winding on a paper tube at the time of spinning. Alternatively, the surface treatment agent may be applied in the step of winding without applying the surface treatment agent and then rewinding to make another winding body. When the surface treatment agent is contained in the polyurethane elastic fiber, the content of the surface treatment agent with respect to the weight of the polyurethane elastic fiber is preferably 1.0% by weight or more and 4.0% by weight or less, and the surface treatment agent. It is preferable that the desired effect is exhibited in the entire range of the content.

表面処理剤の構成としては、特に限定されないが、ポリジメチルシロキサン、ポリエステル変性シリコーン、ポリエーテル変性シリコーン、アミノ変性シリコーンなどのシリコーンオイルや、後述する炭化水素化合物、鉱物性微粒子、例えば、シリカ、コロイダルアルミナ、タルク等、高級脂肪酸金属塩粉末、例えば、ステアリン酸マグネシウム、ステアリン酸カルシウム等、高級脂肪族カルボン酸、高級脂肪族アルコール、パラフィン、及びポリエチレン等の常温で固形状ワックス等の公知の表面処理剤を組み合わせて使用することができる。シリコーンオイルとしてはポリジメチルシロキサンが好ましく、摩擦の低減という観点からは２５℃における動粘度が１５ｍｍ２／ｓ以下であることが好ましい。またシリコーンオイルの含有量としては、単糸バラけを抑制できるという観点から、ポリウレタン弾性繊維に対して２．０重量％以下が好ましく、より好ましくは１．５重量％以下、さらに好ましくは１．０重量％以下である。The composition of the surface treatment agent is not particularly limited, but is limited to silicone oils such as polydimethylsiloxane, polyester-modified silicone, polyether-modified silicone, and amino-modified silicone, hydrocarbon compounds described later, mineral fine particles, for example, silica, colloidal. Known surface treatment agents such as higher fatty acid metal salt powders such as alumina and talc, for example, higher aliphatic carboxylic acids such as magnesium stearate and calcium stearate, higher aliphatic alcohols, paraffins, and polyethylene solid wax at room temperature. Can be used in combination. Polydimethylsiloxane is preferable as the silicone oil, and the kinematic viscosity at 25 ° C. is preferably 15 mm 2 / s or less from the viewpoint of reducing friction. The content of the silicone oil is preferably 2.0% by weight or less, more preferably 1.5% by weight or less, still more preferably 1. It is 0% by weight or less.

本実施形態のポリウレタン弾性繊維が含有する炭化水素化合物は、炭素と水素のみからなる化合物である。本実施形態のポリウレタン弾性繊維は、前記特定化合物以外の炭化水素化合物を含有してもよい。 The hydrocarbon compound contained in the polyurethane elastic fiber of the present embodiment is a compound consisting only of carbon and hydrogen. The polyurethane elastic fiber of the present embodiment may contain a hydrocarbon compound other than the specific compound.

本実施形態のポリウレタン弾性繊維は、後述の方法にてヘキサンで抽出した溶液のＧＣ／ＭＳによって測定される前記特定化合物のピーク面積と前記特定化合物以外の炭化水素化合物のピーク面積の和で示される炭化水素化合物由来のピークの全面積のうち、保持時間が同条件で測定されるトリアコンタンよりも長い成分の面積が５％未満であることが好ましい。前記の炭化水素化合物由来のピークの全面積のうちトリアコンタンの保持時間よりも保持時間の長い成分の面積が５％未満であると、式中、ｎ＝２〜５である前記式（１）の特定化合物の流動性が良好となるため、式中、ｎ＝２〜５である前記式（１）の特定化合物がポリウレタン弾性繊維の表面上に局在化しやすくなり、解舒性をさらに高めることができると考えている。トリアコンタンの保持時間よりも保持時間の長い成分のより好ましい面積としては３％未満である。
本実施形態のポリウレタン弾性繊維は、後述の方法にてヘキサンで抽出したＧＣ／ＭＳによって測定される前記特定化合物のピーク面積と前記特定化合物以外の炭化水素化合物のピーク面積の和で示される炭化水素化合物由来のピークの全面積のうち、保持時間が同条件で測定されるオクトコサンよりも長い成分の面積が５％未満であることがさらに好ましい。前記の炭化水素化合物由来のピークの全面積のうちオクトコサンの保持時間よりも保持時間の長い成分の面積が５％未満であると、式中、ｎ＝２〜５である前記式（１）の特定化合物の流動性が良好となるため、式中、ｎ＝２〜５である前記式（１）の特定化合物がポリウレタン弾性繊維の表面上にさらに局在化しやすくなり、解舒性をよりいっそう高めることができると考えている。オクトコサンの保持時間よりも保持時間の長い成分のより好ましい面積としては３％未満である。The polyurethane elastic fiber of the present embodiment is represented by the sum of the peak area of the specific compound measured by GC / MS of the solution extracted with hexane by the method described later and the peak area of a hydrocarbon compound other than the specific compound. Of the total area of the peak derived from the hydrocarbon compound, the area of the component having a retention time longer than that of triacontane measured under the same conditions is preferably less than 5%. When the area of the component having a retention time longer than that of triacontane is less than 5% of the total area of the peak derived from the hydrocarbon compound, n = 2 to 5 in the formula (1). Since the fluidity of the specific compound of the above formula is improved, the specific compound of the above formula (1) having n = 2 to 5 in the formula is easily localized on the surface of the polyurethane elastic fiber, further enhancing the solubilization property. I think I can do it. A more preferred area of the component having a longer retention time than the retention time of triacontane is less than 3%.
The polyurethane elastic fiber of the present embodiment is a hydrocarbon represented by the sum of the peak area of the specific compound measured by GC / MS extracted with hexane by the method described later and the peak area of a hydrocarbon compound other than the specific compound. It is more preferable that the area of the component having a retention time longer than that of octocosan measured under the same conditions is less than 5% of the total area of the peak derived from the compound. When the area of the component having a retention time longer than that of octocosan is less than 5% of the total area of the peak derived from the hydrocarbon compound, n = 2 to 5 in the formula (1). Since the fluidity of the specific compound becomes good, the specific compound of the above formula (1) having n = 2 to 5 in the formula is more easily localized on the surface of the polyurethane elastic fiber, further improving the solubilization property. I think it can be enhanced. A more preferable area of the component having a retention time longer than that of octocosan is less than 3%.

本実施形態のポリウレタン弾性繊維は、後述の方法にてヘキサンで抽出したＧＣ／ＭＳによって測定される前記特定化合物のピーク面積と前記特定化合物以外の炭化水素化合物のピーク面積の和で示される炭化水素化合物由来のピークの全面積のうち、保持時間が同条件で測定されるヘキサデカンよりも短い成分の面積が５％未満であることが好ましい。前記の炭化水素化合物由来のピークの全面積のうちヘキサデカンの保持時間よりも保持時間の短い成分の面積が５％未満であると、炭化水素化合物の流動性が適度であるためポリウレタン弾性繊維の単糸バラけが起こりにくくなり、糸切れ等が起こりにくくなると考えられる。ヘキサデカンの保持時間よりも保持時間が短い成分のより好ましい面積としては３％未満である。 The polyurethane elastic fiber of the present embodiment is a hydrocarbon represented by the sum of the peak area of the specific compound measured by GC / MS extracted with hexane by the method described later and the peak area of a hydrocarbon compound other than the specific compound. Of the total area of the peak derived from the compound, it is preferable that the area of the component having a retention time shorter than that of hexadecane measured under the same conditions is less than 5%. When the area of the component whose retention time is shorter than the retention time of hexadecane is less than 5% of the total area of the peak derived from the hydrocarbon compound, the fluidity of the hydrocarbon compound is appropriate, so that the polyurethane elastic fiber is simply used. It is considered that thread loosening is less likely to occur and thread breakage is less likely to occur. A more preferable area of the component having a shorter retention time than the retention time of hexadecane is less than 3%.

本実施形態のポリウレタン弾性繊維は、後述の方法にてヘキサンで抽出したＧＣ／ＭＳによって測定される前記特定化合物のピーク面積と前記特定化合物以外の炭化水素化合物のピーク面積の和で示される炭化水素化合物由来のピークの全面積のうち、保持時間が同条件で測定されるオクタデカンよりも短い成分の面積が２０％未満であることが好ましい。前記の炭化水素化合物由来のピークの全面積のうちオクタデカンの保持時間よりも保持時間の短い成分の面積が２０％未満であると、炭化水素の流動性がより適度となるためポリウレタン弾性繊維の単糸バラけが起こりにくくなり、糸切れ等が起こりにくくなると考えられる。オクタデカンの保持時間よりも保持時間が短い成分のより好ましい面積としては１５％未満である。 The polyurethane elastic fiber of the present embodiment is a hydrocarbon represented by the sum of the peak area of the specific compound measured by GC / MS extracted with hexane by the method described later and the peak area of a hydrocarbon compound other than the specific compound. Of the total area of the peak derived from the compound, the area of the component having a retention time shorter than that of octadecane measured under the same conditions is preferably less than 20%. If the area of the component whose retention time is shorter than the retention time of octadecane is less than 20% of the total area of the peak derived from the hydrocarbon compound, the fluidity of the hydrocarbon becomes more appropriate, so that the polyurethane elastic fiber is simply used. It is considered that thread loosening is less likely to occur and thread breakage is less likely to occur. A more preferred area of the component having a shorter retention time than the retention time of octadecane is less than 15%.

本実施形態のポリウレタン弾性繊維は、後述の方法にてヘキサンで抽出したＧＣ／ＭＳによって測定される前記特定化合物のピーク面積と前記特定化合物以外の炭化水素化合物のピーク面積の和で示される炭化水素化合物由来のピークの全面積のうち、保持時間が同条件で測定されるオクタデカンとオクトコサンの保持時間の間に含まれる成分の面積が８０％以上であることが好ましい。前記の炭化水素化合物由来のピークの全面積のうち、保持時間がオクタデカンとオクトコサンの保持時間の間に含まれる成分の面積が８０％以上であると、炭化水素化合物の流動性がさらに適度になり、単糸バラけの発生率を上げることなく、解舒性向上効果をさらに改善することができる。オクタデカンとオクトコサンの保持時間の間の成分の面積としては９０％以上であることが好ましく、より好ましくは９５％以上である。 The polyurethane elastic fiber of the present embodiment is a hydrocarbon represented by the sum of the peak area of the specific compound measured by GC / MS extracted with hexane by the method described later and the peak area of a hydrocarbon compound other than the specific compound. Of the total area of the peak derived from the compound, the area of the component contained between the retention times of octadecane and octokosan measured under the same conditions is preferably 80% or more. When the area of the component contained in the retention time between the retention time of octadecane and the retention time of octocosan is 80% or more of the total area of the peak derived from the hydrocarbon compound, the fluidity of the hydrocarbon compound becomes more appropriate. , The effect of improving the solvability can be further improved without increasing the occurrence rate of single yarn disintegration. The area of the component during the retention time of octadecane and octocosan is preferably 90% or more, more preferably 95% or more.

尚、前記ＧＣ／ＭＳによって測定される各成分の面積は、本発明の他の実施形態である表面処理剤においても同様である。 The area of each component measured by the GC / MS is the same for the surface treatment agent according to another embodiment of the present invention.

前記特定化合物以外の炭化水素化合物としては、炭素と水素のみからなる化合物であれば特に限定はないが、軽質イソパラフィン、合成スクワラン、植物性スクワラン、スクワラン、セレシン、パラフィン、ワセリン、マシン油、スピンドル油、ナフテン油、流動パラフィン、流動イソパラフィン、ポリアルファオレフィン、ポリイソブチレン、ポリブテン等が挙げられ、１種又は２種以上を使用してもよい。また、それらの炭化水素化合物の中に前記特定化合物が予め含まれていても構わない。式中、ｎ＝２〜５である前記式（１）の化合物との相乗効果の得られる好適な例としては、流動パラフィンが好ましく、その平均分子量は４５０未満であることがより好ましい。また、それらは飽和炭化水素のみからなることが好ましい。さらに好ましくは流動パラフィンのパラフィン／ナフテン比が５０／５０〜８０／２０の範囲である。さらにより好ましくは流動パラフィンの製法が水素化法ではなく、硫酸洗浄による不純物除去を得て製造されたものであると前述の特徴を満たす炭化水素化合物を得やすい。前記特定化合物と前記特定化合物以外の炭化水素化合物の合計含有量としては、単糸バラけを抑制できるという観点から糸に対して２．０重量％以下がよく、１．５重量％以下がより好ましい。 The hydrocarbon compound other than the specific compound is not particularly limited as long as it is a compound consisting only of carbon and hydrogen, but is light isoparaffin, synthetic squalane, vegetable squalane, squalane, ceresin, paraffin, vaseline, machine oil, and spindle oil. , Naften oil, liquid paraffin, liquid isoparaffin, polyalphaolefin, polyisobutylene, polybutene and the like, and one or more of them may be used. Further, the specific compound may be contained in advance in those hydrocarbon compounds. In the formula, liquid paraffin is preferable as a preferable example for obtaining a synergistic effect with the compound of the formula (1) in which n = 2 to 5, and the average molecular weight thereof is more preferably less than 450. Also, they preferably consist only of saturated hydrocarbons. More preferably, the paraffin / naphthenic ratio of liquid paraffin is in the range of 50/50 to 80/20. Even more preferably, if the method for producing liquid paraffin is not a hydrogenation method but a method obtained by removing impurities by washing with sulfuric acid, it is easy to obtain a hydrocarbon compound satisfying the above-mentioned characteristics. The total content of the specific compound and the hydrocarbon compound other than the specific compound is preferably 2.0% by weight or less, and more preferably 1.5% by weight or less with respect to the yarn from the viewpoint of suppressing single yarn dispersal. preferable.

本実施形態のポリウレタン弾性繊維は、綿、絹、羊毛等の天然繊維、ナイロン６やナイロン６６等のポリアミド繊維、ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、ポリテトラメチレンテレフタレート等のポリエステル繊維、カチオン可染ポリエステル繊維、銅アンモニア再生レーヨン、ビスコースレーヨン、及びアセテートレーヨン等と交編織したり、又は、これらの繊維を用いて被覆、交絡、合撚等により加工糸とした後、交編織することによって斑のない高品位な布帛を得ることができる。特にポリウレタン弾性繊維を用いた布帛では生産量が多く、ベア糸で供給されるため、原糸の品位の影響が大きい経編物に好適である。経編生地には、パワーネット、サテンネット、ラッセルレース、ツーウェイトリコットなどがあるが、本実施形態のポリウレタン弾性繊維を用いることで、経方向の筋の少ない高品位な布帛を得ることができる。 The polyurethane elastic fiber of the present embodiment is a natural fiber such as cotton, silk and wool, a polyamide fiber such as nylon 6 and nylon 66, a polyester fiber such as polyethylene terephthalate, polytrimethylene terephthalate and polytetramethylene terephthalate, and a cationic dyeable polyester. By cross-knitting with fibers, copper-ammonia regenerated rayon, viscous rayon, acetate rayon, etc., or by using these fibers to make processed yarn by coating, entanglement, twisting, etc., and then cross-knitting, the spots can be seen. It is possible to obtain a high-quality fabric that does not have any quality. In particular, fabrics using polyurethane elastic fibers have a large production volume and are supplied as bare yarns, and are therefore suitable for warp knits that are greatly affected by the quality of the raw yarns. The warp knitted fabric includes a power net, a satin net, a Russell lace, a two-weight ricott, and the like. By using the polyurethane elastic fiber of the present embodiment, a high-quality fabric with few streaks in the warp direction can be obtained.

本実施形態のポリウレタン弾性繊維を用いた布帛は、水着、ガードル、ブラジャー、タイツ、パンティストッキング、ウェストバンド、ボディースーツ、スパッツ、ストレッチスポーツウェアー、ストレッチアウター、医療用ウェア、ストレッチ裏地等の用途に用いることができる。 The fabric using the polyurethane elastic fiber of the present embodiment is used for swimwear, girdles, bras, tights, pantyhose, waistbands, bodysuits, spats, stretch sportswear, stretch outerwear, medical wear, stretch lining, etc. be able to.

本実施形態のポリウレタン弾性繊維は、生理用品や紙おむつ等の衛生材料製品にも好適に用いることができ、平滑性が良好であり、摩擦性の変動が小さいため、高い生産性と製品の安定性を得ることができる。また式中、ｎ＝２〜５の前記式（１）の特定化合物の解舒性向上効果により、各種接着方法における接着性の阻害因子であるシリコーンオイルを減量することが可能となるため、ホットメルト接着剤や熱プレス、超音波接着等の衛生材料製造装置における各種接着法に対しても好適で、尿漏れ等の問題を引き起こす製品欠陥の一つであるポリウレタン弾性繊維のスリップインと呼ばれる現象の発生率が低く、ストレッチ性の高い衛生材料製品を得ることができる。 The polyurethane elastic fiber of the present embodiment can be suitably used for sanitary material products such as sanitary napkins and disposable diapers, has good smoothness, and has small fluctuation in frictional properties, so that high productivity and product stability are achieved. Can be obtained. Further, in the formula, the effect of improving the unfoldability of the specific compound of the above formula (1) with n = 2 to 5 makes it possible to reduce the amount of silicone oil, which is an inhibitor of adhesiveness in various adhesive methods, and thus is hot. It is also suitable for various bonding methods in sanitary material manufacturing equipment such as melt adhesives, hot presses, and ultrasonic bonding, and is a phenomenon called slip-in of polyurethane elastic fibers, which is one of the product defects that cause problems such as urine leakage. It is possible to obtain a sanitary material product with a low incidence of swelling and high stretchability.

本発明の他の実施形態は、前記したように、式中、ｎが２〜５の整数である前記式（１）の特定化合物を０．１０重量％以上２５重量％以下含有することを特徴とするポリウレタン弾性繊維用表面処理剤である。式中、ｎが２〜５の整数である前記式（１）の特定化合物を上記特定範囲の含有量とすることでポリウレタン弾性繊維の解舒性が向上する理由は定かではないが、そうすることで、上記特定化合物がポリウレタン弾性繊維の表面上に局在化しやすくなり、表面での上記特定化合物の高い含有量に因り解舒性を向上させることができると考えられる。より高い解舒性が得られるという観点からは、上記特定化合物の含有量が、０．１０重量％以上２０重量％以下が好ましく、より好ましくは０．１０重量％以上１７重量％以下である。 As described above, another embodiment of the present invention is characterized by containing 0.10% by weight or more and 25% by weight or less of the specific compound of the formula (1) in which n is an integer of 2 to 5 in the formula. It is a surface treatment agent for polyurethane elastic fibers. In the formula, the reason why the unfoldability of the polyurethane elastic fiber is improved by setting the content of the specific compound of the above formula (1) in which n is an integer of 2 to 5 in the above specific range is not clear, but it does so. Therefore, it is considered that the specific compound is easily localized on the surface of the polyurethane elastic fiber, and the unfoldability can be improved due to the high content of the specific compound on the surface. From the viewpoint of obtaining higher solvability, the content of the specific compound is preferably 0.10% by weight or more and 20% by weight or less, and more preferably 0.10% by weight or more and 17% by weight or less.

本実施形態の繊維用表面処理剤に含有される炭化水素化合物は、炭素と水素のみからなる化合物である。本実施形態の繊維用表面処理剤は、前記特定化合物以外の炭化水素化合物を含有してもよい。前記特定化合物以外の炭化水素化合物としては、軽質イソパラフィン、合成スクワラン、植物性スクワラン、スクワラン、セレシン、パラフィン、ワセリン、マシン油、スピンドル油、ナフテン油、流動パラフィン、流動イソパラフィン、ポリアルファオレフィン、ポリイソブチレン、ポリブテン等が挙げられ、１種又は２種以上を使用してもよい。またそれらの炭化水素化合物の中に前記特定化合物があらかじめ含まれていても構わない。式中、ｎ＝２〜５である前記式（１）の特定化合物との相乗効果の得られる好適な例としては、流動パラフィンが好ましく、その平均分子量は４５０未満であることがより好ましい。またそれらは飽和炭化水素のみからなることが好ましい。さらに好ましくは流動パラフィンのパラフィン／ナフテン比が５０／５０〜８０／２０の範囲である。さらにより好ましくは流動パラフィンの製法が水素化法ではなく、硫酸洗浄による不純物除去を得て製造されたものが好ましい。 The hydrocarbon compound contained in the surface treatment agent for fibers of the present embodiment is a compound consisting only of carbon and hydrogen. The surface treatment agent for fibers of the present embodiment may contain a hydrocarbon compound other than the specific compound. Hydrocarbon compounds other than the above-mentioned specific compounds include light isoparaffin, synthetic squalane, vegetable squalane, squalane, selecin, paraffin, vaseline, machine oil, spindle oil, naphthenic oil, liquid paraffin, liquid isoparaffin, polyalphaolefin, and polyisobutylene. , Polybutene and the like, and one kind or two or more kinds may be used. Further, the specific compound may be contained in advance in those hydrocarbon compounds. In the formula, liquid paraffin is preferable as a preferable example for obtaining a synergistic effect with the specific compound of the formula (1) in which n = 2 to 5, and the average molecular weight thereof is more preferably less than 450. Also, they preferably consist only of saturated hydrocarbons. More preferably, the paraffin / naphthenic ratio of liquid paraffin is in the range of 50/50 to 80/20. Even more preferably, the liquid paraffin is not produced by a hydrogenation method, but is produced by removing impurities by washing with sulfuric acid.

本実施形態の繊維用表面処理剤は、シリコーンオイルを２０重量％以上７０重量％以下でさらに含有することが好ましい。式中、ｎ＝２〜５である前記式（１）の特定化合物を含有し、さらにシリコーンオイルの含有量を上記範囲内とすることで、シリコーンオイルの含有量が７０重量％以下であるにも拘わらず、シリコーンオイルの含有量が７０重量％を超える含有量の繊維用表面処理剤と同等以上の解舒性能を発揮することができる。またシリコーンオイルの含有量が少ないため、単糸バラけの発生を抑制することができ、また高価なシリコーンオイルの使用量を減らすことができるため、シリコーンオイルの含有量が７０重量％を超える含有量の繊維用葉面処理剤に比べて、コストダウン効果が期待できる。シリコーンオイルの含有量が２０重量％未満であると十分な解舒性能を得ることができず、また７０重量％を超えると、単糸バラけが発生しやすくなってしまい、また、コスト面も課題となってしまう。シリコーンオイルとしては、ポリジメチルシロキサンが上げられ、摩擦を低減できるという観点から、２５℃における動粘度が１５ｍｍ２／ｓ以下であることが好ましい。The surface treatment agent for fibers of the present embodiment preferably further contains silicone oil in an amount of 20% by weight or more and 70% by weight or less. By containing the specific compound of the formula (1) in which n = 2 to 5 and further setting the content of the silicone oil within the above range, the content of the silicone oil is 70% by weight or less. Nevertheless, it is possible to exhibit unwinding performance equal to or higher than that of a surface treatment agent for fibers having a silicone oil content of more than 70% by weight. Further, since the content of the silicone oil is small, the occurrence of single yarn loosening can be suppressed, and the amount of expensive silicone oil used can be reduced, so that the content of the silicone oil exceeds 70% by weight. Compared to the amount of foliar treatment agent for fibers, cost reduction effect can be expected. If the content of the silicone oil is less than 20% by weight, sufficient unwinding performance cannot be obtained, and if it exceeds 70% by weight, single yarn disintegration is likely to occur, and cost is also an issue. Will be. As the silicone oil, the kinematic viscosity at 25 ° C. is preferably 15 mm 2 / s or less from the viewpoint that polydimethylsiloxane can be raised and friction can be reduced.

本実施形態の繊維用表面処理剤は、上述のシリコーンオイル、特定化合物、特定化合物以外の炭化水素化合物の他にポリエステル変性シリコーン、ポリエーテル変性シリコーン、アミノ変性シリコーン、鉱物性微粒子、例えば、シリカ、コロイダルアルミナ、タルク等、高級脂肪酸金属塩粉末、例えば、ステアリン酸マグネシウム、ステアリン酸カルシウム等、高級脂肪族カルボン酸、イソステアリルアルコールに代表される高級脂肪族アルコール、パラフィン、及びポリエチレン等の常温で固形状ワックス等の公知の表面処理剤を組み合わせて使用することができる。
また、単糸のバラけを抑制するためにアルコールとカルボン酸又はリン酸の縮合物からなるエステル化合物やリン酸エステル化合物を繊維用表面処理剤に含有してもよい。エステル化合物やリン酸エステル化合物の好適な例としては、クエン酸トリメチルやアジピン酸ビス（２−エチルヘキシル）、安息香酸メチル、安息香酸ベンジル、ジ安息香酸ジエチレングリコール、ジ安息香酸ジプロピレングリコール、トリメット酸トリメチル、フタル酸ジブチル、リン酸トリクレジル、リン酸ジフェニル２−エチルヘキシル等が挙げられ、また、上記化合物のいずれか２つ以上を組み合わせて使用してもよい。The surface treatment agent for fibers of the present embodiment includes polyester-modified silicone, polyether-modified silicone, amino-modified silicone, mineral fine particles such as silica, in addition to the above-mentioned silicone oil, specific compound, and hydrocarbon compound other than the specific compound. Higher fatty acid metal salt powders such as colloidal alumina and talc, for example, higher aliphatic carboxylic acids such as magnesium stearate and calcium stearate, higher aliphatic alcohols typified by isostearyl alcohol, paraffin, and solids at room temperature such as polyethylene. A known surface treatment agent such as wax can be used in combination.
Further, in order to suppress the disintegration of the single yarn, an ester compound composed of a condensate of alcohol and a carboxylic acid or a phosphoric acid or a phosphoric acid ester compound may be contained in the surface treatment agent for fibers. Suitable examples of ester compounds and phosphate ester compounds are trimethyl citrate, bis (2-ethylhexyl) adipate, methyl benzoate, benzyl benzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, trimethyl trimetate. , Dibutyl phthalate, tricresyl phosphate, diphenyl 2-ethylhexyl phosphate and the like, and any two or more of the above compounds may be used in combination.

本実施形態の繊維用表面処理剤は、ロールオイリング、ガイドオイリング、スプレーオイリング等の公知の方法において適用することができる。 The surface treatment agent for fibers of the present embodiment can be applied by known methods such as roll oiling, guide oiling, and spray oiling.

以下、実施例、比較例を挙げて本発明を具体的に説明するが、本発明は実施例により何ら限定されるものではない。尚、以下の実施例、比較例に使用した測定法、評価法等は下記の通りのものであった。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples. The measurement methods, evaluation methods, etc. used in the following examples and comparative examples were as follows.

（１）式中、ｎ＝２〜５である式（１）の特定化合物の同定・定量方法
２ｇに精秤したポリウレタン弾性繊維を５０ｇのヘキサンに浸漬して１０分間超音波をかけて抽出した後、エバポレータでヘキサンを留去した。その後、同じ容器にて抽出後のポリウレタン弾性繊維を再度５０ｇのヘキサンに浸漬し、１０分間超音波をかけて抽出した後、ポリウレタン弾性繊維を取り除き、エバポレータでヘキサンを留去することでヘキサンによる抽出物を得た。この抽出物の濃度が１６００ｐｐｍとなるようヘキサンで希釈したサンプルを抽出液サンプルとして、ＧＣ／ＭＳ測定に供した。尚、抽出物の量が少ない場合は、ポリウレタン弾性繊維を適宜増量して同様の操作を行ってもよい。
詳細なＧＣ／ＭＳの条件は下記の通りであった。
装置 ：Ａｇｉｌｅｎｔ ６８９０ ＧＣ, ＭＳＤ-５９７３
カラム ：ＤＢ−５ＭＳ （３０ｍ、０．２５μｍ、ＩＤ ０．２５ｍｍ）
オーブン：４０℃（２分）−８℃／分―３２０℃（５分）
ＩＮＪ／ＤＥＴ ：３２５℃／３２５℃
ガス ：ヘリウム
流量 ：１．０ｍｌ／分
注入量 ：１．０μｌ
注入方法：Ｓｐｌｉｔ １０：１Method for identifying and quantifying the specific compound of the formula (1) in the formula (1) in which n = 2 to 5 The polyurethane elastic fiber precisely weighed in 2 g was immersed in 50 g of hexane and extracted by ultrasonication for 10 minutes. Later, hexane was distilled off with an evaporator. Then, the extracted polyurethane elastic fiber is immersed in 50 g of hexane again in the same container, extracted by applying ultrasonic waves for 10 minutes, then the polyurethane elastic fiber is removed, and hexane is distilled off with an evaporator to extract with hexane. I got something. A sample diluted with hexane so that the concentration of this extract was 1600 ppm was used as an extract sample for GC / MS measurement. When the amount of the extract is small, the amount of polyurethane elastic fiber may be appropriately increased and the same operation may be performed.
The detailed GC / MS conditions were as follows.
Equipment: Agilent 6890 GC, MSD-5973
Column: DB-5MS (30m, 0.25μm, ID 0.25mm)
Oven: 40 ° C (2 minutes) -8 ° C / min-320 ° C (5 minutes)
INJ / DET: 325 ° C / 325 ° C
Gas: Helium Flow rate: 1.0 ml / min Injection amount: 1.0 μl
Injection method: Split 10: 1

（２）ＧＣ／ＭＳ測定における炭化水素化合物の各面積の算出
前記（１）と同様にしてポリウレタン弾性繊維からの抽出物をＧＣ／ＭＳにて測定し、炭化水素化合物由来の全ピーク面積に対するトリアコンタンよりも保持時間の長い成分の面積をＣ３０以上の成分の面積、オクトコサンよりも保持時間の長い成分の面積をＣ２８以上の成分の面積、ヘキサデカンよりも保持時間の短い成分の面積をＣ１６以下の成分の面積、オクタデカンよりも保持時間の短い成分の面積をＣ１８以下の成分の面積、ヘキサデカンとトリアコンタンの保持時間の間に保持時間を有する成分の面積をＣ１６−Ｃ３０の成分の面積、オクタデカンとトリアコンタンの保持時間の間に保持時間を有する成分の面積をＣ１８−Ｃ３０の成分の面積、オクタデカンとオクトコサンの保持時間の間に保持時間を有する成分の面積をＣ１８−Ｃ２８の成分の面積としてそれぞれ百分率にて算出した。各面積の算出においてＧＣ／ＭＳにて炭化水素化合物由来ではない成分は除去して計算した。炭化水素化合物のピークは混合物の場合、ブロードに検出される場合があるため、その場合はピークの立ち上がり始めを始点とし、ピークの検出値が無視できるレベルまでなくなり始めた点を終点とし、始点と終点を直線で結んだベースラインから面積を算出した。(2) Calculation of each area of the hydrocarbon compound in GC / MS measurement The extract from the polyurethane elastic fiber was measured by GC / MS in the same manner as in (1) above, and the tria with respect to the total peak area derived from the hydrocarbon compound. The area of the component with a longer retention time than Contan is the area of the component with C30 or more, the area of the component with a longer retention time than Octadecane is the area of the component with C28 or more, and the area of the component with a shorter retention time than hexadecane is C16 or less. The area of the component, the area of the component whose retention time is shorter than that of octadecane is the area of the component C18 or less, the area of the component having the retention time between the retention time of hexadecane and triadecane is the area of the component of C16-C30, and octadecane. The area of the component having a retention time during the retention time of triacontan is the area of the component of C18-C30, and the area of the component having the retention time between the retention time of octadecane and octodecane is the area of the component of C18-C28, respectively. Calculated as a percentage. In the calculation of each area, components not derived from the hydrocarbon compound were removed by GC / MS. In the case of a mixture, the peak of the hydrocarbon compound may be detected broadly. In that case, the starting point is the start of the peak rise, and the end point is the point where the detected value of the peak begins to disappear to a negligible level. The area was calculated from the baseline connecting the end points with a straight line.

（３）ＧＣ／ＭＳ測定における繊維用表面処理剤中の炭化水素化合物の各面積の算出
表面処理剤を１６００ｐｐｍまでヘキサンで希釈し、前記（１）、（２）と同様に、表面処理剤中の各成分の値を算出した。尚、表面処理剤の混合前の原料を入手可能な場合は、測定をより簡易にするために炭化水素化合物そのものをヘキサンで１６００ｐｐｍまで希釈して、前記（１）、（２）と同様に測定した。(3) Calculation of each area of the hydrocarbon compound in the surface treatment agent for fibers in GC / MS measurement Dilute the surface treatment agent with hexane to 1600 ppm, and in the same manner as in (1) and (2) above, in the surface treatment agent. The value of each component of was calculated. If a raw material before mixing the surface treatment agent is available, the hydrocarbon compound itself is diluted with hexane to 1600 ppm for easier measurement, and the measurement is carried out in the same manner as in (1) and (2) above. did.

（４）解舒性
紙管に巻幅６０ｍｍで総重量３ｋｇになるように巻き取った後、ポリウレタン弾性繊維を２０℃６０％ＲＨの環境に２日間静置した後、紙管から２ｃｍのところまで糸を剥ぎ取って測定サンプルとし、測定サンプルの端面方向に１５ｍ／ｍｉｎで糸を消極解舒し、その時の張力を５分間測定し、その平均値を解舒張力とし、下記評価基準に従い７段階で判定した。解舒張力が低いほど、ポリウレタン弾性繊維がスムーズに解舒され、解舒時の糸切れが起こりにくいことが期待できる。ここでいう消極解舒とは、タテどり方式で解舒する方法のことをいう。
７：１０ｇ未満
６：１０ｇ以上１３ｇ未満
５：１３ｇ以上１５ｇ未満
４：１５ｇ以上２５ｇ未満
３：２５ｇ以上３０ｇ未満
２：：３０ｇ以上３５ｇ未満
１：３５ｇ以上または糸切れ(4) Releasability After winding around a paper tube with a winding width of 60 mm and a total weight of 3 kg, the polyurethane elastic fiber was allowed to stand in an environment of 20 ° C. and 60% RH for 2 days, and then 2 cm from the paper tube. The thread is stripped off to make a measurement sample, the thread is passively unwound at 15 m / min in the direction of the end face of the measurement sample, the tension at that time is measured for 5 minutes, the average value is taken as the unwinding tension, and 7 according to the following evaluation criteria. Judgment was made in stages. It can be expected that the lower the unwinding tension, the smoother the polyurethane elastic fiber is unwound, and the less likely it is that the yarn breaks during unwinding. The passive unraveling here refers to a method of unraveling in a vertical manner.
7:10 g or less 6: 10 g or more and less than 13 g 5: 13 g or more and less than 15 g 4: 15 g or more and less than 25 g 3: 25 g or more and less than 30 g 2:: 30 g or more and less than 35 g 1: 35 g or more or thread breakage

（５）単糸バラけ発生率（％）
長さ４０ｍｍのマルチフィラメントを１０本平行に並ぶようにデマッチャー試験機にセットし、２４０ｍｍの長さになるまで糸長方向に伸張し、再び元の４０ｍｍまで緩める伸張繰り返し操作を２００ｒｐｍの速度で５０００回行う。その後、図４に示すように、長さ４０ｍｍのマルチフィラメントを平らに置いた状態で、マルチフィラメント中の最も単糸が収束している部分からの距離が最大で０．５ｍｍ以上離れている単糸が発生した場合と単糸が切れた場合に単糸バラけが発生したとする。測定は同一サンプルあたり１組１０本で５回測定を行い、合計５０本の糸のうち何本バラけが発生したかをカウントし、発生率を計算し、下記７段階で評価した。単糸バラけ発生率が低いほど、ポリウレタン弾性繊維の使用時に単糸割れに由来する糸切れが起こりにくいことが期待できる。
７：発生率０％以上３％未満
６：発生率３％以上５％未満
５：発生率発生率５％未満
４：発生率５％以上１０％未満
３：発生率１０％以上１５未満
２：発生率１５％以上２０％未満
１：発生率２０％以上(5) Single yarn loosening rate (%)
Set 10 multifilaments with a length of 40 mm in parallel on the dematcher tester, stretch in the thread length direction until the length reaches 240 mm, and loosen again to the original 40 mm. Repeated stretching operation at a speed of 200 rpm is 5000. Do it once. After that, as shown in FIG. 4, in a state where the multifilament having a length of 40 mm is laid flat, the distance from the portion of the multifilament where the single yarn is most converged is 0.5 mm or more at the maximum. It is assumed that the single yarn is loosened when the yarn is generated and when the single yarn is broken. The measurement was performed 5 times with a set of 10 threads per same sample, the number of loose threads out of a total of 50 threads was counted, the occurrence rate was calculated, and the evaluation was made in the following 7 steps. It can be expected that the lower the rate of occurrence of single yarn loosening, the less likely it is that yarn breakage due to single yarn cracking will occur when the polyurethane elastic fiber is used.
7: Incidence rate 0% or more and less than 3% 6: Incidence rate 3% or more and less than 5% 5: Incidence rate occurrence rate less than 5% 4: Incidence rate 5% or more and less than 10% 3: Incidence rate 10% or more and less than 15 2: Incidence rate 15% or more and less than 20% 1: Incidence rate 20% or more

［式中、ｎ＝２〜５である式（１）の特定化合物の紡糸原液への練り込みによる実施例１〜１２、比較例１〜７］
［実施例１］
数平均分子量２０００のポリテトラメチレンエーテルグリコール２０００ｇと、４，４’−ジフェニルメタンジイソシアネート４００ｇとを、乾燥窒素雰囲気化、６０℃で３時間、撹拌下で反応させて、末端がイソシアネートでキャップされたポリウレタンプレポリマーを得た。これを室温まで冷却した後、ジメチルアセトアミドを加え、溶解してポリウレタンプレポリマー溶液とした。別途、エチレンジアミンとジエチルアミンを乾燥ジメチルアセトアミドに溶解したアミン溶液を作製し、ウレタンプレポリマー中のイソシアネート基とアミン溶液中のアミノ基の比率が１：１．０３となるように添加し、１０℃で冷却しながら反応させることで、ポリウレタン固形分濃度３０質量％、粘度４５０Ｐａ・ｓ（３０℃）のポリウレタン溶液を得た。
ポリウレタン固形分に対し、４，４’−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）を１ｗｔ％、２−（２’−ヒドロキシ−３’−ｔ−ブチル−５’−メチルフェニル）−５−クロロベンゾトリアゾールを０．５ｗｔ％、および、２５℃における動粘度が１０ｍｍ２／ｓのポリジメチルシロキサンを糸重量に対して０．５ｗｔ％、式中、ｎ＝２〜５である式（１）の特定化合物としてフィタン（ｎ＝３）を糸重量に対して５０ｐｐｍになるように秤量し、ジメチルアセトアミドに溶解した後で、ポリウレタン溶液と混合して、均一な溶液とした後、室温、減圧下で脱泡し、これを紡糸原液とした。
この紡糸原液を、巻き取り速度５００ｍ／分、熱風温度３００℃で、４８個のノズルからなる紡口を用いて乾式紡糸し、圧縮空気による仮撚装置で集束した後、紙製の紙管に巻き取り、４７０ｄｔ／４８フィラメントのポリウレタン弾性繊維の巻き取りパッケージを得た。[Examples 1 to 12 and Comparative Examples 1 to 7 by kneading the specific compound of the formula (1) having n = 2 to 5 into the spinning stock solution in the formula]
[Example 1]
2000 g of polytetramethylene ether glycol having a number average molecular weight of 2000 and 400 g of 4,4'-diphenylmethane diisocyanate are reacted in a dry nitrogen atmosphere at 60 ° C. for 3 hours under stirring, and the end is capped with isocyanate. A prepolymer was obtained. After cooling this to room temperature, dimethylacetamide was added and dissolved to obtain a polyurethane prepolymer solution. Separately, an amine solution prepared by dissolving ethylenediamine and diethylamine in dry dimethylacetamide was added so that the ratio of the isocyanate group in the urethane prepolymer to the amino group in the amine solution was 1: 1.03, and the mixture was added at 10 ° C. By reacting while cooling, a polyurethane solution having a polyurethane solid content concentration of 30% by mass and a viscosity of 450 Pa · s (30 ° C.) was obtained.
1 wt% of 4,4'-butylidenebis (3-methyl-6-t-butylphenol) and 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5 with respect to the polyurethane solid content. -Chlorobenzotriazole is 0.5 wt%, and polydimethylsiloxane having a kinematic viscosity at 25 ° C. of 10 mm 2 / s is 0.5 wt% with respect to the thread weight, and n = 2-5 in the formula (1). ) As a specific compound, phytan (n = 3) is weighed so as to be 50 ppm with respect to the thread weight, dissolved in dimethylacetamide, mixed with a polyurethane solution to form a uniform solution, and then at room temperature and reduced pressure. The foam was defoamed below, and this was used as the undiluted spinning solution.
This undiluted spinning solution is dry-spun at a winding speed of 500 m / min and a hot air temperature of 300 ° C. using a spun consisting of 48 nozzles, focused by a false twisting device using compressed air, and then put into a paper tube. A take-up package of 470 dt / 48 filament polyurethane elastic fibers was obtained.

［実施例２〜１２］
以下の表１に示す特定化合物の含有量、炭化水素化合物の面積比率となるように、特定化合物と特定化合物以外の炭化水素化合物からなる炭化水素混合物を適宜含有させた以外は、実施例１と同様にしてポリウレタン弾性繊維を得た。[Examples 2 to 12]
Example 1 and Example 1 except that a hydrogen mixture composed of a specific compound and a hydrogen compound other than the specific compound is appropriately contained so as to have the content of the specific compound and the area ratio of the hydrocarbon compound shown in Table 1 below. Similarly, polyurethane elastic fibers were obtained.

［比較例１］
フィタン含有させない以外は、実施例１と同様にしてポリウレタン弾性繊維を得た。[Comparative Example 1]
Polyurethane elastic fibers were obtained in the same manner as in Example 1 except that they did not contain phytane.

［比較例２］
ポリジメチルシロキサンの含有量を１．０ｗｔ％に変更した以外は、比較例１と同様にしてポリウレタン弾性繊維を得た。[Comparative Example 2]
Polyurethane elastic fibers were obtained in the same manner as in Comparative Example 1 except that the content of polydimethylsiloxane was changed to 1.0 wt%.

［比較例３〜６］
以下の表１に示す、特定化合物の含有量、炭化水素化合物の面積比率となるように、特定化合物と特定化合物以外の炭化水素化合物からなる炭化水素混合物、特定化合物以外の炭化水素化合物を適宜含有させた以外は、実施例１と同様にしてポリウレタン弾性繊維を得た。[Comparative Examples 3 to 6]
A hydrogen mixture composed of a specific compound and a hydrogen compound other than the specific compound, and a hydrogen compound other than the specific compound are appropriately contained so as to have the content of the specific compound and the area ratio of the hydrogen compound shown in Table 1 below. Polyurethane elastic fibers were obtained in the same manner as in Example 1 except that the compound was allowed to grow.

［比較例７］
以下の表１に示すポリジメチルシロキサンの含有量となるようにした以外は、比較例４と同様にしてポリウレタン弾性繊維を得た。[Comparative Example 7]
Polyurethane elastic fibers were obtained in the same manner as in Comparative Example 4 except that the content was adjusted to the polydimethylsiloxane content shown in Table 1 below.

Figure 2020250994
Figure 2020250994

［ポリウレタン弾性繊維用表面処理剤の調製方法である実施例１３〜２０、比較例８〜１２］
以下の表２に示す、特定化合物の含有量、炭化水素化合物の面積比率となるように、ポリジメチルシロキサンと、特定化合物、特定化合物と特定化合物以外の炭化水素化合物からなる炭化水素の混合物、または、特定化合物以外の炭化水素化合物とを適宜混合し、室温で３０分間攪拌羽にて混合して、ポリウレタン弾性繊維用処理剤を得た。[Examples 13 to 20, Comparative Examples 8 to 12, which are methods for preparing a surface treatment agent for polyurethane elastic fibers]
A mixture of polydimethylsiloxane and a specific compound, a mixture of a specific compound and a hydrocarbon compound other than the specific compound, or a hydrocarbon compound other than the specific compound, or a mixture of the specific compound and the area ratio of the hydrocarbon compound shown in Table 2 below. , A hydrocarbon compound other than the specific compound was appropriately mixed and mixed with a stirring blade at room temperature for 30 minutes to obtain a treatment agent for polyurethane elastic fibers.

Figure 2020250994
Figure 2020250994

表２中、ポリジメチルシロキサンの含有量が７０％を超えるものを、ポリウレタン弾性繊維用処理剤としての原料コストが高いとして「×」、７０％を下回るものを原料コストが低いとして「〇」とした。 In Table 2, those with a polydimethylsiloxane content of more than 70% are marked with "x" as the raw material cost as a treatment agent for polyurethane elastic fibers is high, and those with a polydimethylsiloxane content of less than 70% are marked with "○" as the raw material cost is low. did.

［ポリウレタン弾性繊維用処理剤を付与したポリウレタン弾性繊維の実施例２１〜２８、比較例１３〜１８］
数平均分子量２０００のポリテトラメチレンエーテルグリコール２０００ｇと、４，４’−ジフェニルメタンジイソシアネート４００ｇとを、乾燥窒素雰囲気化、６０℃で３時間、撹拌下で反応させて、末端がイソシアネートでキャップされたポリウレタンプレポリマーを得た。これを室温まで冷却した後、ジメチルアセトアミドを加え、溶解してポリウレタンプレポリマー溶液とした。別途、エチレンジアミンとジエチルアミンを乾燥ジメチルアセトアミドに溶解したアミン溶液を作製し、ウレタンプレポリマー中のイソシアネート基とアミン溶液中のアミノ基の比率が１：１．０３となるように添加し、１０℃で冷却しながら反応させることで、ポリウレタン固形分濃度３０質量％、粘度４５０Ｐａ・ｓ（３０℃）のポリウレタン溶液を得た。
ポリウレタン固形分に対し、４，４’−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）を１ｗｔ％、２−（２’−ヒドロキシ−３’−ｔ−ブチル−５’−メチルフェニル）−５−クロロベンゾトリアゾールを０．５ｗｔ％になるように秤量し、ジメチルアセトアミドに溶解した後で、ポリウレタン溶液と混合して、均一な溶液とした後、室温、減圧下で脱泡し、これを紡糸原液とした。
この紡糸原液を、巻き取り速度５００ｍ／分、熱風温度３００℃で、真円形状の孔４８個からなる紡口を用いて乾式紡糸し、圧縮空気による仮撚装置で集束した後、表３に記載した付与量と種類の表面処理剤をノズルオイリングにてポリウレタン弾性繊維に付与した後、紙製の紙管に巻き取り、４７０ｄｔ／４８フィラメントのポリウレタン弾性繊維の巻き取りパッケージを得た。[Examples 21 to 28 and Comparative Examples 13 to 18 of polyurethane elastic fibers provided with a treatment agent for polyurethane elastic fibers]
2000 g of polytetramethylene ether glycol having a number average molecular weight of 2000 and 400 g of 4,4'-diphenylmethane diisocyanate are reacted in a dry nitrogen atmosphere at 60 ° C. for 3 hours under stirring, and the end is capped with isocyanate. A prepolymer was obtained. After cooling this to room temperature, dimethylacetamide was added and dissolved to obtain a polyurethane prepolymer solution. Separately, an amine solution prepared by dissolving ethylenediamine and diethylamine in dry dimethylacetamide was added so that the ratio of the isocyanate group in the urethane prepolymer to the amino group in the amine solution was 1: 1.03, and the mixture was added at 10 ° C. By reacting while cooling, a polyurethane solution having a polyurethane solid content concentration of 30% by mass and a viscosity of 450 Pa · s (30 ° C.) was obtained.
1 wt% of 4,4'-butylidenebis (3-methyl-6-t-butylphenol) and 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5 with respect to the polyurethane solid content -Weighing chlorobenzotriazole to 0.5 wt%, dissolving it in dimethylacetamide, mixing it with a polyurethane solution to make a uniform solution, defoaming at room temperature under reduced pressure, and spinning this. It was used as a stock solution.
This undiluted spinning solution is dry-spun at a winding speed of 500 m / min and a hot air temperature of 300 ° C. using a spun consisting of 48 round holes, and is focused by a false twisting device using compressed air. After applying the described amount and type of surface treatment agent to the polyurethane elastic fiber by nozzle oiling, the polyurethane elastic fiber was wound into a paper tube to obtain a winding package of the polyurethane elastic fiber of 470 dt / 48 filament.

［実施例２９、比較例１９］
ポリウレタン弾性繊維用処理剤をノズルオイリングではなく、紡糸原液に練り込んだ以外は、実施例２１〜２８、比較例１３〜１８と同様に、４７０ｄｔ／４８フィラメントのポリウレタン弾性繊維の巻き取りパッケージを得た。[Example 29, Comparative Example 19]
Similar to Examples 21 to 28 and Comparative Examples 13 to 18, a take-up package of 470 dt / 48 filament polyurethane elastic fibers was obtained, except that the treatment agent for polyurethane elastic fibers was kneaded into the spinning stock solution instead of nozzle oiling. rice field.

Figure 2020250994
Figure 2020250994

本発明に係る特定の分岐炭化水素化合物を特定量含有したポリウレタン弾性繊維は、シリコーンオイルの含有量が少なくても、解舒性が良好であり、マルチフィラメントの単糸バラけが少ないポリウレタン弾性繊維である。それゆえ、本発明に係るポリウレタン弾性繊維のポリウレタン弾性繊維は、布帛、衛生材料製品等に好適に利用可能である。 The polyurethane elastic fiber containing a specific amount of a specific branched hydrocarbon compound according to the present invention is a polyurethane elastic fiber having good detonability even if the content of silicone oil is small and having little variation in single yarn of a multifilament. be. Therefore, the polyurethane elastic fiber of the polyurethane elastic fiber according to the present invention can be suitably used for fabrics, sanitary material products and the like.

Claims (19)

下記式（１）：
Figure 2020250994
 ｛式中、ｎは２〜５の整数である。｝で表される炭化水素化合物を、ポリウレタン弾性繊維重量に対して１０ｐｐｍ以上１００００ｐｐｍ以下で含有することを特徴とするポリウレタン弾性繊維。The following formula (1):
Figure 2020250994
 {In the formula, n is an integer of 2-5. }, The polyurethane elastic fiber is characterized by containing the hydrocarbon compound represented by} in an amount of 10 ppm or more and 10000 ppm or less with respect to the weight of the polyurethane elastic fiber. 式中、ｎ＝３である前記式（１）で表される炭化水素化合物をポリウレタン弾性繊維重量に対して１０ｐｐｍ以上８０００ｐｐｍ以下で含有する、請求項１に記載のポリウレタン弾性繊維。 The polyurethane elastic fiber according to claim 1, wherein the hydrocarbon compound represented by the formula (1) having n = 3 in the formula is contained in an amount of 10 ppm or more and 8000 ppm or less with respect to the weight of the polyurethane elastic fiber. 式中、ｎが２〜５の整数である前記式（１）で表される炭化水素化合物以外の炭化水素化合物をさらに含有する、請求項１又は２に記載のポリウレタン弾性繊維。 The polyurethane elastic fiber according to claim 1 or 2, further containing a hydrocarbon compound other than the hydrocarbon compound represented by the formula (1) in which n is an integer of 2 to 5. ヘキサンによる抽出液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうち、トリアコンタンの保持時間より長い保持時間を占める成分の面積が５％未満である、請求項１〜３のいずれか１項に記載のポリウレタン弾性繊維。 In the GC / MS measurement of the extract with hexane, the area of the component occupying the retention time longer than the retention time of triacontane is less than 5% of the total area of the peak derived from the hydrocarbon compound, according to claims 1 to 3. The polyurethane elastic fiber according to any one item. ヘキサンによる抽出液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうち、オクトコサンの保持時間より長い保持時間を占める成分の面積が５％未満である、請求項１〜４のいずれか１項に記載のポリウレタン弾性繊維。 Any of claims 1 to 4, wherein in the GC / MS measurement of the extract with hexane, the area of the component occupying the retention time longer than the retention time of octocosan is less than 5% in the total area of the peak derived from the hydrocarbon compound. The polyurethane elastic fiber according to item 1. ヘキサンによる抽出液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうち、ヘキサデカンの保持時間よりも短い保持時間を占める成分の面積が５％未満である、請求項１〜５のいずれか１項に記載のポリウレタン弾性繊維。 According to claims 1 to 5, in the GC / MS measurement of the extract with hexane, the area of the component occupying the holding time shorter than the holding time of hexadecane in the total area of the peak derived from the hydrocarbon compound is less than 5%. The polyurethane elastic fiber according to any one item. ヘキサンによる抽出液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうち、オクタデカンの保持時間よりも短い保持時間を占める面積が２０％未満である、請求項１〜６のいずれか１項に記載のポリウレタン弾性繊維。 Any of claims 1 to 6, wherein in the GC / MS measurement of the extract with hexane, less than 20% of the total area of the peak derived from the hydrocarbon compound occupies a holding time shorter than the holding time of octadecane. The polyurethane elastic fiber according to item 1. ヘキサンによる抽出液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうち、オクタデカンとオクトコサンの保持時間の間を占める成分の面積が８０％以上である、請求項１〜７のいずれか１項に記載のポリウレタン弾性繊維。 Any of claims 1 to 7, wherein in the GC / MS measurement of the extract with hexane, the area of the component occupying the retention time between octadecane and octocosan is 80% or more of the total area of the peak derived from the hydrocarbon compound. The polyurethane elastic fiber according to item 1. 請求項１〜８のいずれか１項に記載のポリウレタン弾性繊維を含む布帛。 A fabric containing the polyurethane elastic fiber according to any one of claims 1 to 8. 請求項１〜８のいずれか１項に記載のポリウレタン弾性繊維を含む衛生材料製品。 A sanitary material product containing the polyurethane elastic fiber according to any one of claims 1 to 8. 下記式（１）：
Figure 2020250994
 ｛式中、ｎは２〜５の整数である。｝で表される炭化水素化合物を、０．１０重量％以上２５重量％以下で含有することを特徴とするポリウレタン弾性繊維用表面処理剤。The following formula (1):
Figure 2020250994
 {In the formula, n is an integer of 2-5. } Is contained in an amount of 0.10% by weight or more and 25% by weight or less of the hydrocarbon compound, which is a surface treatment agent for polyurethane elastic fibers. 式中、ｎ＝３である前記式（１）で表される炭化水素化合物を、０．１０重量％以上２０重量％以下で含有する、請求項１１に記載のポリウレタン弾性繊維用表面処理剤。 The surface treatment agent for polyurethane elastic fibers according to claim 11, which contains the hydrocarbon compound represented by the formula (1) in the formula in an amount of 0.10% by weight or more and 20% by weight or less. 式中、ｎが２〜５の整数である前記式（１）で表される炭化水素化合物以外の炭化水素化合物をさらに含有する、請求項１１又は１２に記載のポリウレタン弾性繊維用表面処理剤。 The surface treatment agent for polyurethane elastic fibers according to claim 11 or 12, further containing a hydrocarbon compound other than the hydrocarbon compound represented by the above formula (1) in which n is an integer of 2 to 5. 前記ヘキサンに溶解した溶液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうちトリアコンタンの保持時間より長い保持時間を占める成分の面積が５％未満である、請求項１１〜１３のいずれか１項に記載のポリウレタン弾性繊維用表面処理剤。 In the GC / MS measurement of the solution dissolved in hexane, the area of the component occupying the retention time longer than the retention time of triacontane in the total area of the peak derived from the hydrocarbon compound is less than 5%, claims 11 to 13. The surface treatment agent for polyurethane elastic fibers according to any one of the above items. 前記ヘキサンに溶解した溶液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうち、オクトコサンの保持時間より長い保持時間を占める成分の面積が５％未満である、請求項１１〜１４のいずれか１項に記載のポリウレタン弾性繊維用表面処理剤。 In the GC / MS measurement of the solution dissolved in hexane, the area of the component occupying the retention time longer than the retention time of octocosan is less than 5% in the total area of the peak derived from the hydrocarbon compound, claims 11-14. The surface treatment agent for polyurethane elastic fibers according to any one of the above items. 前記ヘキサンに溶解した溶液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうち、ヘキサデカンの保持時間よりも短い保持時間を占める面積が５％未満である、請求項１１〜１５のいずれか１項に記載のポリウレタン弾性繊維用表面処理剤。 15. Of claims 11 to 15, in the GC / MS measurement of the solution dissolved in hexane, less than 5% of the total area of the peak derived from the hydrocarbon compound occupies a holding time shorter than that of hexadecane. The surface treatment agent for polyurethane elastic fibers according to any one item. 前記ヘキサンに溶解した溶液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうち、オクタデカンの保持時間よりも短い保持時間を占める面積が２０％未満である、請求項１１〜１６のいずれか１項に記載のポリウレタン弾性繊維用表面処理剤。 22. Of claims 11 to 16, in the GC / MS measurement of the solution dissolved in hexane, less than 20% of the total area of the peak derived from the hydrocarbon compound occupies a holding time shorter than the holding time of octadecane. The surface treatment agent for polyurethane elastic fibers according to any one item. 前記ヘキサンに溶解した溶液のＧＣ／ＭＳ測定において、炭化水素化合物由来のピークの全面積のうち、オクタデカンとオクトコサンの保持時間の間に占める成分の面積が８０％以上である炭化水素化合物をさらに含有する、請求項１１〜１７のいずれか１項に記載のポリウレタン弾性繊維用表面処理剤。 In the GC / MS measurement of the solution dissolved in hexane, the hydrocarbon compound in which the area of the component occupied during the retention time of octadecane and octocosan is 80% or more of the total area of the peak derived from the hydrocarbon compound is further contained. The surface treatment agent for polyurethane elastic fibers according to any one of claims 11 to 17. シリコーンオイルを２０重量％以上７０重量％以下でさらに含有する、請求項１１〜１８のいずれか１項に記載のポリウレタン弾性繊維用表面処理剤。 The surface treatment agent for polyurethane elastic fibers according to any one of claims 11 to 18, further containing 20% by weight or more and 70% by weight or less of silicone oil.
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