JP2004162187A - Treating agent for polyurethane elastic fiber and method for treating polyurethane elastic fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a treating agent for polyurethane elastic fibers affording a package having an excellent winding form in a production process of the polyurethane elastic fibers and simultaneously imparting excellent unwinding properties, smoothness and antistatic properties to the polyurethane elastic fibers used in a processing step thereof and to provide a method for treating the polyurethane elastic fibers. <P>SOLUTION: A binary system comprising a specific lubricating oil component and a specified silicone resin in a prescribed ratio or a ternary system further comprising a specific organophosphoric ester salt in a prescribed ratio is used as the treating agent for the polyurethane elastic fibers. <P>COPYRIGHT: (C)2004,JPO

Description

【式２】

【式３】

【式４】

【式５】

【００１２】
式１〜式５において、
Ｒ^１〜Ｒ^５：炭素数１〜２４の炭化水素基
Ｘ^１，Ｘ^２：下記の式６で示される有機基
【００１３】
【式６】

【００１４】
式６において、
Ｒ^６，Ｒ^７：炭素数１〜５のアルキレン基
Ｒ^８：水素原子、炭素数１〜５のアルキル基、フェニル基、炭素数４〜２２の１〜４価の脂肪族カルボン酸から一つの水酸基を除いた残基又は炭素数６〜２２の１〜４価の芳香族カルボン酸から一つの水酸基を除いた残基
ｆ：０又は１
【００１５】
第３成分：下記の式７で示される有機リン酸エステル塩及び又は下記の式８で示される有機リン酸エステル塩
【００１６】
【式７】

【式８】

【００１７】
式７，式８において、
Ｒ^９，Ｒ^１０：炭素数１２〜２６の脂肪族炭化水素基
ｍ，ｎ，ｒ，ｓ：１又は２であって、ｍ＋ｎ＝３、ｒ＋ｓ＝３を満足する整数
Ｍ^１，Ｍ^２：アルカノールアミン又はアルカリ金属
Ｙ：オキシエチレン単位又はオキシエチレン単位とオキシプロピレン単位とからなるオキシアルキレン単位の繰り返し数が１〜１０の（ポリ）オキシアルキレンジオールから全ての水酸基を除いた残基
【００１８】
本発明の処理剤に供する第１成分は潤滑油成分である。かかる第１成分には、１）シリコーンオイル、２）炭化水素油、３）シリコーンオイルと炭化水素油との混合物が含まれる。シリコーンオイル及び炭化水素油としては共に２５℃における粘度が２×１０^−６〜１００×１０^−６ｍ^２／ｓのものを用いるが、２５℃における粘度が１０×１０^−６〜３０×１０^−６ｍ^２／ｓのものを用いるのが好ましく、なかでも第１成分としては２５℃における粘度が１０×１０^−６〜３０×１０^−６ｍ^２／ｓのシリコーンオイルがより好ましい。かかる粘度は、ＪＩＳ−Ｋ２２８３（石油製品動粘度試験方法）に記載された方法で測定される値である。
【００１９】
前記のようなシリコーンオイルとしては、１）繰り返し単位がジメチルシロキサン単位であるポリジメチルシロキサン、２）繰り返し単位がジメチルシロキサン単位と炭素数２〜４のアルキル基を有するジアルキルシロキサン単位であるポリジアルキルシロキサン、３）繰り返し単位がジメチルシロキサン単位とメチルフェニルシロキサン単位であるポリジオルガノシロキサン等が挙げられるが、なかでもポリジメチルシロキサンが好ましい。また前記のような炭化水素油としては、１）石油留分から得られる流動パラフィン、２）α−オレフィンを重合して得られるポリα−オレフィン等が挙げられるが、なかでも精製流動パラフィンが好ましい。
【００２０】
本発明の処理剤に供する第２成分は、シロキサン単位Ａとシロキサン単位Ｂとシロキサン単位Ｃとを主構成単位とするシリコーン樹脂である。ここで、シロキサン単位Ａは式１で示されるシロキサン単位であり、シロキサン単位Ｂは式２で示されるシロキサン単位及び／又は式３で示されるシロキサン単位であって、シロキサン単位Ｃは式４で示されるシロキサン単位及び／又は式５で示されるシロキサン単位である。
【００２１】
したがって、第２成分として用いる前記のようなシリコーン樹脂には、１）式１で示されるシロキサン単位、式３で示されるシロキサン単位、式４で示されるシロキサン単位及び式５で示されるシロキサン単位を主構成単位とするシリコーン樹脂、２）式１で示されるシロキサン単位、式２で示されるシロキサン単位、式４で示されるシロキサン単位及び式５で示されるシロキサン単位を主構成単位とするシリコーン樹脂、３）式１で示されるシロキサン単位、式２で示されるシロキサン単位、式３で示されるシロキサン単位、式４で示されるシロキサン単位及び式５で示されるシロキサン単位を主構成単位とするシリコーン樹脂、４）式１で示されるシロキサン単位、式２で示されるシロキサン単位及び式４で示されるシロキサン単位を主構成単位とするシリコーン樹脂、５）式１で示されるシロキサン単位、式３で示されるシロキサン単位及び式４で示されるシロキサン単位を主構成単位とするシリコーン樹脂、６）式１で示されるシロキサン単位、式２で示されるシロキサン単位、式３で示されるシロキサン単位及び式４で示されるシロキサン単位を主構成単位とするシリコーン樹脂、７）式１で示されるシロキサン単位、式２で示されるシロキサン単位及び式５で示されるシロキサン単位を主構成単位とするシリコーン樹脂、８）式１で示されるシロキサン単位、式３で示されるシロキサン単位及び式５で示されるシロキサン単位を主構成単位とするシリコーン樹脂、９）式１で示されるシロキサン単位、式２で示されるシロキサン単位、式３で示されるシロキサン単位及び式５で示されるシロキサン単位を主構成単位とするシリコーン樹脂が含まれる。かかるシリコーン樹脂は、対応するシラン化合物を用いる公知の合成方法、例えば特開平５−２４７２１２号公報に記載の合成方法で合成できる。
【００２２】
シロキサン単位Ａとしての式１で示されるシロキサン単位において、式１中のＲ^１、Ｒ^２、Ｒ^３は、いずれも炭素数１〜２４の炭化水素基である。これには例えば、１）メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ヘキシル基、ペンチル基、オクチル基、デシル基、ドデシル基、トリデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、ドコシル基、テトラコシル基等の、炭素数１〜２４の脂肪族炭化水素基、２）シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロオクチル基、３−ピナニル基等の、炭素数３〜２４の脂環族炭化水素基、３）フェニル基、ナフチル基、ベンジル基、アントラセニル基、ピレニル基、ナフトピレニル基、２−ナフタレンドデシル基等の、炭素数６〜２４の芳香族炭化水素基等が挙げられるが、なかでもメチル基、エチル基、プロピル基、フェニル基が好ましい。式１で示されるシロキサン単位のうちで好ましいシロキサン単位としては、トリメチルシロキサン単位、メチルジエチルシロキサン単位、メチルジプロピルシロキサン単位、ジメチルフェニルシロキサン単位等が挙げられるが、なかでもトリメチルシロキサン単位がより好ましい。
【００２３】
シロキサン単位Ｂとしての式２で示されるシロキサン単位において、式２中のＲ^４は炭素数１〜２４の炭化水素基であり、これについては式１中のＲ^１〜Ｒ^３について前記したことと同じである。また式２中のＸ^１は式６で示される有機基である。かかる式６で示される有機基には、１）式６中のｆが０であって、Ｒ^８が水素原子である場合のアミノアルキル基、２）式６中のｆが０であって、Ｒ^８が炭素数１〜５のアルキル基である場合の置換イミノアルキル基、３）式６中のｆが０であって、Ｒ^８がフェニル基である場合のＮ−フェニルイミノアルキル基、４）式６中のｆが０であって、Ｒ^８が炭素数４〜２２の１〜４価の脂肪族カルボン酸から一つの水酸基を除いた残基である場合のＮ−置換脂肪族アミドアルキル基、５）式６中のｆが０であって、Ｒ^８が炭素数６〜２２の１〜４価の芳香族カルボン酸から一つの水酸基を除いた残基である場合のＮ−置換芳香族アミドアルキル基、６）式６中のｆが１であって、Ｒ^８が水素原子である場合のアミノアルキルイミノアルキル基、７）式６中のｆが１であって、Ｒ^８が炭素数１〜５のアルキル基である場合の置換イミノアルキルイミノアルキル基、８）式６中のｆが１であって、Ｒ^８がフェニル基である場合のＮ−フェニルイミノアルキルイミノアルキル基、９）式６中のｆが１であって、Ｒ^８が炭素数４〜２２の１〜４価の脂肪族カルボン酸から一つの水酸基を除いた残基である場合のＮ−置換脂肪族アミドアルキルイミノアルキル基、１０）式６中のｆが１であって、Ｒ^８が炭素数６〜２２の１〜４価の芳香族カルボン酸から一つの水酸基を除いた残基である場合のＮ−置換芳香族アミドアルキルイミノアルキル基が挙げられる。
【００２４】
式６中のｆが０である場合の式６で示される有機基について、前記１）のアミノアルキル基としては、アミノエチル基、３−アミノプロピル基、４−アミノブチル基等が挙げられるが、なかでも３−アミノプロピル基が好ましい。前記２）のイミノアルキル基としては、Ｎ−エチル−３−イミノプロピル基、Ｎ−エチル−２−イミノエチル基等が挙げられるが、なかでもＮ−エチル−３−イミノプロピル基が好ましい。前記３）のＮ−フェニルイミノアルキル基としては、Ｎ−フェニル−３−イミノプロピル基、Ｎ−フェニル−２−イミノエチル基等が挙げられるが、なかでもＮ−フェニル−３−イミノプロピル基が好ましい。前記４）のＮ−置換脂肪族アミドアルキル基としては、Ｎ−アセトイル−２−イミノエチル基、Ｎ−ドデカノイル−２−イミノエチル基、Ｎ−オクタデカノイル−２−イミノエチル基、Ｎ−オクタデセノイル−２−イミノエチル基、Ｎ−アセトイル−３−イミノプロピル基、Ｎ−ドデカノイル−３−イミノプロピル基、Ｎ−オクタデカノイル−３−イミノプロピル基、Ｎ−オクタデセノイル−３−イミノプロピル基、Ｎ−アセトイル−４−イミノブチル基、Ｎ−ドデカノイル−４−イミノブチル基、Ｎ−オクタデカノイル−４−イミノブチル基、Ｎ−オクタデセノイル−４−イミノブチル基、Ｎ−（２−カルボキシエチルカルボニル）−２−イミノエチル基、Ｎ−（２−カルボキシエチルカルボニル）−３−イミノプロピル基、Ｎ−（２−カルボキシエチルカルボニル）−４−イミノブチル基等が挙げられるが、なかでもＮ−（２−カルボキシエチルカルボニル）−３−イミノプロピル基が好ましい。前記５）のＮ−置換芳香族アミドアルキル基としては、Ｎ−（２，４−ジカルボキシベンゼン−カルボニル）−２−イミノエチル基、Ｎ−（２，５−ジカルボキシベンゼン−カルボニル）−２−イミノエチル基、Ｎ−（３，４−ジカルボキシベンゼン−カルボニル）−２−イミノエチル基、Ｎ−（２，４−ジカルボキシベンゼン−カルボニル）−３−イミノプロピル基、Ｎ−（２，５−ジカルボキシベンゼン−カルボニル）−３−イミノプロピル基、Ｎ−（３，４−ジカルボキシベンゼン−カルボニル）−３−イミノプロピル基、Ｎ−（２，４−ジカルボキシベンゼン−カルボニル）−４−イミノブチル基、Ｎ−（２，５−ジカルボキシベンゼン−カルボニル）−４−イミノブチル基、Ｎ−（３，４−ジカルボキシベンゼン−カルボニル）−４−イミノブチル基、Ｎ−（２，４，５−トリカルボキシベンゼン−カルボニル）−２−イミノエチル基、Ｎ−（２，４，５−トリカルボキシベンゼン−カルボニル）−３−イミノプロピル基、Ｎ−（２，４，５−トリカルボキシベンゼン−カルボニル）−４−イミノブチル基等が挙げられるが、なかでもＮ−（２，４−ジカルボキシベンゼン−カルボニル）−３−イミノプロピル基、Ｎ−（２，５−ジカルボキシベンゼン−カルボニル）−３−イミノプロピル基が好ましい。
【００２５】
また式６中のｆが１である場合の式６で示される有機基について、前記６）のアミノアルキルイミノアルキル基としては、Ｎ−（２−アミノエチル）−２−イミノエチル基、Ｎ−（２−アミノエチル）−３−イミノプロピル基、Ｎ−（２−アミノエチル）−４−イミノブチル基等が挙げられるが、なかでもＮ−（２−アミノエチル）−３−イミノプロピル基が好ましい。前記７）の置換イミノアルキルイミノアルキル基としては、Ｎ−（Ｎ’−エチル−２−イミノエチル）−３−イミノプロピル基、Ｎ−（Ｎ’−プロピル−２−イミノエチル）−３−イミノプロピル基等が挙げられるが、なかでもＮ−（Ｎ’−エチル−２−イミノエチル）−３−イミノプロピル基が好ましい。前記８）のＮ−フェニルイミノアルキルイミノアルキル基としては、Ｎ−（Ｎ’−フェニル−２−イミノエチル）−３−イミノプロピル基、Ｎ−（Ｎ’−フェニル−２−イミノエチル）−２−イミノエチル基等が挙げられるが、なかでもＮ−（Ｎ’−フェニル−２−イミノエチル）−３−イミノプロピル基が好ましい。前記９）のＮ−置換脂肪族アミドアルキルイミノアルキル基としては、Ｎ−（Ｎ’−アセトイル−２−イミノエチル）−２−イミノエチル基、Ｎ−（Ｎ’−ドデカノイル−２−イミノエチル）−２−イミノエチル基、Ｎ−（Ｎ’−オクタデカノイル−２−イミノエチル）−２−イミノエチル基、Ｎ−（Ｎ’−オクタデセノイル−２−イミノエチル）−２−イミノエチル基、Ｎ−（Ｎ’−アセトイル−２−イミノエチル）−３−イミノプロピル基、Ｎ−（Ｎ’−ドデカノイル−２−イミノエチル）−３−イミノプロピル基、Ｎ−（Ｎ’−オクタデカノイル−２−イミノエチル）−３−イミノプロピル基、Ｎ−（Ｎ’−オクタデセノイル−２−イミノエチル）−３−イミノプロピル基、Ｎ−（Ｎ’−アセトイル−２−イミノエチル）−４−イミノブチル基、Ｎ−（Ｎ’−ドデカノイル−２−イミノエチル）−４−イミノブチル基、Ｎ−（Ｎ’−オクタデカノイル−２−イミノエチル）−４−イミノブチル基、Ｎ−（Ｎ’−オクタデセノイル−２−イミノエチル）−４−イミノブチル基、Ｎ−［Ｎ’−（２−カルボキシエチルカルボニル）−２−イミノエチル］−２−イミノエチル基、Ｎ−［Ｎ’−（２−カルボキシエチルカルボニル）−２−イミノエチル］−３−イミノプロピル基、Ｎ−［Ｎ’−（２−カルボキシエチルカルボニル）−２−イミノエチル］−４−イミノブチル基等が挙げられるが、なかでもＮ−［Ｎ’−（２−カルボキシエチルカルボニル）−２−イミノエチル］−３−イミノプロピル基が好ましい。前記１０）のＮ−置換芳香族アミドアルキルイミノアルキル基としては、Ｎ−［Ｎ’−（２，４−ジカルボキシベンゼン−カルボニル）−２−イミノエチル］−２−イミノエチル基、Ｎ−［Ｎ’−（２，５−ジカルボキシベンゼン−カルボニル）−２−イミノエチル］−２−イミノエチル基、Ｎ−［Ｎ’−（３，４−ジカルボキシベンゼン−カルボニル）−２−イミノエチル］−２−イミノエチル基、Ｎ−［Ｎ’−（２，４−ジカルボキシベンゼン−カルボニル）−２−イミノエチル］−３−イミノプロピル基、Ｎ−［Ｎ’−（２，５−ジカルボキシベンゼン−カルボニル）−２−イミノエチル］−３−イミノプロピル基、Ｎ−［Ｎ’−（３，４−ジカルボキシベンゼン−カルボニル）−２−イミノエチル］−３−イミノプロピル基、Ｎ−［Ｎ’−（２，４−ジカルボキシベンゼン−カルボニル）−２−イミノエチル］−４−イミノブチル基、Ｎ−［Ｎ’−（２，５−ジカルボキシベンゼン−カルボニル）−２−イミノエチル］−４−イミノブチル基、Ｎ−［Ｎ’−（３，４−ジカルボキシベンゼン−カルボニル）−２−イミノエチル］−４−イミノブチル基、Ｎ−［Ｎ’−（２，４，５−トリカルボキシベンゼン−カルボニル）−２−イミノエチル］−２−イミノエチル基、Ｎ−［Ｎ’−（２，４，５−トリカルボキシベンゼン−カルボニル）−２−イミノエチル］−３−イミノプロピル基、Ｎ−［Ｎ’−（２，４，５−トリカルボキシベンゼン−カルボニル）−２−イミノエチル］−４−イミノブチル基等が挙げられるが、なかでもＮ−［Ｎ’−（２，４−ジカルボキシベンゼン−カルボニル）−２−イミノエチル］−３−イミノプロピル基、Ｎ−［Ｎ’−（２，５−ジカルボキシベンゼン−カルボニル）−２−イミノエチル］−３−イミノプロピル基が好ましい。
【００２６】
式２で示されるシロキサン単位のうちで好ましいシロキサン単位としては、３−アミノプロピルメチルシロキサン単位、Ｎ−フェニル−３−イミノプロピルメチルシロキサン単位、Ｎ−（２−カルボキシエチルカルボニル）−３−イミノプロピルメチルシロキサン単位、Ｎ−（２，４−ジカルボキシベンゼン−カルボニル）−３−イミノプロピルメチルシロキサン単位、Ｎ−（２，５−ジカルボキシベンゼン−カルボニル）−３−イミノプロピルメチルシロキサン単位、Ｎ−（２−アミノエチル）−３−イミノプロピルメチルシロキサン単位等が挙げられるが、なかでもＮ−（２−アミノエチル）−３−イミノプロピルメチルシロキサン単位がより好ましい。
【００２７】
シロキサン単位Ｂとしての式３で示されるシロキサン単位において、式３中のＸ^２は式６で示される有機基であり、これについては式２中のＸ^１について前記したことと同じである。式３で示されるシロキサン単位のうちで好ましいシロキサン単位としては、３−アミノプロピルシロキサン単位、Ｎ−フェニル−３−イミノプロピルシロキサン単位、Ｎ−（２−カルボキシエチルカルボニル）−３−イミノプロピルシロキサン単位、Ｎ−（２，４−ジカルボキシベンゼン−カルボニル）−３−イミノプロピルシロキサン単位、Ｎ−（２，５−ジカルボキシベンゼン−カルボニル）−３−イミノプロピルシロキサン単位、Ｎ−（２−アミノエチル）−３−イミノプロピルシロキサン単位等が挙げられるが、なかでもＮ−（２−アミノエチル）−３−イミノプロピルシロキサン単位がより好ましい。
【００２８】
シロキサン単位Ｃとしての式４で示されるシロキサン単位は４価のシロキサン単位である。またシロキサン単位Ｃとしての式５で示されるシロキサン単位において、式５中のＲ^５は炭素数１〜２４の炭化水素基であり、これについては式１中のＲ^１〜Ｒ^３について前記したことと同じである。式５で示されるシロキサン単位のうちで好ましいシロキサン単位としては、フェニルシロキサン単位、ｎ−デシルシロキサン単位、ベンジルシロキサン単位等が挙げられるが、なかでもフェニルシロキサン単位がより好ましい。
【００２９】
本発明の処理剤に第２成分として用いるシリコーン樹脂は、以上説明したようなシロキサン単位Ａ、シロキサン単位Ｂ及びシロキサン単位Ｃを主構成単位とするものであって、且つ１分子中にシロキサン単位Ａを１〜５５０個、シロキサン単位Ｂを１〜２００個、シロキサン単位Ｃを１〜１８００個有し、シロキサン単位Ｃとして式４で示されるシロキサン単位を有する場合には式１で示されるシロキサン単位の個数／式４で示されるシロキサン単位の個数＝０．８〜１．５、またシロキサン単位Ｃとして式５で示されるシロキサン単位を有する場合には式１で示されるシロキサン単位の個数／式５で示されるシロキサン単位の個数＝０．５〜１．５のものである。かかるシリコーン樹脂のなかでも、１）１分子中に、シロキサン単位Ａとして式１で示されるシロキサン単位を１〜３９０個、シロキサン単位Ｂとして式３で示されるシロキサン単位を１〜７０個、シロキサン単位Ｃとして式４で示されるシロキサン単位を１〜５６０個及び式５で示されるシロキサン単位を１〜６５０個有するシリコーン樹脂、２）１分子中に、シロキサン単位Ａとして式１で示されるシロキサン単位を１〜３９０個、シロキサン単位Ｂとして式２で示されるシロキサン単位を１〜７０個、シロキサン単位Ｃとして式４で示されるシロキサン単位を１〜５６０個及び式５で示されるシロキサン単位を１〜６５０個有するシリコーン樹脂、３）１分子中に、シロキサン単位Ａとして式１で示されるシロキサン単位を１〜３９０個、シロキサン単位Ｂとして式２で示されるシロキサン単位を１〜７０個及び式３で示されるシロキサン単位を１〜７０個、シロキサン単位Ｃとして式４で示されるシロキサン単位を１〜５６０個及び式５で示されるシロキサン単位を１〜６５０個有するシリコーン樹脂、４）１分子中に、シロキサン単位Ａとして式１で示されるシロキサン単位を１〜３９０個、シロキサン単位Ｂとして式２で示されるシロキサン単位を１〜７０個、シロキサン単位Ｃとして式４で示されるシロキサン単位を１〜５６０個有するシリコーン樹脂、５）１分子中に、シロキサン単位Ａとして式１で示されるシロキサン単位を１〜３９０個、シロキサン単位Ｂとして式３で示されるシロキサン単位を１〜７０個、シロキサン単位Ｃとして式４で示されるシロキサン単位を１〜５６０個有するシリコーン樹脂、６）１分子中に、シロキサン単位Ａとして式１で示されるシロキサン単位を１〜３９０個、シロキサン単位Ｂとして式２で示されるシロキサン単位を１〜７０個及び式３で示されるシロキサン単位を１〜７０個、シロキサン単位Ｃとして式４で示されるシロキサン単位を１〜５６０個有するシリコーン樹脂、７）１分子中に、シロキサン単位Ａとして式１で示されるシロキサン単位を１〜３７０個、シロキサン単位Ｂとして式２で示されるシロキサン単位を１〜７０個、シロキサン単位Ｃとして式５で示されるシロキサン単位を１〜６５０個有するシリコーン樹脂、８）１分子中に、シロキサン単位Ａとして式１で示されるシロキサン単位を１〜３７０個、シロキサン単位Ｂとして式３で示されるシロキサン単位を１〜７０個、シロキサン単位Ｃとして式５で示されるシロキサン単位を１〜６５０個有するシリコーン樹脂、９）１分子中に、シロキサン単位Ａとして式１で示されるシロキサン単位を１〜３７０個、シロキサン単位Ｂとして式２で示されるシロキサン単位を１〜７０個及び式３で示されるシロキサン単位を１〜７０個、シロキサン単位Ｃとして式５で示されるシロキサン単位を１〜６５０個有するシリコーン樹脂が好ましい。
【００３０】
本発明の処理剤に第２成分として用いるシリコーン樹脂は、アミノ当量１０００〜１０００００のものとするが、１５００〜３００００のものとするのが好ましく、また重量平均分子量１０００〜１０００００のものとするが、５０００〜５００００のものとするのが好ましい。
【００３１】
本発明の処理剤に第２成分として用いるシリコーン樹脂は、以上説明したように、シロキサン単位Ａとシロキサン単位Ｂとシロキサン単位Ｃとを主構成単位とし、通常は全構成単位中にこれらのシロキサン単位を合計で６５モル％以上有するものであるが、これらのシロキサン単位を合計で７０モル％以上有するものが好ましく、これらのシロキサン単位を合計で８５モル％以上有するものがより好ましい。
【００３２】
本発明の処理剤に第２成分として用いるシリコーン樹脂において、シロキサン単位Ａ、シロキサン単位Ｂ及びシロキサン単位Ｃ以外のシロキサン単位としては、これらのシロキサン単位Ａ〜Ｃを形成するために用いた相当する各シラン化合物から結果として形成されるシロキサン単位が挙げられる。一般的には、ケイ素原子に水酸基、アルキルオキシ基又は置換基を有するアルキルオキシ基が直結したシロキサン単位が挙げられ、具体的には、（ＨＯ）_３ＳｉＯ_１／２、（ＨＯ）_２ＳｉＯ_２／２、（ＨＯ）ＳｉＯ_３／２、（ＨＯ）Ｘ^１Ｒ^４ＳｉＯ_１／２、（ＨＯ）_２Ｘ^２ＳｉＯ_１／２、（ＨＯ）Ｘ^２ＳｉＯ_２／２、（ＨＯ）_２Ｒ^５ＳｉＯ_１／２、（ＨＯ）Ｒ^５ＳｉＯ_２／２、（ＨＯ）_２（Ｒ^１１Ｏ）ＳｉＯ_１／２、（ＨＯ）（Ｒ^１１Ｏ）_２ＳｉＯ_１／２、（ＨＯ）（Ｒ^１１Ｏ）ＳｉＯ_２／２、（Ｒ^１１Ｏ）_２ＳｉＯ_２／２、（Ｒ^１１Ｏ）ＳｉＯ_３／２、（Ｒ^１１Ｏ）Ｘ^１Ｒ^４ＳｉＯ_１／２、（ＨＯ）（Ｒ^１１Ｏ）Ｘ^２ＳｉＯ_１／２、（Ｒ^１１Ｏ）_２Ｘ^２ＳｉＯ_１／２、（Ｒ^１１Ｏ）Ｘ^２ＳｉＯ_２／２、（ＨＯ）（Ｒ^１１Ｏ）Ｒ^５ＳｉＯ_１／２、（Ｒ^１１Ｏ）_２Ｒ^５ＳｉＯ_１／２、（Ｒ^１１Ｏ）Ｒ^５ＳｉＯ_２／２で示されるシロキサン単位が挙げられる（但し、Ｒ^４，Ｒ^５，Ｘ^１，Ｘ^２は式２〜式５について前記したことと同じ、またＲ^１１Ｏはアルキルオキシ基又は置換基を有するアルキルオキシ基）。
【００３３】
本発明の処理剤に供する第３成分は、式７で示される有機リン酸エステル塩及び／又は式８で示される有機リン酸エステル塩である。
【００３４】
式７で示される有機リン酸エステル塩には、１）式７中のｎが１である場合の有機リン酸モノエステル塩、２）式７中のｎが２である場合の有機リン酸ジエステル塩、３）これらの混合物が含まれる。
【００３５】
式７で示される有機リン酸エステル塩において、式７中のＲ^９は、炭素数１２〜２６の脂肪族炭化水素基である。これには例えば、１）ドデシル基、トリデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、ドコシル基、テトラコシル基、ヘキサコシル基等の炭素数１２〜２６の直鎖状脂肪族炭化水素基、２）イソドデシル基、イソトリデシル基、イソテトラデシル基、イソヘキサデシル基、イソオクタデシル基、イソエイコシル基、イソドコシル基、イソテトラコシル基、イソヘキサコシル基等の炭素数１２〜２６の分岐状脂肪族炭化水素基等が挙げられるが、なかでもイソドデシル基、イソトリデシル基、イソテトラデシル基、イソヘキサデシル基、イソオクタデシル基等の炭素数１２〜１８の分岐状脂肪族炭化水素基が好ましい。
【００３６】
式７で示される有機リン酸エステル塩において、式７中のＭ^１としては、１）モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、トリイソプロパノールアミン等の低級アルカノールアミン、２）メチルジエタノ−ルアミン、ブチルジエタノ−ルアミン、ジブチルエタノ−ルアミン、ブチルモノエタノ−ルアミン、オクチルジエタノールアミン、ドデシルジエタノールアミン等のＮ−アルキル置換アルカノールアミン、３）ナトリウム、カリウム、リチウム等のアルカリ金属が挙げられるが、なかでもＮ−アルキル置換アルカノールアミン、ナトリウム、カリウムが好ましい。
【００３７】
式７で示される有機リン酸エステル塩は、公知の方法で合成できる。例えば、高級アルコールに無水リン酸を反応させて相当する酸性有機リン酸エステルを得た後、この酸性有機リン酸エステルをアルカノールアミン又は水酸化アルカリを用いて中和することにより合成できる。
【００３８】
式８で示される有機リン酸エステル塩には、１）式８中のｓが１である場合の有機リン酸モノエステル塩、２）式８中のｓが２である場合の有機リン酸ジエステル塩、３）これらの混合物が含まれる。
【００３９】
式８で示される有機リン酸エステル塩において、式８中のＲ^１０は、式７中のＲ^９について前記したことと同じである。また式８中のＭ^２も、式７中のＭ^１について前記したことと同じである。式８中のＹとしては、１）オキシエチレン単位の繰り返し数が１〜１０の（ポリ）オキシエチレンジオールから全ての水酸基を除いた残基、２）オキシプロピレン単位の繰り返し数が１〜１０の（ポリ）オキシプロピレンジオールから全ての水酸基を除いた残基、３）オキシエチレン単位及びオキシプロピレン単位の繰り返し数が２〜１０のポリオキシアルキレンジオールから全ての水酸基を除いた残基が挙げられるが、なかでもオキシエチレン単位及び／又はオキシプロピレン単位の繰り返し数が２〜６のポリオキシアルキレンジオールから全ての水酸基を除いた残基が好ましく、オキシエチレン単位の繰り返し数が２〜６のポリオキシエチレンジオールから全ての水酸基を除いた残基がより好ましい。
【００４０】
式８で示される有機リン酸エステル塩は、公知の方法で合成できる。例えば、高級アルコールのアルキレンオキサイド付加物に無水リン酸を反応させて相当する酸性有機リン酸エステルを得た後、この酸性有機リン酸エステルをアルカノールアミン又は水酸化アルカリを用いて中和することにより合成できる。
【００４１】
本発明の処理剤に供する第３成分としては、式７で示される有機リン酸エステル塩又は式８で示される有機リン酸エステル塩を単独で用いることができ、また式７で示される有機リン酸エステル塩と式８で示される有機リン酸エステル塩とを混合して用いることもできるが、なかでも式８で示される有機リン酸エステル塩が好ましく、有機リン酸エステルアルカリ金属塩がより好ましい。
【００４２】
本発明の処理剤は、以上説明した第１成分と第２成分との２成分系から成るもの、又は以上説明した第１成分と第２成分と第３成分との３成分系から成るものである。本発明の処理剤において、それが第１成分と第２成分との２成分系から成るものの場合、第１成分／第２成分＝１００／０．１〜１００／３０（重量比）の割合で含有して成るものとするが、第１成分／第２成分＝１００／１〜１００／１０（重量比）の割合で含有して成るものとするのが好ましい。またそれが第１成分と第２成分と第３成分との３成分系から成るものの場合、第１成分と第２成分との含有割合については前記と同様とし、更に第１成分と第２成分と第３成分との合計／第３成分＝１００／０．０１〜１００／２０（重量比）の割合で含有して成るものとするが、第１成分と第２成分と第３成分との合計／第３成分＝１００／０．０５〜１００／５（重量比）の割合で含有して成るものとするのが好ましい。
【００４３】
本発明の処理剤は、以上説明したような２成分系から成るもの又は３成分系から成るものであるが、目的に応じて他の成分を併用することもできる。かかる他の成分としては、いずれもそれ自体は公知の、ポリエーテル変性シリコーン、アミノ変性シリコーン、アルキル変性シリコーン、アルキルアラルキル変性シリコーン等の平滑性向上剤、ＭＱレジン、ＭＴＱレジン、ＭＤＴＱレジンと称されるアミノ基を有しないシリコーン樹脂、高級脂肪酸のアルカリ土類金属塩、タルク等の解舒性向上剤、他のアニオン界面活性剤、カチオン界面活性剤、両性界面活性剤等の静電気防止剤等が挙げられる。
【００４４】
本発明の処理剤は、乾式紡糸、溶融紡糸、湿式紡糸等、いずれの方式で製造されるポリウレタン系弾性繊維に対しても適用できるが、なかでも溶融紡糸で製造されるポリウレタン系弾性繊維に適用するのが好ましい。
【００４５】
本発明の処理方法は、以上説明した本発明の処理剤を、溶剤等で希釈することなくそのまま給油するニート給油法により、ポリウレタン系弾性繊維に付着させる方法である。その付着工程は、紡糸後でパッケージに巻き取るまでの間の工程である。付着方法としては、ローラー給油法、ガイド給油法、スプレー給油法等の公知の方法が適用できる。本発明の処理剤の付着量は、ポリウレタン系弾性繊維に対し０．１〜１０重量％となるようにするが、３〜７重量％となるようにするのが好ましい。
【００４６】
【発明の実施の形態】
本発明の処理剤の実施形態としては、次の１）〜９）が挙げられる。
１）下記の第１成分（Ｅ−１）と下記の第２成分（Ｓ−１）と下記の第３成分（Ｄ−１）とから成り、且つ該第１成分（Ｅ−１）／該第２成分（Ｓ−１）＝１００／１．５４（重量比）の割合で、また該第１成分（Ｅ−１）と該第２成分（Ｓ−１）と該第３成分（Ｄ−１）との合計／該第３成分（Ｄ−１）＝１００／１（重量比）の割合で含有して成る処理剤（Ｐ−１）。
第１成分（Ｅ−１）：２５℃における粘度が１０×１０^−６ｍ^２／ｓのシリコーンオイル
第２成分（Ｓ−１）：全構成単位中にシロキサン単位Ａとシロキサン単位Ｂとシロキサン単位Ｃとを合計で９２モル％有するシリコーン樹脂であり、該シロキサン単位Ａがトリメチルシロキサン単位、該シロキサン単位ＢがＮ−（２−アミノエチル）―３―イミノプロピルシロキサン単位、該シロキサン単位Ｃが式４で示されるシロキサン単位であって、且つ１分子中に該シロキサン単位Ａを２６５個、該シロキサン単位Ｂを１個、該シロキサン単位Ｃを３１１個有し、該シロキサン単位Ａの個数／該シロキサン単位Ｃの個数＝０．８５である、アミノ当量２０１７０、重量平均分子量４０３００のシリコーン樹脂（Ｓ−１）
第３成分（Ｄ−１）：リン酸α−イソドデシル−ω−ヒドロキシ（ポリオキシエチレン）ナトリウム（但し、オキシエチレン単位の繰り返し数は２、以下、ｖ＝２とする）
【００４７】
２）前記の第１成分（Ｅ−１）と下記の第２成分（Ｓ−２）と前記の第３成分（Ｄ−１）とから成り、且つ該第１成分（Ｅ−１）／該第２成分（Ｓ−２）＝１００／５．８８（重量比）の割合で、また該第１成分（Ｅ−１）と該第２成分（Ｓ−２）と該第３成分（Ｄ−１）との合計／該第３成分（Ｄ−１）＝１００／１（重量比）の割合で含有して成る処理剤（Ｐ−２）。
第２成分（Ｓ−２）：全構成単位中にシロキサン単位Ａとシロキサン単位Ｂとシロキサン単位Ｃとを合計で８８モル％有するシリコーン樹脂であり、該シロキサン単位Ａがトリメチルシロキサン単位、該シロキサン単位ＢがＮ−フェニル―３―イミノプロピルシロキサン単位、該シロキサン単位Ｃが式４で示されるシロキサン単位であって、且つ１分子中に該シロキサン単位Ａを１０７個、該シロキサン単位Ｂを２個、該シロキサン単位Ｃを１０７個有し、該シロキサン単位Ａの個数／該シロキサン単位Ｃの個数＝１である、アミノ当量７７４０、重量平均分子量１５５００のシリコーン樹脂（Ｓ−２）
【００４８】
３）下記の第１成分（Ｅ−２）と下記の第２成分（Ｓ−３）と下記の第３成分（Ｄ−２）とから成り、且つ該第１成分（Ｅ−２）／該第２成分（Ｓ−３）＝１００／０．５１（重量比）の割合で、また該第１成分（Ｅ−３）と該第２成分（Ｓ−３）と該第３成分（Ｄ−２）との合計／該第３成分（Ｄ−２）＝１００／１（重量比）の割合で含有して成る処理剤（Ｐ−３）。
第１成分（Ｅ−２）：２５℃における粘度が１０×１０^−６ｍ^２／ｓのシリコーンオイル
第２成分（Ｓ−３）：全構成単位中にシロキサン単位Ａとシロキサン単位Ｂとシロキサン単位Ｃとを合計で８９モル％有するシリコーン樹脂であり、該シロキサン単位Ａがオクタデシルジメチルシロキサン単位、該シロキサン単位ＢがＮ−（２，４−ジカルボキシベンゼン−カルボニル）―３―イミノプロピルシロキサン単位、該シロキサン単位Ｃが式４で示されるシロキサン単位であって、且つ１分子中に該シロキサン単位Ａを１３２個、該シロキサン単位Ｂを４個、該シロキサン単位Ｃを１３２個有し、該シロキサン単位Ａの個数／該シロキサン単位Ｃの個数＝１である、アミノ当量１２１００、重量平均分子量４８７００のシリコーン樹脂（Ｓ−３）
第３成分（Ｄ−２）：リン酸α−イソオクタデシル−ω−ヒドロキシ（ポリオキシエチレン）カリウム（ｖ＝２）
【００４９】
４）前記の第１成分（Ｅ−１）と前記の第２成分（Ｓ−１）と下記の第３成分（Ｄ−３）とから成り、且つ該第１成分（Ｅ−１）／該第２成分（Ｓ−１）＝１００／１．５４（重量比）の割合で、また該第１成分（Ｅ−１）と該第２成分（Ｓ−１）と該第３成分（Ｄ−３）との合計／該第３成分（Ｄ−３）＝１００／１（重量比）の割合で含有して成る処理剤（Ｐ−４）。
第３成分（Ｄ−３）：リン酸イソドデシル＝ジブチルエタノールアミン
【００５０】
５）前記の第１成分（Ｅ−１）と前記の第２成分（Ｓ−２）と前記の第３成分（Ｄ−３）とから成り、且つ該第１成分（Ｅ−１）／該第２成分（Ｓ−２）＝１００／１．５７（重量比）の割合で、また該第１成分（Ｅ−１）と該第２成分（Ｓ−２）と該第３成分（Ｄ−３）との合計／該第３成分（Ｄ−３）＝１００／３（重量比）の割合で含有して成る処理剤（Ｐ−５）。
【００５１】
６）前記の第１成分（Ｅ−２）と前記の第２成分（Ｓ−３）と下記の第３成分（Ｄ−４）とから成り、且つ該第１成分（Ｅ−２）／該第２成分（Ｓ−３）＝１００／３．６５（重量比）の割合で、また該第１成分（Ｅ−２）と該第２成分（Ｓ−３）と該第３成分（Ｄ−４）との合計／該第３成分（Ｄ−４）＝１００／０．５（重量比）の割合で含有して成る処理剤（Ｐ−６）。
第３成分（Ｄ−４）：リン酸ドデシル＝ジブチルエタノールアミン
【００５２】
７）前記の第１成分（Ｅ−１）と前記の第２成分（Ｓ−１）とから成り、且つ該第１成分（Ｅ−１）／該第２成分（Ｓ−１）＝１００／１．５２（重量比）の割合で含有して成る処理剤（Ｐ−２０）。
【００５３】
８）前記の第１成分（Ｅ−１）と前記の第２成分（Ｓ−２）とから成り、且つ該第１成分（Ｅ−１）／該第２成分（Ｓ−２）＝１００／５．８２（重量比）の割合で含有して成る処理剤（Ｐ−２１）。
【００５４】
９）前記の第１成分（Ｅ−２）と前記の第２成分（Ｓ−３）とから成り、且つ該第１成分（Ｅ−２）／該第２成分（Ｓ−３）＝１００／０．５０（重量比）の割合で含有して成る処理剤（Ｐ−２２）。
【００５５】
本発明の処理方法の実施形態としては、次の１０）が挙げられる。
１０）前記１）〜９）の処理剤を、希釈することなくニート給油法により、紡糸後でパッケージに捲き取るまでの間のポリウレタン系弾性繊維に対し、３〜７重量％となるよう付着させるポリウレタン系弾性繊維の処理方法。
【００５６】
以下、本発明の構成及び効果をより具体的にするため実施例を挙げるが、本発明が該実施例に限定されるというものではない。尚、以下の実施例等において、別に記載しない限り部は重量部を示し、％は重量％を示す。
【００５７】
【実施例】
・試験区分１（第２成分としてのシリコーン樹脂の合成）
・シリコーン樹脂（Ｓ−１）の合成
ヘキサメチルジシロキサン２１５ｇ（１．３モル）、水２４０ｇ、メタンスルホン酸２．０ｇ及びテトラエトキシシラン６４７ｇ（３．１モル）を反応容器に仕込み、加温して反応系の温度を７８℃に保ち、２４時間加温撹拌した。次いで、炭酸水素ナトリウム１．７８ｇを加えて中和した後、５時間還流し、熟成した。その後、キシレン６４０ｇを反応容器に仕込み、水及び反応により副生したエタノールを留去してキシレン溶液に置換後、濾過した。得られた濾液の有効濃度（キシレン溶液中の樹脂濃度）を５０％に調整した後、その２００ｇを別の反応容器に仕込み、Ｎ−（２−アミノエチル）−３−イミノプロピルトリメトキシシラン０．５５ｇ（２．５×１０^−３モル）と水０．１３ｇを加え、８０℃で０．１時間反応を行なった。反応溶液からキシレン、水及びメタノールを減圧下に留去して、シリコーン樹脂（Ｓ−１）を得た。シリコーン樹脂（Ｓ−１）について、以下の分析を行なったところ、このシリコーン樹脂（Ｓ−１）は、全構成単位中に、式１中のＲ^１、Ｒ^２、Ｒ^３がメチル基である場合の式１で示されるシロキサン単位と、式３中のＸ^２がＮ−（２−アミノエチル）−３−イミノプロピル基である場合の式３で示されるシロキサン単位と、式４で示されるシロキサン単位とを合計で９２モル％有し、分子中に式１で示されるシロキサン単位を２６５個、式３で示されるシロキサン単位を１個、式４で示されるシロキサン単位を３１１個有する、アミノ当量２０１７０、重量平均分子量４３０００のシリコーン樹脂であった。
【００５８】
・結合シロキンサン単位の分析：シリコーン樹脂（Ｓ−１）を、元素分析、ＩＣＰ発光分光分析、ＦＴ−ＩＲスペクトル分析に供して、全炭素含有量及びケイ素含有量を測定すると共に、ケイ素−炭素結合、ケイ素―酸素―ケイ素結合を確認した。これらの分析値、固体の^２９ＳｉについてＣＰ／ＭＡＳのＮＭＲスペクトルの積分値、原料として用いたヘキサメチルジシロキサンの炭素数及びＮ−（２−アミノエチル）−３−イミノプロピルトリメトキシシランの炭素数より、式１で示されるシロキサン単位、式３で示されるシロキサン単位、式４で示されるシロキサン単位の割合を算出した。
【００５９】
・分子中のシロキサン単位の個数の算出：前記で求めた結合シロキンサン単位の割合、シリコーン樹脂（Ｓ−１）を構成するシロキサン単位の理論分子量及び下記の重量平均分子量の測定値から分子中のシロキサン単位の個数を算出した。
【００６０】
・重量平均分子量
シリコーン樹脂（Ｓ−１）について、ＴＳＫ−ＧＥＬ ＳＵＰＥＲ４０００、ＴＳＫ−ＧＥＬ ＳＵＰＥＲ３０００及びＴＳＫ−ＧＥＬ ＳＵＰＥＲ２０００（いずれも東ソー社製の商品名）のポリスチレン系カラムを直列に接続したカラムを用い、移動層をＴＨＦの条件で測定して、ポリスチレン換算により、重量平均分子量を求めた。
【００６１】
・アミノ当量
キシレン／無水酢酸＝８０／２０（容積比）混合物に、シリコーン樹脂（Ｓ−１）を溶解させた後、滴定液として０．１モル／Ｌの過塩素酸メタノール溶液を用い、電位差滴定により測定した。
【００６２】
・シリコーン樹脂（Ｓ−２）〜（Ｓ−１４）及び（ｒ−１）〜（ｒ−１２）の合成
シリコーン樹脂（Ｓ−１）の場合と同様にして、シリコーン樹脂（Ｓ−２）〜（Ｓ−１４）及び（ｒ−１）〜（ｒ−１２）を合成し、分析した。合成した各シリコーン樹脂の内容を表１に示した。
【００６３】
【表１】

【００６４】
表１において、
個数：１分子中のシロキサン単位の個数
＊１：第２成分としてのシリコーン樹脂を構成する全構成単位中のシロキサン単位Ａとシロキサン単位Ｂとシロキサン単位Ｃとの合計モル％
＊２：式１で示されるシロキサン単位Ａの個数／式４で示されるシロキサン単位Ｃの個数
＊３：式１で示されるシロキサン単位Ａの個数／式５で示されるシロキサン単位Ｃの個数
＊４：アミノ当量
＊５：重量平均分子量
【００６５】
Ａ−１：トリメチルシロキサン単位［Ｒ^１＝ＣＨ_３、Ｒ^２＝ＣＨ_３、Ｒ^３＝ＣＨ_３である場合の式１で示されるシロキサン単位］
Ａ−２：オクタデシルジメチルシロキサン単位［Ｒ^１＝Ｃ_１８Ｈ_３７、Ｒ^２＝ＣＨ_３、Ｒ^３＝ＣＨ_３である場合の式１で示されるシロキサン単位］
Ｂ−１：３−アミノプロピルメチルシロキサン単位［Ｘ^１＝ＮＨ_２Ｃ_３Ｈ_６、Ｒ^４＝ＣＨ_３である場合の式２で示されるシロキサン単位］
Ｂ−２：Ｎ−フェニル−３−イミノプロピルメチルシロキサン単位（Ｘ^１＝Ｃ_６Ｈ_５−ＮＨＣ_３Ｈ_６、Ｒ＝ＣＨ_３である場合の式２で示されるシロキサン単位）
Ｂ−３：Ｎ−（２−カルボキシエチルカルボニル）−３−イミノプロピルメチルシロキサン単位（Ｘ^１＝ＨＯＯＣ−Ｃ_２Ｈ_４−ＣＯＮＨ−Ｃ_２Ｈ_４−ＮＨＣ_３Ｈ_６、Ｒ^４＝ＣＨ_３である場合の式２で示されるシロキサン単位）
Ｂ−４：Ｎ−（２，４−ジカルボキシベンゼン−カルボニル）−３−イミノプロピルメチルシロキサン単位［Ｘ^１＝（ＨＯＯＣ）_２Ｃ_６Ｈ_３ＣＯＮＨＣ_３Ｈ_６、Ｒ^４＝ＣＨ_３である場合の式２で示されるシロキサン単位］
Ｂ−５：Ｎ−（２−アミノエチル）―３―イミノプロピルメチルシロキサン単位（Ｘ^１＝ＮＨ_２−Ｃ_２Ｈ_４ＮＨＣ_３Ｈ_６、Ｒ^４＝ＣＨ_３である場合の式２で示されるシロキサン単位）
Ｂ−６：３−アミノプロピルシロキサン単位（Ｘ^２＝ＮＨ_２Ｃ_３Ｈ_６である場合の式３で示されるシロキサン単位）
Ｂ−７：Ｎ−フェニル−３−イミノプロピルシロキサン単位（Ｘ^２＝Ｃ_６Ｈ_５−ＮＨＣ_３Ｈ_６である場合の式３で示されるシロキサン単位）
Ｂ−８：Ｎ−（２−カルボキシエチルカルボニル）−３−イミノプロピルシロキサン単位（Ｘ^２＝ＨＯＯＣ−Ｃ_２Ｈ_４−ＣＯＮＨ−Ｃ_３Ｈ_６である場合の式３で示されるシロキサン単位）
Ｂ−９：Ｎ−（２，４−ジカルボキシベンゼン−カルボニル）−３−イミノプロピルシロキサン単位［Ｘ^２＝（ＨＯＯＣ）_２Ｃ_６Ｈ_３ＣＯＮＨ−Ｃ_３Ｈ_６である場合の式３で示されるシロキサン単位］
Ｂ−１０：Ｎ−（２−アミノエチル）―３―イミノプロピルシロキサン単位（Ｘ^２＝ＮＨ_２Ｃ_２Ｈ_４−ＮＨ−Ｃ_３Ｈ_６である場合の式３で示されるシロキサン単位）
Ｃ−１：式４で示されるシロキサン単位
Ｃ−２：フェニルシロキサン単位（Ｒ^５＝Ｃ_６Ｈ_５である場合の式５で示されるシロキサン単位）
Ｃ−３：ｎ−デシルシロキサン単位（Ｒ^５＝Ｃ_１０Ｈ_２１である場合の式５で示されるシロキサン単位）
【００６６】
・試験区分２（処理剤の調製）
・実施例１｛処理剤（Ｐ−１）の調製｝
第１成分として２５℃における粘度が１０×１０^−６ｍ^２／ｓのシリコーンオイル（Ｅ−１）９７．５部、第２成分として試験区分１で合成したシリコーン樹脂（Ｓ−１）１．５部及び第３成分としてリン酸α−イソドデシル−ω−ヒドロキシ（ポリオキシエチレン）ナトリウム（ｖ＝２）（Ｄ−１）１部を混合し、２０〜２５℃の温度で均一になるまで攪拌して処理剤（Ｐ−１）を調製した。
【００６７】
・実施例２〜３３及び比較例１〜１４｛処理剤（Ｐ−２）〜（Ｐ−３３）及び処理剤（Ｒ−１）〜（Ｒ−１４）の調製｝
実施例１の処理剤（Ｐ−１）と同様にして、実施例２〜３３の処理剤（Ｐ−２）〜（Ｐ−３３）及び比較例１〜１４の処理剤（Ｒ−１）〜（Ｒ−１４）を調製した。これらの処理剤の内容を表２と表３にまとめて示した。
【００６８】
【表２】

【００６９】
【表３】

【００７０】
表２及び表３において、
割合：部
＊６：第１成分／第２成分＝１００／ｘ（重量比）におけるｘの値
＊７：（第１成分＋第２成分＋第３成分）／第３成分＝１００／ｙ（重量比）におけるｙの値
＊８：第１成分／第２成分等＝１００／ｚ（重量比）におけるｚの値
【００７１】
Ｅ−１：２５℃における粘度が１０×１０^−６ｍ^２／ｓのシリコーンオイル
Ｅ−２：２５℃における粘度が２０×１０^−６ｍ^２／ｓのシリコーンオイル
Ｅ−３：（２５℃における粘度が２０×１０^−６ｍ^２／ｓのシリコーンオイル）／（２５℃における粘度が１９×１０^−６ｍ^２／ｓの精製パラフィン油）＝７５／２５（重量比）の混合物
Ｅ−４：（２５℃における粘度が１０×１０^−６ｍ^２／ｓのシリコーンオイル）／（２５℃における粘度が１９×１０^−６ｍ^２／ｓのポリαオレフィン油）＝８５／１５（重量比）の混合物
Ｓ−１〜Ｓ−１４，ｒ−１〜ｒ−１２：試験区分１で合成したシリコーン樹脂
Ｄ−１：リン酸α−イソドデシル−ω−ヒドロキシ（ポリオキシエチレン）＝ナトリウム（ｖ＝２）
Ｄ−２：リン酸α−イソオクタデシル−ω−ヒドロキシ（ポリオキシエチレン）＝カリウム（ｖ＝２）
Ｄ−３：リン酸イソドデシル＝ジブチルエタノールアミン
Ｄ−４：リン酸ドデシル＝ジブチルエタノールアミン
【００７２】
・試験区分３（ポリウレタン系弾性繊維の処理）
・実施例３４〜６６及び比較例１５〜２８
分子量１０００のポリテトラメチレングリコールとジフェニルメタンジイソシアネートとから得たポリウレタン重合体を用いて溶融紡糸したポリウレタン系弾性繊維に、試験区分２で調整した各処理剤をローラーオイリング法で表４及び表５に記載の付着量となるようニート給油し、引き続き６００ｍ／分の速度で糸管に巻き取り、捲き幅３８ｍｍ、捲き量４００ｇの、繊度２２デシテックスの処理済みポリウレタン系弾性繊維から成るパッケージを得た。
【００７３】
試験区分４（評価）
試験区分３で得たパッケージを下記の評価に供した。結果を表４及び表５にまとめて示した。
・捲形状の評価
パッケージについて、バルジとサドルを計測すると共に、端面における綾落ちを肉眼観察し、捲形状を評価した。
【００７４】
バルジ（単位：ｍｍ）：パッケージの捲き幅の最大値と最小値を計測し、双方の差を下記の基準で評価した。
◎：４ｍｍ未満
◎〜○：４ｍｍ以上５ｍｍ未満
○：５ｍｍ以上６ｍｍ未満
△：６ｍｍ以上７ｍｍ未満
×：７ｍｍ以上
【００７５】
サドル（単位：ｍｍ）：ポリウレタン系弾性繊維の捲き幅が正面に見えるようにしてパッケージを置き、パッケージの最大円周部分の直径と最小円周部分の直径を計測し、双方の差を下記の基準で評価した。
◎：１ｍｍ未満
◎〜○：１ｍｍ以上２ｍｍ未満
○：２ｍｍ以上３ｍｍ未満
△：３ｍｍ以上４ｍｍ未満
×：４ｍｍ以上
【００７６】
綾落ち：パッケージの端面において、巻き取られた処理済みポリウレタン系弾性繊維が円周面から滑落している程度を肉眼観察し、下記の基準で評価した。
○：綾落ちが認められない
×：綾落ちが認められる
【００７７】
・解舒性の評価
第１駆動ローラとこれに常時接する第１遊離ローラ−とで送り出し部を構成し、また第２駆動ローラ−とこれに常時接する第２遊離ローラ−とで巻き取り部を構成して、該送り出し部に対し該巻き取り部を水平方向に２０ｃｍ離して設置した。第１駆動ローラ−にパッケージを装着し、糸巻の厚さが２ｍｍになるまで解舒して、試料とした。この試料から処理済みポリウレタン系弾性繊維を第２駆動ローラ−に巻き取った。第１駆動ローラ−からの処理済みポリウレタン系弾性繊維の送り出し速度を５０ｍ／分で固定する一方、第２駆動ローラ−への該処理済みポリウレタン系弾性繊維の巻き取り速度を５０ｍ／分より徐々に上げて、該処理済みポリウレタン系弾性繊維をパッケージから強制解舒した。この強制解舒時において、送り出し部分と巻き取り部分との間で処理済みポリウレタン系弾性繊維の踊りがなくなる時点での巻き取り速度Ｖ（ｍ／分）を測定した。そして下記の式により解舒性（％）を求め、下記の基準で評価した。
解舒性（％）＝（Ｖ−５０）×２
◎：解舒性１１０％未満（全く問題なく、安定に解舒できる）
◎〜○：解舒性１１０以上１２５％未満（糸の引き出しに僅かに抵抗があるものの、糸切れの発生は無く、安定に解舒できる）
○：解舒性１２５以上１３５％未満（糸の引き出しにやや抵抗があるものの、糸切れの発生は無く、安定に解舒できる）
△：解舒性１３５以上１４５％未満（糸の引き出しに明らかに抵抗があり、若干の糸切れもあって、操業にやや問題がある。）
×：解舒性１４５％以上（糸の引き出しに大きな抵抗があり、糸切れが多発して、操業に大きな問題がある。）
【００７８】
・平滑性の評価
エイコー測器社製μメーターを用い、パッケージから引き出した処理済みポリウレタン系弾性繊維に初期張力（Ｔ^１）５ｇをかけ、糸速度１００ｍ／分の速度で走行させたときの２次張力（Ｔ^２）を測定した。そして下記の式により摩擦係数を算出し、下記の基準で評価した。
摩擦係数＝（Ｔ^２−Ｔ^１）／（Ｔ^２＋Ｔ^１）
◎：０．１５０以上０．２００未満
◎〜○：０．２００以上０．２１５未満
○：０．２１５以上０．２３０未満
△：０．２３０以上０．２４５未満
×：０．２４５以上
【００７９】
・制電性の評価
パッケージから引き出した処理済みポリウレタン系弾性繊維１０ｇの電気抵抗値を、２５℃×４０％ＲＨの雰囲気下で、電気抵抗測定器（東亜電波工業社製のＳＭ−５Ｅ型）を用いて測定し、測定値を次の基準で評価した。
◎：電気抵抗値１．０×１０^９Ω未満（全く問題無く、安定に操業できる）
◎〜○：電気抵抗値１．０×１０^９Ω以上５．０×１０^１０Ω未満（ごくわずかに整経工程で寄りつきがあることがあるが、安定に操業できる）
○：電気抵抗値５．１×１０^１０Ω以上１．０×１０^１１Ω未満（整経工程で若干の寄りつきがあるが、問題なく安定に操業できる）
△：電気抵抗値１．１×１０^１１Ω以上１．０×１０^{１ ２}Ω未満（整経工程での寄りつき及び丸編み工程での風綿の付着があるものの、操業性には問題が無い）
×：電気抵抗値１．０×１０^{１ ２}Ω以上（整経工程での寄りつきが激しく、丸編み工程での風綿の付着も激しくて、操業できない）
【００８０】
【表４】

【００８１】
【表５】

【００８２】
【発明の効果】
既に明らかなように、以上説明した本発明には、ポリウレタン系弾性繊維の製造工程において優れた捲形状のパッケージを得ることができ、同時にその加工工程において用いるポリウレタン系弾性繊維に優れた解舒性、平滑性及び制電性を付与できるという効果がある。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a treatment agent for polyurethane elastic fibers (hereinafter simply referred to as treatment agent) and a method for treating polyurethane elastic fibers (hereinafter simply referred to as treatment method). In the thread making process of polyurethane-based elastic fibers, it is required to obtain an excellent wound package due to its properties. In the processing step using polyurethane-based elastic fibers, the polyurethane-based elastic fibers are also used due to their properties. It is required to stabilize the operation by simultaneously imparting excellent unwinding property, smoothness and antistatic property to the fiber. The present invention relates to a treating agent and a treating method that meet such demands.
[0002]
[Prior art]
Conventionally, as processing agents, those described in the following Patent Documents 1 to 11 are known. Patent Document 1 discloses a composition containing amyl silicone as a treating agent. Patent Document 2 describes a treating agent comprising a phenyl group-containing silicone resin, a polydimethylsiloxane fluid end-capped with a trimethylsilyl group, and an organic finish. Patent Documents 3 and 4 disclose a processing agent obtained by mixing a mineral oil and / or a linear polyorganosiloxane with an amino-modified silicone and a polyorganosiloxane having a cyclic structure. Patent Documents 5, 6, and 7 disclose those containing a silicone resin composed of a monovalent siloxane unit and a tetravalent siloxane unit as a treating agent. Patent Literature 8 discloses a treatment agent in which an aminoalkyl silicone resin and an alkyl silicone resin are blended with a mineral oil and / or a polyorganosiloxane. Patent Document 9 discloses a treatment agent comprising a polyorganosiloxane or mineral oil, a silicone resin, and a polyether-modified silicone. Patent Document 10 discloses a treatment agent containing a mineral oil, a polyalkylsiloxane, a metal salt of an alkyl phosphate, and an alkyl phosphate amine salt as a treating agent. Patent Literature 11 discloses a treatment agent containing a mineral oil, a polyalkylsiloxane, a polyether-modified silicone, a metal salt of an alkyl phosphate, and an alkyl phosphate amine salt as a treating agent. However, these conventional treating agents include poor winding shape of the obtained package in the process of spinning the polyurethane elastic fiber, and unwinding property, smoothness and static control of the package in the processing step using the same. There is a problem that one or more of the sexes are insufficient. Such a problem is large in polyurethane-based elastic fibers having fineness, for example, fineness such as 11 to 22 dtex.
[0003]
[Patent Document 1]
JP-B-42-8438
[Patent Document 2]
JP-B-63-12197
[Patent Document 3]
JP-A-3-294524
[Patent Document 4]
Japanese Patent No. 2788097
[Patent Document 5]
JP-A-8-74179
[Patent Document 6]
JP-A-9-188974
[Patent Document 7]
Japanese Patent No. 2852887
[Patent Document 8]
Japanese Patent No. 2960224
[Patent Document 9]
JP-A-4-343770
[Patent Document 10]
JP-A-7-173770
[Patent Document 11]
JP-A-9-49167
[0004]
[Problems to be solved by the invention]
The problem to be solved by the present invention is that it is possible to obtain an excellent wound-shaped package in the process of spinning polyurethane-based elastic fibers, and at the same time, excellent unwinding properties and smoothness of the polyurethane-based elastic fibers used in the processing step. An object of the present invention is to provide a treating agent and a treating method capable of imparting antistatic properties.
[0005]
[Means for Solving the Problems]
Thus, the present inventors have studied to solve the above-mentioned problems, and as a result, a treating agent composed of a specific two-component system or three-component system and containing each at a predetermined ratio is correct and suitable, It has been found that a treatment method in which such a treatment agent is adhered to a polyurethane elastic fiber at a predetermined ratio after dilution by a neat lubrication method after spinning and before winding the package has been found to be correct and suitable.
[0006]
That is, the present invention comprises the following first component and the following second component, and contains the first component / the second component in a ratio of 100 / 0.1 to 100/30 (weight ratio). A treating agent characterized by the following.
[0007]
Further, the present invention comprises the following first component, the following second component, and further the following third component, and the first component / the second component = 100 / 0.1 to 100/30 ( Weight ratio) and the total of the first component, the second component, and the third component / the third component = 100 / 0.01 to 100/20 (weight ratio). A treating agent characterized by the following.
[0008]
Further, the present invention provides the above-mentioned treating agent of the present invention by a neat lubrication method without diluting the treating agent of the present invention in an amount of 0.1 to 10% by weight based on the amount of polyurethane-based elastic fibers after spinning and before winding into a package. The present invention relates to a processing method characterized in that it is adhered so that
[0009]
First component: Both have a viscosity of 2 × 10 at 25 ° C.^-6~ 100 × 10^-6m²/ S silicone oil and / or hydrocarbon oil
[0010]
Second component: a silicone resin having a siloxane unit A, a siloxane unit B and a siloxane unit C as main constituent units, wherein the siloxane unit A is a siloxane unit represented by the following formula 1, and the siloxane unit B is a compound represented by the following formula: And / or the siloxane unit C is a siloxane unit represented by the following formula 4 and / or a siloxane unit represented by the following formula 5; and One molecule has 1 to 550 siloxane units A, 1 to 200 siloxane units B, and 1 to 1800 siloxane units C in one molecule, and has a siloxane unit represented by Formula 4 as the siloxane unit C. In this case, the number of siloxane units represented by the formula 1 / the number of siloxane units represented by the formula 4 = 0.8 to 1.5, and the siloxane unit In the case of having a siloxane unit represented by Formula 5, the number of siloxane units represented by Formula 1 / the number of siloxane units represented by Formula 5 = 0.5 to 1.5, an amino equivalent of 1,000 to 100,000, and a weight Silicone resin with average molecular weight of 1,000 to 100,000
[0011]
(Equation 1)

[Equation 2]

[Equation 3]

(Equation 4)

(Equation 5)

[0012]
In Equations 1 to 5,
R¹~ R⁵: A hydrocarbon group having 1 to 24 carbon atoms
X¹, X²: An organic group represented by the following formula 6
[0013]
(Equation 6)

[0014]
In Equation 6,
R⁶, R⁷: An alkylene group having 1 to 5 carbon atoms
R⁸: A hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, a residue obtained by removing one hydroxyl group from 1 to 4 aliphatic carboxylic acids having 4 to 22 carbon atoms, or 1 to 4 having 6 to 22 carbon atoms. Residue obtained by removing one hydroxyl group from a divalent aromatic carboxylic acid
f: 0 or 1
[0015]
Third component: an organic phosphate ester salt represented by the following formula 7 and / or an organic phosphate ester salt represented by the following formula 8
[0016]
[Equation 7]

[Equation 8]

[0017]
In Equations 7 and 8,
R⁹, R¹⁰: An aliphatic hydrocarbon group having 12 to 26 carbon atoms
m, n, r, s: 1 or 2 and an integer satisfying m + n = 3 and r + s = 3
M¹, M²: Alkanolamine or alkali metal
Y: a residue obtained by removing all hydroxyl groups from a (poly) oxyalkylene diol having a repeating number of 1 to 10 of an oxyethylene unit or an oxyalkylene unit composed of an oxyethylene unit and an oxypropylene unit
[0018]
The first component provided to the treatment agent of the present invention is a lubricating oil component. Such first components include 1) silicone oil, 2) hydrocarbon oil, 3) a mixture of silicone oil and hydrocarbon oil. Both silicone oil and hydrocarbon oil have a viscosity of 2 × 10 at 25 ° C.^-6~ 100 × 10^-6m²/ S, but the viscosity at 25 ° C. is 10 × 10^-6~ 30 × 10^-6m²/ S is preferably used, and as the first component, the viscosity at 25 ° C. is 10 × 10^-6~ 30 × 10^-6m²/ S of silicone oil is more preferred. The viscosity is a value measured by a method described in JIS-K2283 (Kinematic viscosity test method for petroleum products).
[0019]
Examples of the silicone oil include 1) polydimethylsiloxane having a repeating unit of a dimethylsiloxane unit, and 2) polydialkylsiloxane having a repeating unit of a dimethylsiloxane unit and a dialkylsiloxane unit having an alkyl group having 2 to 4 carbon atoms. 3) Polydiorganosiloxane whose repeating units are a dimethylsiloxane unit and a methylphenylsiloxane unit, etc., among which polydimethylsiloxane is preferable. Examples of the above-mentioned hydrocarbon oil include 1) liquid paraffin obtained from petroleum fraction, and 2) poly α-olefin obtained by polymerizing α-olefin. Among them, purified liquid paraffin is preferable.
[0020]
The second component provided to the treatment agent of the present invention is a silicone resin having a siloxane unit A, a siloxane unit B, and a siloxane unit C as main constituent units. Here, the siloxane unit A is a siloxane unit represented by Formula 1, the siloxane unit B is a siloxane unit represented by Formula 2 and / or a siloxane unit represented by Formula 3, and the siloxane unit C is represented by Formula 4. And / or a siloxane unit represented by Formula 5.
[0021]
Therefore, the above-mentioned silicone resin used as the second component includes 1) a siloxane unit represented by Formula 1, a siloxane unit represented by Formula 3, a siloxane unit represented by Formula 4, and a siloxane unit represented by Formula 5. A silicone resin having a main structural unit, 2) a siloxane unit represented by the formula 1, a siloxane unit represented by the formula 2, a siloxane unit represented by the formula 4, and a siloxane unit represented by the formula 5 as a main structural unit; 3) a silicone resin having a siloxane unit represented by the formula 1, a siloxane unit represented by the formula 2, a siloxane unit represented by the formula 3, a siloxane unit represented by the formula 4, and a siloxane unit represented by the formula 5 as main constituent units; 4) a siloxane unit represented by the formula 1, a siloxane unit represented by the formula 2, and a siloxane unit represented by the formula 4 A silicone resin having a constitutional unit, 5) a siloxane unit represented by the formula 1, a siloxane unit represented by the formula 3 and a siloxane unit represented by the formula 4, and 6) a siloxane unit represented by the formula 1 A silicone resin having a siloxane unit represented by the formula 2, a siloxane unit represented by the formula 3 and a siloxane unit represented by the formula 4 as a main constituent unit; 7) a siloxane unit represented by the formula 1 and a siloxane unit represented by the formula 2 And a silicone resin having a siloxane unit represented by the formula 5 as a main constituent unit; 8) a silicone resin having a siloxane unit represented by the formula 1, a siloxane unit represented by the formula 3 and a siloxane unit represented by the formula 5 as a main constituent unit. , 9) a siloxane unit represented by the formula 1, a siloxane unit represented by the formula 2, a siloxane unit represented by the formula 3, and It includes silicone resin having a siloxane unit represented by the formula 5 as a main structural unit. Such a silicone resin can be synthesized by a known synthesis method using a corresponding silane compound, for example, a synthesis method described in JP-A-5-247212.
[0022]
In the siloxane unit represented by the formula 1 as the siloxane unit A, R in the formula 1¹, R², R³Is a hydrocarbon group having 1 to 24 carbon atoms. Examples include 1) methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, pentyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl. An aliphatic hydrocarbon group having 1 to 24 carbon atoms such as a group, an eicosyl group, a docosyl group, or a tetracosyl group; 2) a carbon number such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, or a 3-pinanyl group; An alicyclic hydrocarbon group having 3 to 24 carbon atoms; 3) an aromatic hydrocarbon group having 6 to 24 carbon atoms such as a phenyl group, a naphthyl group, a benzyl group, an anthracenyl group, a pyrenyl group, a naphthopyrenyl group and a 2-naphthalendodecyl group. And the like, and among them, a methyl group, an ethyl group, a propyl group, and a phenyl group are preferable. Among the siloxane units represented by the formula 1, preferred siloxane units include a trimethylsiloxane unit, a methyldiethylsiloxane unit, a methyldipropylsiloxane unit, and a dimethylphenylsiloxane unit. Among them, the trimethylsiloxane unit is more preferred.
[0023]
In the siloxane unit represented by the formula 2 as the siloxane unit B, R in the formula 2⁴Is a hydrocarbon group having 1 to 24 carbon atoms.¹~ R³Is the same as described above. In addition, X in Expression 2¹Is an organic group represented by Formula 6. In the organic group represented by the formula 6, 1) f in the formula 6 is 0 and R⁸Is an aminoalkyl group when is a hydrogen atom, 2) f in the formula 6 is 0, and R⁸Is a substituted iminoalkyl group when is an alkyl group having 1 to 5 carbon atoms, 3) f in the formula 6 is 0 and R⁸Is a phenyl group, an N-phenyliminoalkyl group, 4) f in Formula 6 is 0, and R is⁸Is a residue obtained by removing one hydroxyl group from a monovalent to tetravalent aliphatic carboxylic acid having 4 to 22 carbon atoms, 5) f in formula 6 is 0, , R⁸Is a residue obtained by removing one hydroxyl group from a monovalent to tetravalent aromatic carboxylic acid having 6 to 22 carbon atoms, and 6) f in the formula 6 is 1 , R⁸Is an aminoalkyliminoalkyl group in which is a hydrogen atom, 7) f in the formula 6 is 1 and R⁸Is an alkyl group having 1 to 5 carbon atoms, a substituted iminoalkyliminoalkyl group; 8) f in the formula 6 is 1;⁸Is a phenyl group, an N-phenyliminoalkyliminoalkyl group, 9) f in the formula 6 is 1 and R⁸Is an N-substituted aliphatic amide alkyliminoalkyl group when 1 is a residue obtained by removing one hydroxyl group from a monovalent to tetravalent aliphatic carboxylic acid having 4 to 22 carbon atoms; 10) When f in Formula 6 is 1, Oh, R⁸Is a residue obtained by removing one hydroxyl group from a monovalent to tetravalent aromatic carboxylic acid having 6 to 22 carbon atoms, and an N-substituted aromatic amidoalkyliminoalkyl group is exemplified.
[0024]
Regarding the organic group represented by the formula 6 when f in the formula 6 is 0, the aminoalkyl group of the above 1) includes an aminoethyl group, a 3-aminopropyl group, a 4-aminobutyl group, and the like. Among them, a 3-aminopropyl group is preferable. Examples of the iminoalkyl group of the above 2) include an N-ethyl-3-iminopropyl group and an N-ethyl-2-iminoethyl group, and among them, an N-ethyl-3-iminopropyl group is preferable. Examples of the N-phenyliminoalkyl group of the above 3) include an N-phenyl-3-iminopropyl group and an N-phenyl-2-iminoethyl group, and among them, an N-phenyl-3-iminopropyl group is preferable. . Examples of the N-substituted aliphatic amide alkyl group of 4) include N-acetoyl-2-iminoethyl group, N-dodecanoyl-2-iminoethyl group, N-octadecanoyl-2-iminoethyl group, N-octadecenoyl-2-group. Iminoethyl group, N-acetoyl-3-iminopropyl group, N-dodecanoyl-3-iminopropyl group, N-octadecanoyl-3-iminopropyl group, N-octadecenoyl-3-iminopropyl group, N-acetoyl-4 -Iminobutyl group, N-dodecanoyl-4-iminobutyl group, N-octadecanoyl-4-iminobutyl group, N-octadecenoyl-4-iminobutyl group, N- (2-carboxyethylcarbonyl) -2-iminoethyl group, N- (2-carboxyethylcarbonyl) -3-iminopropyl group, N- (2-ca Bo carboxyethyl) -4- Iminobuchiru of the group, and the like, among which N-(2-carboxyethyl) -3- Iminopuropiru group. Examples of the N-substituted aromatic amide alkyl group of the above 5) include N- (2,4-dicarboxybenzene-carbonyl) -2-iminoethyl group and N- (2,5-dicarboxybenzene-carbonyl) -2- Iminoethyl group, N- (3,4-dicarboxybenzene-carbonyl) -2-iminoethyl group, N- (2,4-dicarboxybenzene-carbonyl) -3-iminopropyl group, N- (2,5-di Carboxybenzene-carbonyl) -3-iminopropyl group, N- (3,4-dicarboxybenzene-carbonyl) -3-iminopropyl group, N- (2,4-dicarboxybenzene-carbonyl) -4-iminobutyl group N- (2,5-dicarboxybenzene-carbonyl) -4-iminobutyl group, N- (3,4-dicarboxybenzene-carbonyl)- -Iminobutyl group, N- (2,4,5-tricarboxybenzene-carbonyl) -2-iminoethyl group, N- (2,4,5-tricarboxybenzene-carbonyl) -3-iminopropyl group, N- ( Examples thereof include a 2,4,5-tricarboxybenzene-carbonyl) -4-iminobutyl group, and among them, an N- (2,4-dicarboxybenzene-carbonyl) -3-iminopropyl group and an N- (2, A 5-dicarboxybenzene-carbonyl) -3-iminopropyl group is preferred.
[0025]
In addition, with respect to the organic group represented by the formula 6 when f in the formula 6 is 1, the aminoalkyliminoalkyl group of the above 6) may be N- (2-aminoethyl) -2-iminoethyl group, N- ( Examples thereof include a 2-aminoethyl) -3-iminopropyl group and an N- (2-aminoethyl) -4-iminobutyl group, and among them, an N- (2-aminoethyl) -3-iminopropyl group is preferable. Examples of the substituted iminoalkyliminoalkyl group of the above 7) include an N- (N′-ethyl-2-iminoethyl) -3-iminopropyl group and an N- (N′-propyl-2-iminoethyl) -3-iminopropyl group And the like, and among them, an N- (N′-ethyl-2-iminoethyl) -3-iminopropyl group is preferable. Examples of the N-phenyliminoalkyliminoalkyl group of the above 8) include N- (N′-phenyl-2-iminoethyl) -3-iminopropyl group and N- (N′-phenyl-2-iminoethyl) -2-iminoethyl. And N- (N′-phenyl-2-iminoethyl) -3-iminopropyl group. The N-substituted aliphatic amidoalkyliminoalkyl group of the above 9) includes N- (N′-acetoyl-2-iminoethyl) -2-iminoethyl group and N- (N′-dodecanoyl-2-iminoethyl) -2- Iminoethyl group, N- (N'-octadecanoyl-2-iminoethyl) -2-iminoethyl group, N- (N'-octadecenoyl-2-iminoethyl) -2-iminoethyl group, N- (N'-acetoyl-2) -Iminoethyl) -3-iminopropyl group, N- (N'-dodecanoyl-2-iminoethyl) -3-iminopropyl group, N- (N'-octadecanoyl-2-iminoethyl) -3-iminopropyl group, N- (N'-octadecenoyl-2-iminoethyl) -3-iminopropyl group, N- (N'-acetoyl-2-iminoethyl) -4-imino Tyl group, N- (N′-dodecanoyl-2-iminoethyl) -4-iminobutyl group, N- (N′-octadecanoyl-2-iminoethyl) -4-iminobutyl group, N- (N′-octadecenoyl-2) -Iminoethyl) -4-iminobutyl group, N- [N '-(2-carboxyethylcarbonyl) -2-iminoethyl] -2-iminoethyl group, N- [N'-(2-carboxyethylcarbonyl) -2-iminoethyl ] -3-iminopropyl group, N- [N '-(2-carboxyethylcarbonyl) -2-iminoethyl] -4-iminobutyl group and the like, among which N- [N'-(2-carboxyethyl) Carbonyl) -2-iminoethyl] -3-iminopropyl group is preferred. Examples of the N-substituted aromatic amidoalkyliminoalkyl group of the above 10) include N- [N '-(2,4-dicarboxybenzene-carbonyl) -2-iminoethyl] -2-iminoethyl group and N- [N' -(2,5-dicarboxybenzene-carbonyl) -2-iminoethyl] -2-iminoethyl group, N- [N '-(3,4-dicarboxybenzene-carbonyl) -2-iminoethyl] -2-iminoethyl group N- [N '-(2,4-dicarboxybenzene-carbonyl) -2-iminoethyl] -3-iminopropyl group, N- [N'-(2,5-dicarboxybenzene-carbonyl) -2- Iminoethyl] -3-iminopropyl group, N- [N '-(3,4-dicarboxybenzene-carbonyl) -2-iminoethyl] -3-iminopropyl group, N- [ '-(2,4-dicarboxybenzene-carbonyl) -2-iminoethyl] -4-iminobutyl group, N- [N'-(2,5-dicarboxybenzene-carbonyl) -2-iminoethyl] -4-iminobutyl Group, N- [N '-(3,4-dicarboxybenzene-carbonyl) -2-iminoethyl] -4-iminobutyl group, N- [N'-(2,4,5-tricarboxybenzene-carbonyl)- 2-iminoethyl] -2-iminoethyl group, N- [N '-(2,4,5-tricarboxybenzene-carbonyl) -2-iminoethyl] -3-iminopropyl group, N- [N'-(2, 4,5-tricarboxybenzene-carbonyl) -2-iminoethyl] -4-iminobutyl group and the like, and among them, N- [N '-(2,4-dicarboxybenzene) - carbonyl) -2-iminoethyl] -3 Iminopuropiru group, N- [N '- (2,5- dicarboxylate benzene - carbonyl) -2-iminoethyl] -3 Iminopuropiru group.
[0026]
Among the siloxane units represented by the formula 2, preferred siloxane units are 3-aminopropylmethylsiloxane unit, N-phenyl-3-iminopropylmethylsiloxane unit, N- (2-carboxyethylcarbonyl) -3-iminopropyl Methylsiloxane unit, N- (2,4-dicarboxybenzene-carbonyl) -3-iminopropylmethylsiloxane unit, N- (2,5-dicarboxybenzene-carbonyl) -3-iminopropylmethylsiloxane unit, N- Examples thereof include (2-aminoethyl) -3-iminopropylmethylsiloxane units, and among them, N- (2-aminoethyl) -3-iminopropylmethylsiloxane units are more preferable.
[0027]
In the siloxane unit represented by the formula 3 as the siloxane unit B, X in the formula 3²Is an organic group represented by the formula 6, wherein X in the formula 2¹Is the same as described above. Among the siloxane units represented by the formula 3, preferred siloxane units include a 3-aminopropylsiloxane unit, an N-phenyl-3-iminopropylsiloxane unit, and an N- (2-carboxyethylcarbonyl) -3-iminopropylsiloxane unit. , N- (2,4-dicarboxybenzene-carbonyl) -3-iminopropylsiloxane unit, N- (2,5-dicarboxybenzene-carbonyl) -3-iminopropylsiloxane unit, N- (2-aminoethyl ) -3-Iminopropylsiloxane unit and the like, and among them, N- (2-aminoethyl) -3-iminopropylsiloxane unit is more preferable.
[0028]
The siloxane unit represented by Formula 4 as the siloxane unit C is a tetravalent siloxane unit. In the siloxane unit represented by the formula 5 as the siloxane unit C, R in the formula 5⁵Is a hydrocarbon group having 1 to 24 carbon atoms.¹~ R³Is the same as described above. Among the siloxane units represented by the formula 5, preferable siloxane units include a phenylsiloxane unit, an n-decylsiloxane unit, a benzylsiloxane unit and the like, and among them, a phenylsiloxane unit is more preferable.
[0029]
The silicone resin used as the second component in the treatment agent of the present invention contains the siloxane unit A, the siloxane unit B and the siloxane unit C as main constituent units as described above, and the siloxane unit A in one molecule. 1 to 550 siloxane units B, 1 to 1800 siloxane units C, and 1 to 1,800 siloxane units C. When the siloxane unit C has a siloxane unit represented by the formula 4, Number / Number of siloxane units represented by Formula 4 = 0.8 to 1.5, and when the siloxane unit C has a siloxane unit represented by Formula 5, the number of siloxane units represented by Formula 1 / Formula 5 The number of siloxane units shown is 0.5 to 1.5. Among these silicone resins, 1) 1 to 390 siloxane units of the formula 1 as the siloxane unit A, 1 to 70 siloxane units of the formula 3 as the siloxane unit B in one molecule, A silicone resin having 1 to 560 siloxane units of the formula 4 as C and 1 to 650 siloxane units of the formula 5; 2) a siloxane unit of the formula 1 as a siloxane unit A in one molecule; 1 to 390 siloxane units, 1 to 70 siloxane units of the formula 2 as the siloxane unit B, 1 to 560 siloxane units of the formula 4 as the siloxane unit C, and 1 to 650 of the siloxane unit of the formula 5 3) In one molecule, 1 to 390 of siloxane units represented by the formula 1 as siloxane units A in one molecule. 1 to 70 siloxane units of the formula 2 and 1 to 70 siloxane units of the formula 3 as the siloxane unit B, and 1 to 560 siloxane units of the formula 4 as the siloxane unit C and the formula 5 4) A silicone resin having 1 to 650 siloxane units represented by the formula: 4) In one molecule, 1 to 390 siloxane units represented by the formula 1 as the siloxane unit A, and a siloxane unit represented by the formula 2 as the siloxane unit B in one molecule. A silicone resin having 1 to 70 siloxane units represented by the formula 4 as the siloxane unit C; 5) 1 to 390 siloxane units represented by the formula 1 as the siloxane unit A in one molecule; 1 to 70 siloxane units represented by the formula 3 as the unit B, and siloxanes represented by the formula 4 as the siloxane unit C Silicone resin having 1 to 560 units; 6) 1 to 390 siloxane units of the formula 1 as siloxane units A and 1 to 70 siloxane units of the formula 2 as siloxane units B in one molecule. And a silicone resin having 1 to 70 siloxane units represented by the formula 3 and 1 to 560 siloxane units represented by the formula 4 as the siloxane unit C; 7) represented by the formula 1 as the siloxane unit A in one molecule. A silicone resin having 1 to 370 siloxane units, 1 to 70 siloxane units represented by Formula 2 as siloxane unit B, and 1 to 650 siloxane units represented by Formula 5 as siloxane unit C; 1 to 370 siloxane units represented by the formula 1 as the siloxane unit A, and represented by the formula 3 as the siloxane unit B A silicone resin having 1 to 70 siloxane units and 1 to 650 siloxane units of the formula 5 as the siloxane unit C; 9) 1 to 370 of the siloxane units of the formula 1 as the siloxane unit A in one molecule; Silicone having 1 to 70 siloxane units of the formula 2 as the siloxane unit B, 1 to 70 siloxane units of the formula 3 as the siloxane unit B, and 1 to 650 siloxane units of the formula 5 as the siloxane unit C Resins are preferred.
[0030]
The silicone resin used as the second component in the treatment agent of the present invention has an amino equivalent of 1,000 to 100,000, preferably 1500 to 30,000, and a weight average molecular weight of 1,000 to 100,000. It is preferred to be 5000 to 50,000.
[0031]
As described above, the silicone resin used as the second component in the treatment agent of the present invention has a siloxane unit A, a siloxane unit B, and a siloxane unit C as main constituent units, and these siloxane units are usually included in all constituent units. Has a total of 65 mol% or more, but preferably has a total of 70 mol% or more of these siloxane units, and more preferably has a total of 85 mol% or more of these siloxane units.
[0032]
In the silicone resin used as the second component in the treatment agent of the present invention, the siloxane units other than the siloxane unit A, the siloxane unit B and the siloxane unit C are the same as those used for forming these siloxane units A to C. Examples include siloxane units formed from silane compounds. In general, a siloxane unit in which a hydroxyl group, an alkyloxy group, or an alkyloxy group having a substituent is directly bonded to a silicon atom is mentioned, and specifically, (HO)₃SiO_1/2, (HO)₂SiO_2/2, (HO) SiO_3/2, (HO) X¹R⁴SiO_1/2, (HO)₂X²SiO_1/2, (HO) X²SiO_2/2, (HO)₂R⁵SiO_1/2, (HO) R⁵SiO_2/2, (HO)₂(R¹¹O) SiO_1/2, (HO) (R¹¹O)₂SiO_1/2, (HO) (R¹¹O) SiO_2/2, (R¹¹O)₂SiO_2/2, (R¹¹O) SiO_3/2, (R¹¹O) X¹R⁴SiO_1/2, (HO) (R¹¹O) X²SiO_1/2, (R¹¹O)₂X²SiO_1/2, (R¹¹O) X²SiO_2/2, (HO) (R¹¹O) R⁵SiO_1/2, (R¹¹O)₂R⁵SiO_1/2, (R¹¹O) R⁵SiO_2/2A siloxane unit represented by the following formula (provided that R is⁴, R⁵, X¹, X²Is the same as described above for Formulas 2-5, and R¹¹O is an alkyloxy group or an alkyloxy group having a substituent).
[0033]
The third component provided to the treating agent of the present invention is an organic phosphate ester salt represented by the formula 7 and / or an organic phosphate ester salt represented by the formula 8.
[0034]
The organic phosphoric acid ester salt represented by the formula 7 includes: 1) an organic phosphoric acid monoester salt when n in the formula 7 is 1; 2) an organic phosphoric acid diester when n in the formula 7 is 2 Salts, 3) mixtures thereof.
[0035]
In the organic phosphate ester salt represented by the formula 7, R in the formula 7⁹Is an aliphatic hydrocarbon group having 12 to 26 carbon atoms. For example, 1) linear aliphatic hydrocarbon groups having 12 to 26 carbon atoms such as dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, docosyl group, tetracosyl group, hexacosyl group, etc. 2) A branched aliphatic hydrocarbon group having 12 to 26 carbon atoms such as an isododecyl group, an isotridecyl group, an isotetradecyl group, an isohexadecyl group, an isooctadecyl group, an isoeicosyl group, an isodocosyl group, an isotetracosyl group, and an isohexacosyl group. Among them, a branched aliphatic hydrocarbon group having 12 to 18 carbon atoms such as an isododecyl group, an isotridecyl group, an isotetradecyl group, an isohexadecyl group, and an isooctadecyl group is preferable.
[0036]
In the organic phosphoric acid ester salt represented by the formula 7,¹Examples thereof include: 1) lower alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, and triisopropanolamine; 2) methyldiethanolamine, butyldiethanolamine, dibutylethanolamine, butylmonoethanolamine, octyldiethanolamine, dodecyldiethanolamine, and the like. And N) alkyl-substituted alkanolamines, 3) alkali metals such as sodium, potassium and lithium. Among them, N-alkyl-substituted alkanolamines, sodium and potassium are preferable.
[0037]
The organic phosphate salt represented by the formula 7 can be synthesized by a known method. For example, it can be synthesized by reacting a higher alcohol with phosphoric anhydride to obtain a corresponding acidic organic phosphate, and then neutralizing the acidic organic phosphate with an alkanolamine or an alkali hydroxide.
[0038]
The organic phosphate ester salt represented by the formula 8 includes 1) an organic phosphate monoester salt when s in the formula 8 is 1 and 2) an organic phosphate diester when the s in the formula 8 is 2 Salts, 3) mixtures thereof.
[0039]
In the organic phosphate salt represented by the formula 8, R in the formula 8¹⁰Is R in Formula 7⁹Is the same as described above. Also, M in equation 8²Also, M in Equation 7¹Is the same as described above. As Y in Formula 8, 1) a residue obtained by removing all hydroxyl groups from a (poly) oxyethylene diol having 1 to 10 oxyethylene units, and 2) a residue having 1 to 10 oxypropylene units. Residues obtained by removing all hydroxyl groups from polyoxyalkylene diols having 2 to 10 repetitions of oxyethylene units and oxypropylene units, and 3) residues obtained by removing all hydroxyl groups from (poly) oxypropylene diol. Among them, a residue obtained by removing all hydroxyl groups from a polyoxyalkylene diol having 2 to 6 oxyethylene units and / or oxypropylene units is preferable, and a polyoxyethylene having 2 to 6 oxyethylene units. A residue obtained by removing all hydroxyl groups from a diol is more preferred.
[0040]
The organic phosphate salt represented by the formula 8 can be synthesized by a known method. For example, by reacting an alkylene oxide adduct of a higher alcohol with phosphoric anhydride to obtain a corresponding acidic organic phosphate, the acid organic phosphate is neutralized with an alkanolamine or an alkali hydroxide. Can be synthesized.
[0041]
As the third component to be provided to the treating agent of the present invention, an organic phosphate ester salt represented by the formula 7 or an organic phosphate ester salt represented by the formula 8 can be used alone. The acid ester salt and the organic phosphoric acid ester salt represented by the formula 8 can be used as a mixture, but among them, the organic phosphoric acid ester salt represented by the formula 8 is preferable, and the organic metal salt of the organic phosphoric acid ester is more preferable. .
[0042]
The treating agent of the present invention is composed of a two-component system of the first component and the second component described above, or is composed of a three-component system of the first component, the second component and the third component described above. is there. In the case of the treating agent of the present invention, which is composed of a two-component system of the first component and the second component, the ratio of the first component / the second component = 100 / 0.1 to 100/30 (weight ratio). It is preferable that the first component / the second component be contained at a ratio of 100/1 to 100/10 (weight ratio). When it is composed of a three-component system of a first component, a second component, and a third component, the content ratio of the first component and the second component is the same as described above, and the first component and the second component are further described. Of the first component, the second component, and the third component in a ratio of 100 / 0.01 to 100/20 (weight ratio). It is preferable to include the total / third component in a ratio of 100 / 0.05 to 100/5 (weight ratio).
[0043]
The treating agent of the present invention is composed of a two-component system or a three-component system as described above, but other components may be used in combination depending on the purpose. Such other components are known per se as smoothness improvers such as polyether-modified silicone, amino-modified silicone, alkyl-modified silicone, and alkylaralkyl-modified silicone, MQ resins, MTQ resins, and MDTQ resins. Silicone resins without amino groups, alkaline earth metal salts of higher fatty acids, unwinding improvers such as talc, other anionic surfactants, cationic surfactants, antistatic agents such as amphoteric surfactants, etc. No.
[0044]
The treating agent of the present invention can be applied to polyurethane-based elastic fibers produced by any method such as dry spinning, melt spinning, and wet spinning, but is particularly applicable to polyurethane-based elastic fibers produced by melt spinning. Is preferred.
[0045]
The treatment method of the present invention is a method in which the above-described treatment agent of the present invention is adhered to polyurethane elastic fibers by a neat lubrication method in which the treatment agent is supplied without dilution with a solvent or the like. The attaching step is a step after the spinning and before winding into a package. Known methods such as a roller lubrication method, a guide lubrication method, and a spray lubrication method can be applied as the adhesion method. The amount of the treatment agent of the present invention is adjusted to be 0.1 to 10% by weight, preferably 3 to 7% by weight, based on the polyurethane elastic fiber.
[0046]
BEST MODE FOR CARRYING OUT THE INVENTION
Embodiments of the treatment agent of the present invention include the following 1) to 9).
1) Consists of the following first component (E-1), the following second component (S-1), and the following third component (D-1), and the first component (E-1) / the The second component (S-1) = 100 / 1.54 (weight ratio), and the first component (E-1), the second component (S-1), and the third component (D- A treating agent (P-1) containing the third component (D-1) in a ratio of 100/1 (weight ratio) with the sum of the components (1) and (3).
First component (E-1): viscosity at 25 ° C. is 10 × 10^-6m²/ S silicone oil
Second component (S-1): a silicone resin having a total of 92 mol% of siloxane unit A, siloxane unit B, and siloxane unit C in all constituent units, wherein siloxane unit A is a trimethylsiloxane unit, and the siloxane unit is B is an N- (2-aminoethyl) -3-iminopropylsiloxane unit, the siloxane unit C is a siloxane unit represented by the formula 4, and 265 of the siloxane units A in one molecule; B, 311 siloxane units C, and the number of the siloxane units A / the number of the siloxane units C = 0.85, a silicone resin having an amino equivalent of 20170 and a weight average molecular weight of 40,300 (S-1 )
Third component (D-1): sodium α-isododecyl-ω-hydroxy (polyoxyethylene) phosphate (however, the number of repeating oxyethylene units is 2, hereinafter, v = 2)
[0047]
2) The first component (E-1), the second component (S-2) and the third component (D-1) described below, and the first component (E-1) / the first component (E-1) The second component (S-2) = 100 / 5.88 (weight ratio), and the first component (E-1), the second component (S-2), and the third component (D- A treating agent (P-2) containing the third component (D-1) at a ratio of 100/1 (weight ratio) with the sum of (1) and (3).
Second component (S-2): a silicone resin having a total of 88 mol% of a siloxane unit A, a siloxane unit B, and a siloxane unit C in all the constituent units, wherein the siloxane unit A is a trimethylsiloxane unit and the siloxane unit B is an N-phenyl-3-iminopropylsiloxane unit, the siloxane unit C is a siloxane unit represented by the formula 4, and 107 siloxane units A and 2 siloxane units B in one molecule; A silicone resin (S-2) having 107 siloxane units C and having an amino equivalent of 7740 and a weight average molecular weight of 15500, wherein the number of the siloxane units A / the number of the siloxane units C = 1.
[0048]
3) The following first component (E-2), the following second component (S-3), and the following third component (D-2), and the first component (E-2) / The second component (S-3) = 100 / 0.51 (weight ratio), and the first component (E-3), the second component (S-3), and the third component (D- A treating agent (P-3) containing the third component (D-2) in a ratio of 100/1 (weight ratio) with the sum of (2) and (3).
First component (E-2): viscosity at 25 ° C. is 10 × 10^-6m²/ S silicone oil
Second component (S-3): a silicone resin having a total of 89 mol% of a siloxane unit A, a siloxane unit B and a siloxane unit C in all the constituent units, wherein the siloxane unit A is an octadecyldimethylsiloxane unit, The unit B is an N- (2,4-dicarboxybenzene-carbonyl) -3-iminopropylsiloxane unit, the siloxane unit C is a siloxane unit represented by the formula 4, and the siloxane unit A is contained in one molecule. 132 silicone units, 4 siloxane units B, 132 siloxane units C, and the number of the siloxane units A / the number of the siloxane units C = 1, wherein the silicone resin has an amino equivalent of 12100 and a weight average molecular weight of 48,700. (S-3)
Third component (D-2): α-isooctadecyl-ω-hydroxy (polyoxyethylene) potassium phosphate (v = 2)
[0049]
4) The first component (E-1), the second component (S-1), and the third component (D-3) described below, and the first component (E-1) / The second component (S-1) = 100 / 1.54 (weight ratio), and the first component (E-1), the second component (S-1), and the third component (D- 3) A treating agent (P-4) containing the third component (D-3) at a ratio of 100/1 (weight ratio).
Third component (D-3): isododecyl phosphate = dibutylethanolamine
[0050]
5) The first component (E-1) / the second component (S-2) and the third component (D-3), and the first component (E-1) / the first component (E-1) The second component (S-2) = 100 / 1.57 (weight ratio), and the first component (E-1), the second component (S-2), and the third component (D- 3) A treating agent (P-5) containing the third component (D-3) at a ratio of 100/3 (weight ratio).
[0051]
6) The first component (E-2) / the second component (S-3) and the third component (D-4) described below, and the first component (E-2) / The second component (S-3) = 100 / 3.65 (weight ratio), and the first component (E-2), the second component (S-3), and the third component (D- 4) A treating agent (P-6) containing the third component (D-4) at a ratio of 100 / 0.5 (weight ratio).
Third component (D-4): dodecyl phosphate = dibutylethanolamine
[0052]
7) The first component (E-1) and the second component (S-1), and the first component (E-1) / the second component (S-1) = 100 / Treatment agent (P-20) containing 1.52 (weight ratio).
[0053]
8) The first component (E-1) and the second component (S-2), and the first component (E-1) / the second component (S-2) = 100 / A treating agent (P-21) containing 5.82 (weight ratio).
[0054]
9) The first component (E-2) and the second component (S-3), and the first component (E-2) / the second component (S-3) = 100 / A treating agent (P-22) containing 0.50 (weight ratio).
[0055]
Embodiments of the processing method of the present invention include the following 10).
10) The treatment agents of the above 1) to 9) are attached by a neat lubrication method without dilution to the polyurethane-based elastic fibers after spinning and before being wound up into a package so as to be 3 to 7% by weight. A method for treating polyurethane-based elastic fibers.
[0056]
Hereinafter, although an example is given in order to make the composition and effect of the present invention more specific, the present invention is not limited to the example. In addition, in the following Examples and the like, parts indicate parts by weight and% indicates% by weight unless otherwise specified.
[0057]
【Example】
・ Test Category 1 (Synthesis of silicone resin as second component)
・ Synthesis of silicone resin (S-1)
215 g (1.3 mol) of hexamethyldisiloxane, 240 g of water, 2.0 g of methanesulfonic acid and 647 g (3.1 mol) of tetraethoxysilane were charged into a reaction vessel and heated to bring the temperature of the reaction system to 78 ° C. The mixture was kept warm and stirred for 24 hours. Then, the mixture was neutralized by adding 1.78 g of sodium hydrogen carbonate, and refluxed for 5 hours to mature. Thereafter, 640 g of xylene was charged into a reaction vessel, and water and ethanol produced as a by-product of the reaction were distilled off, replaced with a xylene solution, and filtered. After adjusting the effective concentration (resin concentration in the xylene solution) of the obtained filtrate to 50%, 200 g of the filtrate was charged into another reaction vessel, and N- (2-aminoethyl) -3-iminopropyltrimethoxysilane was added. .55 g (2.5 × 10^-3Mol) and 0.13 g of water were added and reacted at 80 ° C. for 0.1 hour. Xylene, water and methanol were distilled off from the reaction solution under reduced pressure to obtain a silicone resin (S-1). The following analysis was performed on the silicone resin (S-1). The silicone resin (S-1) contained R¹, R², R³Is a methyl group, and a siloxane unit represented by the formula 1²Is a N- (2-aminoethyl) -3-iminopropyl group, and has a total of 92 mol% of a siloxane unit of the formula 4 and a siloxane unit of the formula 4; And 265 siloxane units represented by the formula, one siloxane unit represented by the formula 3, and 311 siloxane units represented by the formula 4. The silicone resin had an amino equivalent of 2,170 and a weight average molecular weight of 43,000.
[0058]
Analysis of bonded shiroquinsan units: The silicone resin (S-1) is subjected to elemental analysis, ICP emission spectroscopy, and FT-IR spectroscopy to measure the total carbon content and silicon content, and to perform silicon-carbon bonding. A silicon-oxygen-silicon bond was confirmed. These analytical values, solid²⁹Formula 1 shows the integral value of the NMR spectrum of CP / MAS for Si, the carbon number of hexamethyldisiloxane used as a raw material, and the carbon number of N- (2-aminoethyl) -3-iminopropyltrimethoxysilane. The ratios of the siloxane unit, the siloxane unit represented by Formula 3, and the siloxane unit represented by Formula 4 were calculated.
[0059]
Calculation of the number of siloxane units in the molecule: The ratio of the siloxane unit in the molecule obtained in the above, the theoretical molecular weight of the siloxane unit constituting the silicone resin (S-1), and the following measured value of the weight average molecular weight of the siloxane in the molecule. The number of units was calculated.
[0060]
・ Weight average molecular weight
For the silicone resin (S-1), using a column in which polystyrene columns of TSK-GEL SUPER4000, TSK-GEL SUPER3000 and TSK-GEL SUPER2000 (all trade names manufactured by Tosoh Corporation) were connected in series, and the moving layer was THF. And the weight average molecular weight was calculated in terms of polystyrene.
[0061]
・ Amino equivalent
After dissolving the silicone resin (S-1) in a xylene / acetic anhydride = 80/20 (volume ratio) mixture, measurement was performed by potentiometric titration using a 0.1 mol / L methanol solution of perchloric acid as a titrant. did.
[0062]
-Synthesis of silicone resins (S-2) to (S-14) and (r-1) to (r-12)
In the same manner as in the case of the silicone resin (S-1), silicone resins (S-2) to (S-14) and (r-1) to (r-12) were synthesized and analyzed. Table 1 shows the content of each synthesized silicone resin.
[0063]
[Table 1]

[0064]
In Table 1,
Number: Number of siloxane units in one molecule
* 1: Total mole% of siloxane unit A, siloxane unit B and siloxane unit C in all the constituent units constituting the silicone resin as the second component
* 2: Number of siloxane units A represented by Formula 1 / Number of siloxane units C represented by Formula 4
* 3: Number of siloxane units A represented by Formula 1 / Number of siloxane units C represented by Formula 5
* 4: Amino equivalent
* 5: Weight average molecular weight
[0065]
A-1: Trimethylsiloxane unit [R¹= CH₃, R²= CH₃, R³= CH₃A siloxane unit represented by the formula 1 when
A-2: Octadecyldimethylsiloxane unit [R¹= C₁₈H₃₇, R²= CH₃, R³= CH₃A siloxane unit represented by the formula 1 when
B-1: 3-aminopropylmethylsiloxane unit [X¹= NH₂C₃H₆, R⁴= CH₃A siloxane unit of the formula 2 when
B-2: N-phenyl-3-iminopropylmethylsiloxane unit (X¹= C₆H₅-NHC₃H₆, R = CH₃Where the siloxane unit is represented by the formula 2)
B-3: N- (2-carboxyethylcarbonyl) -3-iminopropylmethylsiloxane unit (X¹= HOOC-C₂H₄-CONH-C₂H₄-NHC₃H₆, R⁴= CH₃Where the siloxane unit is represented by the formula 2)
B-4: N- (2,4-dicarboxybenzene-carbonyl) -3-iminopropylmethylsiloxane unit [X¹= (HOOC)₂C₆H₃CONHC₃H₆, R⁴= CH₃A siloxane unit of the formula 2 when
B-5: N- (2-aminoethyl) -3-iminopropylmethylsiloxane unit (X¹= NH₂-C₂H₄NHC₃H₆, R⁴= CH₃Where the siloxane unit is represented by the formula 2)
B-6: 3-aminopropylsiloxane unit (X²= NH₂C₃H₆A siloxane unit of the formula 3 when
B-7: N-phenyl-3-iminopropylsiloxane unit (X²= C₆H₅-NHC₃H₆A siloxane unit of the formula 3 when
B-8: N- (2-carboxyethylcarbonyl) -3-iminopropylsiloxane unit (X²= HOOC-C₂H₄-CONH-C₃H₆A siloxane unit of the formula 3 when
B-9: N- (2,4-dicarboxybenzene-carbonyl) -3-iminopropylsiloxane unit [X²= (HOOC)₂C₆H₃CONH-C₃H₆A siloxane unit of the formula 3 when
B-10: N- (2-aminoethyl) -3-iminopropylsiloxane unit (X²= NH₂C₂H₄-NH-C₃H₆A siloxane unit of the formula 3 when
C-1: a siloxane unit represented by the formula 4
C-2: phenylsiloxane unit (R⁵= C₆H₅A siloxane unit of the formula 5 when
C-3: n-decylsiloxane unit (R⁵= C₁₀H₂₁A siloxane unit of the formula 5 when
[0066]
・ Test Category 2 (Preparation of treatment agent)
-Example 1 {Preparation of treating agent (P-1)}
The first component has a viscosity of 10 × 10 at 25 ° C.^-6m²/ S silicone oil (E-1) 97.5 parts, as a second component 1.5 parts of a silicone resin (S-1) synthesized in Test Category 1, and as a third component α-isododecyl-ω-hydroxyphosphate One part of (polyoxyethylene) sodium (v = 2) (D-1) was mixed and stirred at a temperature of 20 to 25 ° C. until uniform to prepare a treating agent (P-1).
[0067]
-Examples 2-33 and Comparative Examples 1-14 {Preparation of treating agents (P-2) to (P-33) and treating agents (R-1) to (R-14)}
Similarly to the treating agent (P-1) of Example 1, the treating agents (P-2) to (P-33) of Examples 2 to 33 and the treating agents (R-1) to of Comparative Examples 1 to 14 (R-14) was prepared. Tables 2 and 3 summarize the contents of these treating agents.
[0068]
[Table 2]

[0069]
[Table 3]

[0070]
In Tables 2 and 3,
Ratio: part
* 6: The value of x when the first component / the second component = 100 / x (weight ratio)
* 7: y value at (first component + second component + third component) / third component = 100 / y (weight ratio)
* 8: The value of z when the first component / second component, etc. = 100 / z (weight ratio)
[0071]
E-1: the viscosity at 25 ° C. is 10 × 10^-6m²/ S silicone oil
E-2: the viscosity at 25 ° C. is 20 × 10^-6m²/ S silicone oil
E-3: (viscosity at 25 ° C. is 20 × 10^-6m²/ S silicone oil) / (viscosity at 25 ° C. is 19 × 10^-6m²/ S refined paraffin oil) = 75/25 (weight ratio) mixture
E-4: (viscosity at 25 ° C. is 10 × 10^-6m²/ S silicone oil) / (viscosity at 25 ° C. is 19 × 10^-6m²/ S polyalphaolefin oil) = 85/15 (weight ratio) mixture
S-1 to S-14, r-1 to r-12: silicone resin synthesized in Test Category 1
D-1: α-isododecyl phosphate-ω-hydroxy (polyoxyethylene) = sodium (v = 2)
D-2: α-isooctadecyl phosphate-ω-hydroxy (polyoxyethylene) = potassium (v = 2)
D-3: isododecyl phosphate = dibutylethanolamine
D-4: dodecyl phosphate = dibutylethanolamine
[0072]
・ Test Category 3 (Polyurethane-based elastic fiber treatment)
-Examples 34-66 and Comparative Examples 15-28
Each treatment agent adjusted in Test Category 2 is described in Table 4 and Table 5 by roller oiling method on polyurethane-based elastic fibers melt-spun using a polyurethane polymer obtained from polytetramethylene glycol having a molecular weight of 1000 and diphenylmethane diisocyanate. Neat lubrication was performed so that the adhesion amount was obtained, followed by winding the yarn around a yarn tube at a speed of 600 m / min to obtain a package made of treated polyurethane elastic fibers having a winding width of 38 mm and a winding amount of 400 g and a fineness of 22 dtex.
[0073]
Test Category 4 (Evaluation)
The package obtained in Test Category 3 was subjected to the following evaluation. The results are summarized in Tables 4 and 5.
・ Evaluation of winding shape
For the package, the bulge and saddle were measured, and a twill drop on the end face was visually observed to evaluate the winding shape.
[0074]
Bulge (unit: mm): The maximum value and the minimum value of the winding width of the package were measured, and the difference between them was evaluated according to the following criteria.
◎: less than 4 mm
〜 To ：: 4 mm or more and less than 5 mm
：: 5 mm or more and less than 6 mm
Δ: 6 mm or more and less than 7 mm
×: 7 mm or more
[0075]
Saddle (unit: mm): Place the package so that the winding width of the polyurethane-based elastic fiber is visible from the front, measure the diameter of the largest circumferential part and the diameter of the smallest circumferential part of the package, and determine the difference between the two. Evaluation was based on criteria.
◎: less than 1mm
◎ to ○: 1 mm or more and less than 2 mm
：: 2 mm or more and less than 3 mm
Δ: 3 mm or more and less than 4 mm
×: 4 mm or more
[0076]
Aya omission: At the end face of the package, the extent to which the wound treated polyurethane-based elastic fiber has slipped off from the circumferential surface was visually observed and evaluated according to the following criteria.
○: No twill drop
×: Aya omission is observed
[0077]
・ Evaluation of unwinding property
The first driving roller and the first releasing roller which is always in contact therewith constitute a feeding portion, and the second driving roller and the second releasing roller which is always in contact therewith constitute a winding portion, and the feeding portion is formed. The winding part was placed 20 cm apart from the part in the horizontal direction. The package was mounted on the first drive roller, and unwound until the thickness of the thread became 2 mm to obtain a sample. A treated polyurethane elastic fiber was wound from this sample around a second drive roller. The feed speed of the treated polyurethane elastic fiber from the first drive roller is fixed at 50 m / min, while the winding speed of the treated polyurethane elastic fiber to the second drive roller is gradually increased from 50 m / min. The treated polyurethane elastic fiber was forcibly unwound from the package. At the time of the forced unwinding, the winding speed V (m / min) was measured at the time when the treated polyurethane elastic fiber no longer danced between the sending portion and the winding portion. Then, the unwinding property (%) was determined by the following equation, and evaluated according to the following criteria.
Unwinding property (%) = (V−50) × 2
：: Unwinding property is less than 110% (can be unwound stably without any problem)
〜 To ：: Unwinding property of 110 or more and less than 125% (although there is slight resistance in pulling out the yarn, there is no occurrence of yarn breakage and stable unwinding can be performed)
：: Unwinding property of 125 or more and less than 135% (although there is a little resistance in pulling out the yarn, there is no occurrence of yarn breakage and the yarn can be unwound stably)
Δ: Unwinding property of 135 or more and less than 145% (obviously there is resistance in pulling out the yarn, there is some breakage of the yarn, and there is a problem in the operation)
X: Unwinding property of 145% or more (there is a large resistance in pulling out the yarn, and the yarn breakage occurs frequently, causing a serious problem in operation).
[0078]
・ Evaluation of smoothness
Using a μ meter manufactured by Eiko Sokki Co., Ltd., the initial tension (T¹) 5 g and the secondary tension (T) when running at a yarn speed of 100 m / min.²) Was measured. Then, the coefficient of friction was calculated by the following equation, and evaluated according to the following criteria.
Coefficient of friction = (T²−T¹) / (T²+ T¹)
◎: 0.150 or more and less than 0.200
〜 To ：: 0.200 or more and less than 0.215
：: 0.215 or more and less than 0.230
Δ: 0.230 or more and less than 0.245
×: 0.245 or more
[0079]
・ Evaluation of antistatic properties
The electric resistance value of 10 g of the treated polyurethane-based elastic fiber pulled out from the package was measured using an electric resistance measuring instrument (SM-5E manufactured by Toa Denpa Kogyo Co., Ltd.) in an atmosphere of 25 ° C. × 40% RH. The measured values were evaluated according to the following criteria.
：: electric resistance value 1.0 × 10⁹Less than Ω (stable operation without any problem)
〜 To ：: electric resistance value 1.0 × 10⁹Ω or more 5.0 × 10¹⁰Less than Ω (slightly warping may occur in the warping process, but stable operation is possible)
：: electric resistance value 5.1 × 10¹⁰Ω or more 1.0 × 10¹¹Less than Ω (There is slight deviation in the warping process, but stable operation is possible without any problems)
Δ: electric resistance value 1.1 × 10¹¹Ω or more 1.0 × 10^{1 2}Less than Ω (There is no problem in operability although there is sticking in the warping process and adhesion of fly wool in the circular knitting process)
×: electric resistance value 1.0 × 10^{1 2}Ω or more (operation in the warping process is intense, and in the circular knitting process, there is strong adhesion of fly wool, making it impossible to operate)
[0080]
[Table 4]

[0081]
[Table 5]

[0082]
【The invention's effect】
As already apparent, in the present invention described above, it is possible to obtain an excellent wound-shaped package in the polyurethane elastic fiber production process, and at the same time, to obtain excellent unwinding property of the polyurethane elastic fiber used in the processing step. , Smoothness and antistatic properties.

Claims (15)

It is characterized by comprising the following first component and the following second component, and containing the first component / the second component in a ratio of 100 / 0.1 to 100/30 (weight ratio). For polyurethane-based elastic fibers.
First component: a silicone oil and / or a hydrocarbon oil having a viscosity of 2 × 10 ^{−6 to} 100 × 10 ⁻⁶ m ² / s at 25 ° C. Second component: a siloxane unit A, a siloxane unit B, and a siloxane unit C Wherein the siloxane unit A is a siloxane unit represented by the following formula 1, the siloxane unit A is a siloxane unit represented by the following formula 2, and / or a siloxane unit represented by the following formula 3. A siloxane unit, wherein the siloxane unit C is a siloxane unit represented by the following formula 4 and / or a siloxane unit represented by the following formula 5, and 1 to 550 of the siloxane units A in one molecule; In the case where it has 1 to 200 units B and 1 to 1800 siloxane units C, and has a siloxane unit represented by the formula 4 as the siloxane unit C The number of siloxane units represented by the formula 1 / the number of siloxane units represented by the formula 4 = 0.8 to 1.5, and when the siloxane unit C has a siloxane unit represented by the formula 5, A silicone resin having an amino equivalent of 1,000 to 100,000 and a weight average molecular weight of 1,000 to 100,000, wherein the number of siloxane units represented by the formula / the number of siloxane units represented by the formula 5 is 0.5 to 1.5.

[Equation 2]

[Equation 3]

(Equation 4)

(Equation 5)

に お い て In Equations 1 to 5,
R ^{1 to} R ⁵ : a hydrocarbon group having 1 to 24 carbon atoms X ¹ , X ² : an organic group represented by the following formula 6 [formula 6]

(In Equation 6,
R ⁶ , R ⁷ : an alkylene group having 1 to 5 carbon atoms R ⁸ : one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, and a 1 to 4 aliphatic carboxylic acid having 4 to 22 carbon atoms A residue excluding one hydroxyl group from a residue excluding a hydroxyl group or a monovalent to tetravalent aromatic carboxylic acid having 6 to 22 carbon atoms f: 0 or 1)｝ The first component and the second component according to claim 1, and the following third component, and the ratio of the first component / the second component = 100 / 0.1 to 100/30 (weight ratio). And a ratio of the sum of the first component, the second component, and the third component / the third component = 100 / 0.01 to 100/20 (weight ratio). For polyurethane-based elastic fibers.
Third component: an organic phosphate ester salt represented by the following formula 7 and / or an organic phosphate ester salt represented by the following formula 8 [Formula 7]

(Equation 8)

(In Equations 7 and 8,
R ⁹ , R ¹⁰ : aliphatic hydrocarbon groups m, n, r, s having 12 to 26 carbon atoms: 1 or 2, and integers M ¹ , M ² satisfying m + n = 3, r + s = 3: alkanol Amine or alkali metal Y: a residue obtained by removing all hydroxyl groups from a (poly) oxyalkylene diol having 1 to 10 oxyethylene units or a repeating number of oxyalkylene units composed of oxyethylene units and oxypropylene units) The second component has a total of 85 mol% or more of the siloxane unit A, the siloxane unit B, and the siloxane unit C in all the constituent units, and another siloxane unit formed from the siloxane compound for forming the siloxane unit. The treatment agent for a polyurethane-based elastic fiber according to claim 1 or 2, which is a silicone resin having the balance of: In the second component, the siloxane unit A is a siloxane unit represented by the formula 1, the siloxane unit B is a siloxane unit represented by the formula 3, and the siloxane unit C is a siloxane unit represented by the formula 4 and a siloxane unit represented by the formula 5. In one molecule, 1 to 390 siloxane units represented by Formula 1, 1 to 70 siloxane units represented by Formula 3, 1 to 560 siloxane units represented by Formula 4, and 5 The treating agent for polyurethane-based elastic fibers according to any one of claims 1 to 3, wherein the treating agent is a silicone resin having 1 to 650 siloxane units. In the second component, the siloxane unit A is a siloxane unit represented by the formula 1, the siloxane unit B is a siloxane unit represented by the formula 2, and the siloxane unit C is a siloxane unit represented by the formula 4 and a siloxane unit represented by the formula 5. In one molecule, 1 to 390 siloxane units represented by the formula 1, 1 to 70 siloxane units represented by the formula 2, 1 to 560 siloxane units represented by the formula 4, and 5 The treating agent for polyurethane-based elastic fibers according to any one of claims 1 to 3, wherein the treating agent is a silicone resin having 1 to 650 siloxane units. The second component is such that the siloxane unit A is the siloxane unit represented by the formula 1, the siloxane unit B is the siloxane unit represented by the formula 2, and the siloxane unit represented by the formula 3, and the siloxane unit C is the siloxane unit represented by the formula 4. 1 to 390 siloxane units represented by the formula 1, 1 to 70 siloxane units represented by the formula 2, and 1 siloxane unit represented by the formula 3 in one molecule. The polyurethane resin according to any one of claims 1 to 3, which is a silicone resin having from 70 to 70 siloxane units represented by Formula 4 and from 1 to 650 siloxane units represented by Formula 5. A treatment agent for elastic fibers. In the second component, the siloxane unit A is a siloxane unit represented by the formula 1; the siloxane unit B is a siloxane unit represented by the formula 2; the siloxane unit C is a siloxane unit represented by the formula 4; The silicone resin according to claim 1, wherein the silicone resin has 1 to 390 siloxane units represented by 1, 1 to 70 siloxane units represented by Formula 2, and 1 to 560 siloxane units represented by Formula 4. The treatment agent for a polyurethane-based elastic fiber according to any one of the above items. In the second component, the siloxane unit A is a siloxane unit represented by the formula 1, the siloxane unit B is a siloxane unit represented by the formula 3, and the siloxane unit C is a siloxane unit represented by the formula 4. The silicone resin according to claim 1, wherein the silicone resin has 1 to 390 siloxane units represented by 1, 1 to 70 siloxane units represented by Formula 3, and 1 to 560 siloxane units represented by Formula 4. The treatment agent for a polyurethane-based elastic fiber according to any one of the above items. In the second component, the siloxane unit A is a siloxane unit represented by the formula 1, the siloxane unit B is a siloxane unit represented by the formula 2, a siloxane unit represented by the formula 3, and the siloxane unit C is a siloxane unit represented by the formula 4. In one molecule, 1 to 390 siloxane units represented by the formula 1, 1 to 70 siloxane units represented by the formula 2, 1 to 70 siloxane units represented by the formula 3, and 1 The treating agent for polyurethane-based elastic fibers according to any one of claims 1 to 3, which is a silicone resin having 1 to 560 siloxane units. In the second component, the siloxane unit A is a siloxane unit represented by the formula 1, the siloxane unit B is a siloxane unit represented by the formula 2, and the siloxane unit C is a siloxane unit represented by the formula 5. The silicone resin according to claim 1, wherein the silicone resin has 1 to 370 siloxane units represented by 1, 1 to 70 siloxane units represented by Formula 2, and 1 to 650 siloxane units represented by Formula 5. The treatment agent for a polyurethane-based elastic fiber according to any one of the above items. In the second component, the siloxane unit A is a siloxane unit represented by the formula 1, the siloxane unit B is a siloxane unit represented by the formula 3, and the siloxane unit C is a siloxane unit represented by the formula 5. 4. A silicone resin having 1 to 370 siloxane units represented by formula 1, 1 to 70 siloxane units represented by formula 3, and 1 to 650 siloxane units represented by formula 5. The treatment agent for a polyurethane-based elastic fiber according to any one of the above items. In the second component, the siloxane unit A is a siloxane unit represented by the formula 1, the siloxane unit B is a siloxane unit represented by the formula 2, a siloxane unit represented by the formula 3, and the siloxane unit C is a siloxane unit represented by the formula 5. In one molecule, 1 to 370 siloxane units represented by the formula 1, 1 to 70 siloxane units represented by the formula 2, 1 to 70 siloxane units represented by the formula 3, and 1 The treating agent for polyurethane-based elastic fibers according to any one of claims 1 to 3, wherein the treating agent is a silicone resin having 1 to 650 siloxane units. The treatment agent for a polyurethane-based elastic fiber according to any one of claims 1 to 12, wherein the first component is a silicone oil having a viscosity at 25 ° C of 10 × 10 ⁻⁶ to 30 × 10 ⁻⁶ m ² / s. . The polyurethane elastic fiber treating agent according to any one of claims 2 to 13, wherein the third component is an organic phosphate salt represented by the formula (8). The polyurethane-based elastic fiber treating agent according to any one of claims 1 to 14 is diluted by a neat lubrication method with respect to the polyurethane-based elastic fiber after spinning and before being wound into a package. A method for treating a polyurethane elastic fiber, wherein the polyurethane elastic fiber is attached so as to be 1 to 10% by weight.