JP3904332B2 - Additive for spinning oil to be adhered to fiber yarn as aqueous emulsion and spinning oil containing the same - Google Patents

Description

【式２】

【式３】

【０００７】
式１，式２，式３において、
Ｒ¹，Ｒ²，Ｒ³：Ｈ又はＣＨ₃
Ｒ⁴：炭素数１〜２４の炭化水素基
Ｘ¹，Ｘ²：Ｈ、炭素数１〜３のヒドロキシアルキル基又は炭素数１〜８の脂肪族炭化水素基
Ｍ¹：アルカリ金属、ＮＨ₄又は第４級アンモニウムカチオン
【０００８】
本発明の添加剤である両親媒性ビニル共重合体は、式１で示される構成単位Ａ、式２で示される構成単位Ｂ及び式３で示される構成単位Ｃを主構成単位とするものであるが、これら以外の構成単位として下記の式４で示される構成単位Ｄを有するものが好ましい。
【０００９】
【式４】

【００１０】
式４において、
Ｒ⁵：Ｈ又はＣＨ₃
Ｒ⁶：水素又は炭素数１〜６の脂肪族炭化水素基
ｎ：５〜４０の整数
【００１１】
構成単位Ａ〜Ｄの各構成単位は、それぞれ相当するビニル単量体を共重合することで形成される。構成単位Ａを形成することとなるビニル単量体は下記の式５で示されるビニル単量体ａであり、構成単位Ｂを形成することとなるビニル単量体は下記の式６で示されるビニル単量体ｂであって、構成単位Ｃを形成することとなるビニル単量体は下記の式７で示されるビニル単量体ｃである。また構成単位Ｄを形成することとなるビニル単量体は下記の式８で示されるビニル単量体ｄである。
【００１２】
【式５】

【式６】

【式７】

【式８】

【００１３】
式５，式６，式７，式８において、
Ｒ¹〜Ｒ⁶，Ｘ¹，Ｘ²，Ｍ¹，ｎ：式１〜式４と同じ
【００１４】
式１で示される構成単位Ａを形成することとなるビニル単量体ａとしては、１）アクリルアミド、メタクリルアミド、２）Ｎ−メチロールアクリルアミド、Ｎ−２−ヒドロキシエチルアクリルアミド、Ｎ−３−ヒドロキシプロピルアクリルアミド、Ｎ，Ｎ−ビス（２−ヒドロキシエチル）アクリルアミド、Ｎ，Ｎ−ビス（３−ヒドロキシプロピル）アクリルアミド、Ｎ−メチロールメタクリルアミド、Ｎ−２−ヒドロキシエチルメタクリルアミド、Ｎ−３−ヒドロキシプロピルメタクリルアミド、Ｎ，Ｎ−ビス（２−ヒドロキシエチル）メタクリルアミド、Ｎ，Ｎ−ビス（３−ヒドロキシプロピル）メタクリルアミド等の、炭素数１〜３のヒドロキシアルキル基で置換されたＮ置換又はＮ，Ｎ置換（メタ）アクリルアミド、３）Ｎ−メチルアクリルアミド、Ｎ−エチルアクリルアミド、Ｎ−プロピルアクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミド、Ｎ，Ｎ−ジプロピルアクリルアミド、Ｎ−メチルメタクリルアミド、Ｎ−エチルメタクリルアミド、Ｎ−プロピルメタクリルアミド、Ｎ，Ｎ−ジエチルメタクリルアミド、Ｎ，Ｎ−ジプロピルメタクリルアミド等の、炭素数１〜８の脂肪族炭化水素基で置換されたＮ置換又はＮ，Ｎ置換（メタ）アクリルアミドが挙げられるが、なかでもアクリルアミド、メタクリルアミドが好ましい。
【００１５】
式２で示される構成単位Ｂを形成することとなるビニル単量体ｂとしては、１）アクリル酸のアルカリ金属塩、ＮＨ₄塩及び第４級アンモニウム塩、２）メタクリル酸のアルカリ金属塩、ＮＨ₄塩及び第４級アンモニウム塩が上げられるが、なかでもアクリル酸のアルカリ金属塩、メタクリル酸のアルカリ金属塩が好ましい。
【００１６】
式３で示される構成単位Ｃを形成することとなるビニル単量体ｃとしては、１）アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸ヘキシル、アクリル酸オクチル、アクリル酸ラウリル、アクリル酸ステアリル、アクリル酸ベヘニル等の、炭素数１〜２４のアルキル基を有するアクリル酸アルキル、２）メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸ヘキシル、メタクリル酸オクチル、メタクリル酸ラウリル、メタクリル酸ステアリル、メタクリル酸ベヘニル等の、炭素数１〜２４のアルキル基を有するメタクリル酸アルキルが挙げられるが、なかでも炭素数１〜８のアルキル基を有する（メタ）アクリル酸アルキルが好ましい。
【００１７】
式４で示される構成単位Ｄを形成することとなるビニル単量体ｄは、いずれもエトキシ単位の繰り返し数が５〜４０であって、片末端が水素であるヒドロキシポリエトキシエチルアクリレート、片末端が水素であるヒドロキシポリエトキシエチルメタクリレート、また片末端が炭素数１〜６の脂肪族炭化水素基で封鎖された、片末端封鎖型ポリエトキシエチルアクリレート、片末端封鎖型ポリエトキシエチルメタクリレートである。これには例えば、１）ヒドロキシポリエトキシエチルアクリレート、２）ヒドロキシポリエトキシエチルメタクリレート、３）メトキシポリエトキシエチルアクリレート、エトキシポリエトキシエチルアクリレート、プロポキシポリエトキシエチルアクリレート、ブトキシポリエトキシエチルアクリレート、ペントキシポリエトキシエチルアクリレート、ヘキシトキシポリエトキシエチルアクリレート、シクロヘキシトキトポリエトキシエチルアクリレート等の片末端封鎖型ポリエトキシエチルアクリレート、４）メトキシポリエトキシエチルメタクリレート、エトキシポリエトキシエチルメタクリレート、プロポキシポリエトキシエチルメタクリレート、ブトキシポリエトキシエチルメタクリレート、ペントキシポリエトキシエチルメタクリレート、ヘキソキシポリエトキシエチルメタクリレート、シクロヘキソキシポリエトキシエチルメタクリレート等の片末端封鎖型ポリエトキシエチルメタクリレートが挙げられるが、なかでもエトキシ単位の繰り返し数が６〜３０のメトキシポリエトキシエチルアクリレートが好ましい。
【００１８】
本発明の添加剤である両親媒性ビニル共重合体は、以上説明したような構成単位Ａ、構成単位Ｂ及び構成単位Ｃを主構成単位とし、全構成単位中にこれらを合計で８０重量％以上有するものであるが、構成単位Ａ、構成単位Ｂ、構成単位Ｃ及び構成単位Ｄで構成されるものが好ましい。
【００１９】
本発明は、両親媒性ビニル共重合体を構成する各構成単位の割合を特に制限するものではないが、構成単位Ａ〜Ｃを主構成単位とするものの場合、全構成単位中に１０〜５０重量％の構成単位Ａ、１０〜５０重量％の構成単位Ｂ及び３０〜８０重量％の構成単位Ｃ（合計８０〜１００重量％）を有するものが好ましく、全構成単位中に２０〜４５重量％の構成単位Ａ、２０〜４５重量％の構成単位Ｂ及び３５〜６０重量％の構成単位Ｃ（合計８０〜１００重量％）を有するものが更に好ましい。また構成単位Ａ〜Ｃ以外の構成単位として構成単位Ｄを有するものの場合、８〜４０重量％の構成単位Ａ、８〜４０重量％の構成単位Ｂ、２４〜６４重量％の構成単位Ｃ及び１〜２０重量％の構成単位Ｄ（合計１００重量％）で構成されるものが好ましく、１０〜３５重量％の構成単位Ａ、１０〜３５重量％の構成単位Ｂ、３０〜３５重量％の構成単位Ｃ及び３〜１５重量％の構成単位Ｄ（合計１００重量％）で構成されるものが更に好ましい。
【００２０】
本発明の添加剤である両親媒性ビニル共重合体はその数平均分子量（ＧＰＣ法、プルラン換算、以下同じ）を３００００〜３０００００００のものとするが、１００００００〜１５００００００のものとするのが好ましい。
【００２１】
本発明の添加剤である両親媒性ビニル共重合体は、次のような合成方法で得ることができる。例えば鉱物油、ケロシン等の非ラジカル重合性有機溶媒に分子量２０００未満でＨＬＢ８〜１０の非イオン性界面活性剤、分子量２０００以上の油溶性の非イオン性界面活性剤及びＨＬＢ３〜５のソルビタン脂肪酸エステルを溶解し、油相を調製する。別に、各構成単位を形成することとなる所要量の各ビニル単量体を水に溶解し、水相を調製しておく。反応容器に前記油相を入れ、そこへ高速撹拌下に前記水相をゆっくり添加し、油中水系エマルジョンを調製する。その後、撹拌数を抑え、内温を３０℃程度に調節し、反応容器内を窒素置換後、トルエン等の非ラジカル重合性有機溶媒に溶解した油溶性ラジカル開始剤を加えて重合を開始し、所定時間、ビニル単量体混合物を油中水系ラジカル共重合して、両親媒性ビニル共重合体を油中水系エマルジョンとして得る。
【００２２】
上記のような油中水系ラジカル共重合で両親媒性ビニル共重合体を合成する場合、各構成単位を形成することとなるビニル単量体の混合物と水との合計（前記水相）／非ラジカル重合性有機溶媒＝２０／８０〜８０／２０（重量％）の割合となるようにするが、３０／７０〜７０／３０（重量％）の割合となるようにするのが好ましい。構成単位Ａ〜Ｃを主構成単位とし、全構成単位中にこれらを８０重量％以上の割合で有する両親媒性ビニル共重合体を油中水系ラジカル共重合で合成する場合には例えば、構成単位Ａを形成することとなるビニル単量体ａ／構成単位Ｂを形成することとなるビニル単量体ｂ／構成単位Ｃを形成することとなるビニル単量体ｃ＝１０〜５０／１０〜５０／３０〜８０（重量％）の割合で含有し且つこれらを合計で８０重量％以上の割合で含有するビニル単量体混合物を、該ビニル単量体混合物と水との合計／非ラジカル重合性有機溶媒＝２０／８０〜８０／２０（重量％）の割合とした反応系で、油中水系ラジカル共重合する。また構成単位Ａ〜Ｄで構成される両親媒性ビニル共重合体を油中水系ラジカル共重合で合成する場合には例えば、構成単位Ａを形成することとなるビニル単量体ａ／構成単位Ｂを形成することとなるビニル単量体ｂ／構成単位Ｃを形成することとなるビニル単量体ｃ／構成単位Ｄを形成することとなるビニル単量体ｄ＝８〜４０／８〜４０／２４〜６４／１〜２０（重量％）の割合から成るビニル単量体混合物を、該ビニル単量体混合物と水との合計／非ラジカル重合性有機溶媒＝２０／８０〜８０／２０（重量％）の割合とした反応系で、油中水系ラジカル共重合する。
【００２３】
油中水系ラジカル共重合により構成単位Ａ〜Ｄで構成される両親媒性ビニル共重合体を合成する場合、かかる両親媒性ビニル共重合体としては、次の第１工程、第２工程及び第３工程を経て得られるものが特に好ましい。
第１工程：ビニル単量体ａ／ビニル単量体ｂ／ビニル単量体ｃ＝１０〜５０／１０〜５０／３０〜８０（重量％）の割合から成るビニル単量体混合物を、該ビニル単量体混合物と水との合計／非ラジカル重合性有機溶媒＝２０／８０〜８０／２０（重量％）の割合とした反応系で、油溶性ラジカル開始剤存在下に、油中水系ラジカル共重合した後、ラジカル停止し、ラジカル停止した共重合体を得る工程
第２工程：ラジカル停止した共重合体を含む反応系に油溶性ラジカル開始剤を加えて該共重合体をラジカル活性化する工程
第３工程：ラジカル活性化した共重合体を含む反応系にビニル単量体ｄを、第１工程で用いたビニル単量体ａとビニル単量体ｂとビニル単量体ｃとの合計／ビニル単量体ｄ＝８０／２０〜９９／１（重量％）の割合となるように加えて、油中水系ラジカル共重合させ、両親媒性ビニル共重合体を得る工程
【００２４】
第１工程におけるビニル単量体ａ〜ｃの油中水系ラジカル共重合では例えば、予め非ラジカル重合性有機溶媒に分子量２０００未満でＨＬＢ８〜１０の非イオン性界面活性剤、分子量２０００以上の油溶性の非イオン性界面活性剤及びＨＬＢ３〜５のソルビタン脂肪酸エステルを溶解した油相を調製しておき、また別にビニル単量体ａ〜ｃを水に溶解した水相を調製しておく。反応容器に前記油相を入れ、更に高速撹拌下で前記水相をゆっくり添加し、油中水系エマルジョンを調製する。その後、撹拌数を抑え、内温を３０℃程度に調節し、反応容器内を窒素置換後、非ラジカル重合性有機溶媒に溶解したそれ自体は公知の油溶性ラジカル開始剤を加えて油中水系ラジカル共重合を行なう。
【００２５】
第１工程では、ビニル単量体ａ〜ｃの油中水系ラジカル共重合において、その反応系のラジカル停止を適時に行ない、ラジカル停止した共重合体を得る。ラジカル停止の方法としては、ラジカルが反応系から完全に消失してラジカル共重合反応が実質的に停止するまで反応を継続する方法でもよいが、強制的にラジカルを分解消失させるそれ自体は公知のラジカル停止剤を反応系に加える方法が好ましい。後述する第２工程、更には第３工程へと円滑に移行させると共に、得られるラジカル停止した共重合体の分子量調節がし易いからである。
【００２６】
第２工程では、第１工程で得たラジカル停止した共重合体を含む反応系にそれ自体は公知の油溶性ラジカル開始剤を加えて、該共重合体をラジカル活性化する。
【００２７】
第３工程では、第２工程でラジカル活性化した共重合体にビニル単量体ｄを加えて更に油中水系ラジカル共重合を行ない、アルコキシポリオキシエチレン鎖を有する共重合体すなわち本発明の両親媒性ビニル共重合体を得る。第３工程で用いるビニル単量体ｄの量は、第１工程で用いたビニル単量体ａ〜ｃの合計／ビニル単量体ｄ＝８０／２０〜９９／１（重量％）、好ましくは８５／１５〜９７／３（重量％）の割合となるようにする。
【００２８】
第１工程、第２工程及び第３工程によって得られる両親媒性ビニル共重合体は、油中水系エマルジョンの状態にある。かかる油中水系エマルジョンは、もともと本発明が紡糸油剤を水性エマルジョンとして繊維糸条に付着させるものであるから、そのまま添加剤として利用できるが、紡糸油剤の水性エマルジョンを調製する際の便宜上、分子量２０００未満でＨＬＢ８〜１０の非イオン性界面活性剤、水溶性ポリオキシエチレンポリオキシプロピレン誘導体及びＨＬＢ１２〜１４の水溶性非イオン性界面活性剤から成る転相用界面活性剤を加えておくのが好ましい。
【００２９】
本発明は、以上説明した添加剤の使用方法を特に制限するものではない。これには例えば、１）紡糸油剤に添加剤を加えた後、水性エマルジョンとする方法、２）紡糸油剤の水性エマルジョンに、添加剤を加える方法、３）紡糸油剤の水性エマルジョンと添加剤の水性エマルジョンとを混合する方法等が挙げられる。
【００３０】
本発明の紡糸油剤は、以上説明した添加剤を０．００１〜１０重量％、好ましくは０．０１〜５重量％の割合で含有するものである。
【００３１】
添加剤を加える紡糸油剤は一般に、潤滑剤成分と界面活性剤成分とを主成分とするものである。本発明は潤滑剤成分や界面活性剤成分を特に制限するものではないが、潤滑剤成分としては、３０℃の粘度が５×１０^-6〜２×１０^-4ｍ²／ｓの鉱物油、総炭素数が１４〜７０のエステル化合物、総炭素数が１６〜７０のエーテルエステル化合物及び重量平均分子量が５００〜１５０００のポリエーテル化合物から選ばれる一つ又は二つ以上が好ましく、なかでもブチルステアレート、イソオクチルパルミテート、イソオクチルステアレート、ラウリルオレート、イソトリデシルステアレート等の総炭素数２４〜４７の直鎖脂肪酸エステル、３０℃の粘度が１×１０^-5〜８×１０^-5ｍ²／ｓの鉱物油がより好ましい。これらの潤滑剤成分は紡糸油剤中に２０〜９０重量％とするのが好ましく、３０〜８０重量％とするのが更に好ましい。
【００３２】
また界面活性剤成分としては、１）いずれもオキシアルキレン基がオキシエチレン基及び／又はオキシプロピレン基からなる、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルキルフェニルエーテル、ポリオキシアルキレン脂肪酸エステル、ポリオキシアルキレンヒマシ油、ポリオキシアルキレンアルキルアミノエーテル、ポリオキシアルキレン脂肪酸アミド等の、ポリオキシアルキレン基を有する非イオン性界面活性剤、２）ソルビタンモノラウレート、ソルビタントリオレート、グリセリンモノラウレート、ジグリセリンジラウレート等の多価アルコール部分エステル型の非イオン性界面活性剤、３）ジアルキルモノアルカノールアミン、アルキルジアルカノールアミン、脂肪酸モノアルカノールアミド、脂肪酸ジアルカノールアミド、ポリアルキレンポリアミンの脂肪酸アミド等の脂肪族含窒素非イオン性界面活性剤、４）アルキルスルホネート塩、アルキルリン酸エステル塩等のアニオン性界面活性剤、５）アルキルトリメチルアンモニウム塩、アルキルジメチルエチルアンモニウム塩、アルキルイミダゾリニウム塩等のカチオン性界面活性剤、６）アルキルジメチルベタイン、アルキルイミダゾリンのベタイン化合物等の両性界面活性剤が好ましい。かかる界面活性剤成分は紡糸油剤中に５〜７５重量％とするのが好ましく、１５〜６５重量％とするのが更に好ましい。
【００３３】
本発明の紡糸油剤を繊維糸条へ付着させるに際しては、合目的的に他の成分、例えば抗酸化剤、防腐剤、防錆剤等を用いることもできるが、その使用量は可及的に少量とするのが好ましい。
【００３４】
本発明は本発明の紡糸油剤を水性エマルジョンとする以外は、それを繊維糸条に付着させる方法を特に制限するものではなく、これには紡糸油剤の水性エマルジョンを繊維糸条に付着させる公知の方法が適用できる。例えば、紡糸油剤の水性エマルジョンを、合成繊維の紡糸工程における未配向糸、部分配向糸、延伸された配向糸等に対し、ローラー給油法、計量ポンプを用いたガイド給油法、浸漬給油法、スプレー給油法等で、紡糸油剤として０．１〜３重量％付着させる。
【００３５】
本発明の紡糸油剤を付着させる繊維糸条としては、１）エチレンテレフタレートを主たる構成単位とするポリエステルフィラメント糸条、２）ナイロン６、ナイロン６６等のポリアミドフィラメント糸条、３）ポリアクリロニトリル、モダアクリル等のポリアクリルフィラメント糸条、４）ポリエチレン、ポリプロピレン等のポリオレフィンフィラメント糸条が挙げられるが、なかでもポリエステルフィラメント糸条、ポリアミドフィラメント糸条に付着させる場合に効果が高く、ポリエステル部分延伸糸、ポリアミド部分延伸糸及びポリエステル直接紡糸延伸糸に付着させる場合により効果が高い。
【００３６】
【発明の実施の形態】
本発明に係る添加剤の実施形態としては、次の１）〜３）が挙げられる。
１）アクリルアミド／アクリル酸ナトリウム／メタクリル酸エチル＝２５／２５／５０（重量％）の割合から成るビニル単量体混合物を、該ビニル単量体混合物と水との合計／非ラジカル重合性有機溶媒＝６０／４０（重量％）の割合とした反応系で、油中水系ラジカル共重合した両親媒性ビニル共重合体であって、アクリルアミドから形成された構成単位を２５重量％、アクリル酸ナトリウムから形成された構成単位を２５重量％及びメタクリル酸エチルから形成された構成単位を５０重量％の割合で有する数平均分子量１０００００００の両親媒性ビニル共重合体から成る添加剤。
【００３７】
２）アクリルアミド／アクリル酸ナトリウム／メタクリル酸エチル／メトキシポリエトキシ（エトキシ単位の繰り返し数ｎ＝２２）エチルアクリレート＝３０／２０／４０／１０（重量％）の割合から成るビニル単量体混合物を、該ビニル単量体混合物と水との合計／非ラジカル重合性有機溶媒＝６０／４０（重量％）の割合とした反応系で、油中水系ラジカル共重合した両親媒性ビニル共重合体であって、アクリルアミドから形成された構成単位を３０重量％、アクリル酸ナトリウムから形成された構成単位を２０重量％、メタクリル酸エチルから形成された構成単位を４０重量％及びメトキシポリエトキシ（ｎ＝２２）エチルアクリレートから形成された構成単位を１０重量％の割合で有する数平均分子量１５００００００の両親媒性ビニル共重合体から成る添加剤。
【００３８】
３）下記の第１工程、第２工程及び第３工程を経て得られる両親媒性ビニル共重合体から成る添加剤。
第１工程：アクリルアミド／アクリル酸ナトリウム／メタクリル酸エチル＝１７．６／３５．３／４７．１（重量％）の割合から成るビニル単量体混合物を、該ビニル単量体混合物と水との合計／非ラジカル重合性有機溶媒＝６０／４０（重量％）の割合とした反応系で、油溶性ラジカル開始剤としての２，２−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）の存在下に、油中水系ラジカル共重合した後、ラジカル停止剤として３−メルカプト−１，２−プロパンジオールを加えてラジカル停止し、ラジカル停止した共重合体を得る工程
第２工程：ラジカル停止した共重合体を含む反応系に油溶性ラジカル開始剤として２，２−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）を加え、該共重合体をラジカル活性化する工程
第３工程：ラジカル活性化した共重合体に、メトキシポリエトキシ（ｎ＝２２）エチルアクリレートを、第１工程で用いたアクリルアミドとアクリル酸ナトリウムとメタクリル酸エチルとの合計／メトキシポリエトキシ（ｎ＝２２）エチルアクリレート＝８５／１５（重量％）の割合となるように加えて、油中水系ラジカル共重合させ、アクリルアミドから形成された構成単位を１５重量％、アクリル酸ナトリウムから形成された構成単位を３０重量％、メタクリル酸エチルから形成された構成単位を４０重量％及びメトキシポリエトキシ（ｎ＝２２）エチルアクリレートから形成された構成単位を１５重量％の割合で有する数平均分子量８００００００の両親媒性ビニル共重合体を得る工程
【００３９】
また本発明に係る紡糸油剤の実施形態としては、次の４），５）が挙げられる。
４）前記１）の添加剤を０．０５重量％、潤滑剤成分としてラウリルオクタノエート／３０℃の粘度が１．３×１０^-5ｍ²／ｓの鉱物油＝６７／３３（重量比）の割合の混合物を６０重量％及び界面活性剤成分としてポリオキシエチレンオレイルエーテル（ＨＬＢ９．０）／デシルスルホネートカリウム塩／オレイン酸カリウム塩＝９８／１／１（重量比）の割合の混合物を３９．８４重量％の割合で含有する紡糸油剤。
【００４０】
５）前記３）の紡糸油剤用添加剤を０．５重量％、潤滑剤成分として重量平均分子量１０００のポリエーテル／重量平均分子量１００００のポリエーテル／ブトキシポリエトキシエチルラウレート＝６０／１０／１５（重量比）の割合の混合物を８５重量％及び界面活性剤成分としてポリオキシエチレンオレイルエーテル（ＨＬＢ１１．４）／オクタン酸ジエタノールアミド／ラウリルホスフェートジエタノールアミン塩＝４０／３５／２５（重量比）の割合の混合物を１３．３８重量％の割合で含有する紡糸油剤。
【００４１】
【実施例】
以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明が該実施例に限定されるものではない。尚、以下の実施例等において、部は重量部を、また％は重量％を意味する。
【００４２】
試験区分１（両親媒性ビニル共重合体等の合成及び油中水系エマルジョンの調製）
・両親媒性ビニル共重合体Ｐ−１（実施例１）の合成及び油中水系エマルジョンＰＥ−１の調製
イオン交換水４００ｇ、アクリルアミド１２５ｇ（１．７５モル）、アクリル酸ナトリウム１２５ｇ（１．３８モル）及びメタクリル酸エチル２５０ｇ（２．２５モル）を高圧ホモジナイザー処理して水相を調製した。別に、フラスコに３０℃の粘度が４×１０^-6ｍ²／ｓの流動パラフィン６００ｇ及び界面活性剤としてポリオキシエチレンノニルフェニルエーテル（ＨＬＢ９．２）３０ｇとポリ（１２−ヒドロキシステアリン酸）−ポリオキシエチレン−ポリ（１２−ヒドロキシステアリン酸）共重合体（ＨＬＢ５．５）１５ｇとソルビタンオレイン酸エステル（ＨＬＢ１３．２）５ｇとを仕込み、均一に溶解して油相を調製した。調製した油相へ高速撹拌下に前記水相をゆっくりと添加し、１０分間撹拌を続け油中水系エマルジョンを調製した。フラスコ内の雰囲気を窒素置換して反応系の温度を温水浴にて３０℃に調整した。次に１５ｇのトルエンにラジカル開始剤として１ｇの２，２−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）を溶解した溶液を添加してラジカル重合を開始し、８時間重合反応を継続して油中水系ラジカル共重合反応を完結し、両親媒性ビニル共重合体を含有する油中水系エマルジョンを得た。得られた両親媒性ビニル共重合体を分析したところ、アクリルアミドから形成された構成単位／アクリル酸ナトリウムから形成された構成単位／メチルメタクリレートから形成された構成単位＝２５／２５／５０（重量％）の割合で有する数平均分子量１０００００００の両親媒性ビニル共重合体Ｐ−１であった。更に、両親媒性ビニル共重合体Ｐ−１を含有する油中水系エマルジョンの温度を２０℃に調整した後、転相用界面活性剤としてポリオキシエチレンノニルフェニルエーテル（ＨＬＢ９．２）を３０ｇ、ポリオキシエチレンノニルフェニルエーテル（ＨＬＢ１３．７）を３０ｇを添加して両親媒性ビニル共重合体Ｐ−１を３０．８％含有する油中水系エマルジョンＰＥ−１を得た。
【００４３】
・両親媒性ビニル共重合体Ｐ−２〜Ｐ−７（実施例２〜７），ビニル共重合体Ｒ−１〜Ｒ−４（比較例１〜４）の合成及び油中水系エマルジョンＰＥ−２〜ＰＥ−７，ＲＥ−１〜ＲＥ−４の調製
両親媒性ビニル共重合体Ｐ−１の合成及び油中水系エマルジョンＰＥ−１の調製と同様にして、両親媒性ビニル共重合体Ｐ−２〜Ｐ−７，ビニル共重合体Ｒ−１〜Ｒ−４及び対応する油中水系エマルジョンＰＥ−２〜ＰＥ−７，ＲＥ−１〜ＲＥ４を得た。これらの内容を表１にまとめて示した。
【００４４】
・両親媒性ビニル共重合体Ｐ−８（実施例８）の合成及び油中水系エマルジョンＰＥ−８の調製
イオン交換水４３０ｇ、アクリルアミド７５ｇ（１．０５モル）、アクリル酸ナトリウム１５０ｇ（１．６５モル）及びメタクリル酸エチル２００ｇ（１．８モル）を高圧ホモジナイザー処理して水相を調製した。別に、フラスコに３０℃の粘度が２×１０^-6ｍ²／ｓの流動パラフィン５７０ｇ及び界面活性剤としてポリオキシエチレンノニルフェニルエーテル（ＨＬＢ９．２）３０ｇとポリ（１２−ヒドロキシステアリン酸）−ポリオキシエチレン−ポリ（１２−ヒドロキシステアリン酸）共重合体（ＨＬＢ５．５）１５ｇとソルビタンオレイン酸エステル（ＨＬＢ１３．２）５ｇとを仕込み、均一に溶解して油相を調製した。調製した油相へ高速撹拌下に前記水相をゆっくりと添加し、１０分間撹拌を続け油中水系エマルジョンを調製した。フラスコ内の雰囲気を窒素置換して反応系の温度を温水浴にて３０℃に調整した。次に１５ｇのトルエンにラジカル開始剤として１ｇの２，２−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）を溶解した溶液を添加してラジカル重合を開始し、８時間重合反応を継続した（第１工程）。そして３−メルカプト−１，２−プロパンジオールの２０％水溶液２ｇを投入してラジカル停止した（第２工程）。最後に、１５ｇのトルエンに１ｇの２，２−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）を溶解した溶液を添加して、ラジカル停止した共重合体をラジカル活性化した後、メトキシポリエトキシ（ｎ＝２２）エチルアクリレート７５ｇ（０．０７５モル）を投入し、６時間反応を継続して油中水系ラジカル共重合反応を完結し、両親媒性ビニル共重合体を含有する油中水系エマルジョンを得た。得られた両親媒性ビニル共重合体を分析したところ、アクリルアミドから形成された構成単位／アクリル酸ナトリウムから形成された構成単位／メチルメタクリレートから形成された構成単位／メトキシポリエトキシ（ｎ＝２２）エチルメタクリレートから形成された構成単位＝１５／３０／４０／１５（重量％）の割合で有する数平均分子量８００００００の両親媒性ビニル共重合体Ｐ−８であった。更に、両親媒性ビニル共重合体Ｐ−８を含有する油中水系エマルジョンの温度を２０℃に調整した後、転相用界面活性剤としてポリオキシエチレンノニルフェニルエーテル（ＨＬＢ９．２）を３０ｇ及びポリオキシエチレンノニルフェニルエーテル（ＨＬＢ１３．７）を３０ｇを添加して両親媒性ビニル共重合体Ｐ−８を３０．４％含有する油中水系エマルジョンＰＥ−８を得た。
【００４５】
・両親媒性ビニル共重合体Ｐ−９，Ｐ−１０（実施例９，１０）の合成及び油中水系エマルジョンＰＥ−９，ＰＥ−１０の調製
両親媒性ビニル共重合体Ｐ−８の合成及び油中水系エマルジョンＰＥ−８の調製と同様にして、両親媒性ビニル共重合体Ｐ−９，Ｐ−１０及び対応する油中水系エマルジョンＰＥ−９，ＰＥ−１０を得た。これらの内容を表１にまとめて示した。
【００４６】
【表１】

【００４７】
表１において、
＊１：各ビニル単量体の油中水系ラジカル共重合に用いた非ラジカル重合性有機溶媒
＊２：各ビニル単量体を油中水系ラジカル共重合させるときの反応系における、ビニル単量体混合物と水との合計／非ラジカル重合性有機溶媒（重量％）、但し実施例８〜１０は第１工程におけるそれらの割合（重量％）
Ａ−１：アクリルアミドから形成された構成単位
Ａ−２：メタクリルアミドから形成された構成単位
Ｂ−１：アクリル酸ナトリウム塩から形成された構成単位
Ｂ−２：メタクリル酸ＮＨ₄塩から形成された構成単位
Ｃ−１：メタリル酸エチルから形成された構成単位
Ｃ−２：アクリル酸２エチルヘキシルから形成された構成単位
Ｄ−１：メトキシポリエトキシ（ｎ＝２２）エチルアクリレートから形成された構成単位
Ｄ−２：ヒドロキシポリエトキシ（ｎ＝１２）エチルメタクリレートから形成された構成単位
Ｓ−１：３０℃の粘度が４×１０^-6ｍ²／ｓの流動パラフィン
Ｓ−２：３０℃の粘度が２×１０^-6ｍ²／ｓの鉱物油
【００４８】
試験区分２（紡糸油剤の水性エマルジョンの調製）
・紡糸油剤（実施例１１〜２０，比較例５〜８）の水性エマルジョンの調製
試験区分１で調製した両親媒性ビニル共重合体Ｐ−１を３０．８％含有する油中水型エマルジョンＰＥ−１を０．１６部（両親媒性ビニル共重合体Ｐ−１として０．０５部）、潤滑剤成分Ｌ−１｛ラウリルオクタノエート／３０℃の粘度が１．３×１０^-5ｍ²／ｓの鉱物油＝６７／３３（重量比）の割合から成る混合物｝を６０部及び界面活性剤成分ＤＴ−２｛ポリオキシエチレンオレイルエーテル（ＨＬＢ９．０）／デシルスルホネートカリウム塩／オレイン酸カリウム塩＝９８／１／１（重量比）の割合の混合物｝を３９．８４部及び水３．１部をビーカーに秤量し、撹拌して紡糸油剤（実施例１１）の９７％水性エマルジョンを調製した。紡糸油剤（実施例１１）の場合と同様にして、紡糸油剤（実施例１２〜２０），（比較例５〜８）の９７％水性エマルジョンを調製した。これらの内容を表２にまとめて示した。
【００４９】
・紡糸油剤（比較例９〜１２）の水性エマルジョンの調製
前記潤滑剤成分Ｌ−１を６０部、前記界面活性剤成分ＤＴ−１を３９．５部及び水３．１部をビーカーに秤量し、撹拌して、水性エマルジョンとした。別に高分子量ポリエチレンオキサイド（分子量２００００００）を水で希釈して１％水溶液とした。そして前記水性エマルジョン、高分子量ポリエチレンオキサイドの１％水溶液及び水を混合して、潤滑剤成分Ｌ−１と界面活性剤成分ＤＴ−１との合計／高分子量ポリエチレンオキサイド（分子量２００００００）＝９９．５／０．５（重量比）となるようにした紡糸油剤（比較例９）の１０％水性エマルジョンを調製した。紡糸油剤（比較例９）の場合と同様にして、紡糸油剤（比較例１０〜１２）の１０％水性エマルジョンを調製した。これらの内容を表２にまとめて示した。
【００５０】
試験区分３（添加剤及びこれを含有する紡糸油剤の評価）
・紡糸油剤の水性エマルジョンにおける添加剤の相溶性評価
・相溶性試験（相溶性評価１）
試験区分２で調製した各例の紡糸油剤の水性エマルジョンを３０℃で３０日間静置後、その外観を肉眼で観察し、下記の基準で評価した。但し比較例９〜１２については、試験区分２で調製した水性エマルジョンの水分が３％になるまで水分蒸発したものを試験に供した。
○：固形物或はゲル状物の発生が認められず、相溶性良好。
△：固形物或はゲル状物の発生がわずかに認められ、相溶性やや不良。
×：固形物或はゲル状物の発生が顕著に認められ、相溶性不良。
【００５１】
・相溶性試験（相溶性評価２）
試験区分２で調製した各例の紡糸油剤の水性エマルジョンを水で希釈して１０％水性エマルジョンとした。この１０％水性エマルジョン１ｇを直径１００mmのシャーレに採り、１１０℃で２時間熱風乾燥処理した後、以下の基準で評価した。但し、比較例９〜１２についてはそのまま試験に供した。以上の結果を表２にまとめて示した。
○：固形物或はゲル状物の発生が認められず、相溶性は良好。
△：固形物或はゲル状物の発生がわずかに認められ、相溶性やや不良。
×：固形物或はゲル状物の発生が顕著に認められ、相溶性不良。
【００５２】
・走行糸状からの飛散防止性及び飛散物外観の評価
固有粘度０．６４、酸化チタン含有量０．２％のポリエチレンテレフタレートチップを常法により乾燥した後、エクストルーダーを用いて２９５℃で紡糸した。口金から吐出して冷却固化した後の走行糸条に、試験区分２で調製した各例の紡糸油剤の水性エマルジョンを更に水希釈した１０％水性エマルジョン（比較例９〜１２については試験区分２で調製した紡糸油剤の１０％水性エマルジョンそのまま）を、計量ポンプを用いたガイド給油法にて、付着量１．１％となるように付着させた後、引き続きガイドで集束させて、表面速度４０００ｍ／分で表面温度９０℃の第１ゴテッドローラーと、表面速度５０００ｍ／分で表面温度１３０℃の第２ゴテッドローラーとで延伸後、４９００ｍ／分の速度で巻き取り、７５デニール３６フィラメントの延伸糸を得た。ここで延伸糸５００００ｍを製造した時に、給油ガイドの下部、給油ガイドと第１ゴテッドローラーの中間に位置するインターレーサー部分及び第１ゴテッドローラーの下部に飛散した紡糸油剤のエマルジョンを濾紙で回収した。回収濾紙を６０℃×２４時間加熱処理して水分を除去した後、秤量し、回収した紡糸油剤の重量を算出して、飛散防止性を以下の基準で評価した。また飛散物外観の評価は、給油ガイド及び第１ゴテッドローラーへの固状物の堆積を肉眼観察により以下の基準でおこなった。結果をまとめて表２に示した。
【００５３】
飛散防止性
◎：回収紡糸油剤の重量が１０mg未満であり、優れている。
○：回収紡糸油剤の重量が１０mg以上３０mg未満であり、良好である。
△：回収紡糸油剤の重量が３０mg以上１００mg未満であり、やや問題がある。
×：回収紡糸油剤の重量が１００mg以上であり、問題がある。
【００５４】
飛散物外観
◎：固状物の堆積がほとんど観察されない。
○：固状物の堆積が僅かに観察される。
△：固状物の堆積がある程度観察される。
×：固状物の堆積が顕著に観察される。
【００５５】
【表２】

【００５６】
表２において、
Ｐ−１〜Ｐ−１０，Ｒ−１〜Ｒ−４：表１に記載の両親媒性ビニル共重合体等ＰＥ−１〜ＰＥ−１０，ＲＥ−１〜ＲＥ−４：試験区分１で調製した両親媒性ビニル共重合体を含有する油中水系エマルジョン
Ｒ−５：高分子量ポリエチレン（分子量２００万）
Ｒ−６：ポリアクリルアミド（分子量１０００万）
Ｒ−７：ポリオキシアルキレングリコール（エチレングリコールにエチレンオキサイドとプロピレンオキサイドをランダム付加した平均分子量２０００の化合物）と４，４’−ジフェニルメタンジイソシアネートからなるポリウレタン（分子量４０万）
Ｒ−８：ＰＥＧ２０００ジカプレート
Ｌ−１：ラウリルオクタノエート／３０℃の粘度が１．３×１０^-5ｍ²／ｓの鉱物油＝６７／３３（重量比）の割合の混合物
Ｌ−２：重量平均分子量１０００のポリエーテル／重量平均分子量１００００のポリエーテル／ブトキシポリエトキシエチルラウレート＝６０／１０／１５（重量比）の割合の混合物
ＤＴ−１：ポリオキシエチレンオレイルエーテル（ＨＬＢ１１．４）／オクタン酸ジエタノールアミド／ラウリルホスフェートジエタノールアミン塩＝４０／３５／２５（重量比）の割合の混合物
ＤＴ−２：ポリオキシエチレンオレイルエーテル（ＨＬＢ９．０）／デシルスルホネートカリウム塩／オレイン酸カリウム塩＝９８／１／１（重量比）の割合の混合物
Ｅ−１〜Ｅ−４：油中水系ラジカル重合に用いた原料であって、原料のビニル単量体、ラジカル開始剤及びラジカル停止剤を除いた下記構成の原料
Ｅ−１：水（４００部）、非ラジカル重合性溶媒Ｓ−１（６００部）、油中水系ラジカル重合用界面活性剤｛ポリオキシエチレンノニルフェニルエーテル（ＨＬＢ９．２）／ポリ（１２−ヒドロキシステアリン酸）−ポリオキシエチレン−ポリ（１２−ヒドロキシステアリン酸）共重合体（ＨＬＢ５．５）／ソルビタンオレイン酸エステル（ＨＬＢ１３．２）＝６０／３０／１０（重量比）から成る混合物｝５０部、トルエン１５部及び転相用界面活性剤｛ポリオキシエチレンノニルフェニルエーテル（ＨＬＢ９．２）／ポリオキシエチレンノニルフェニルエーテル（ＨＬＢ１３．７）＝５０／５０（重量比）から成る混合物｝６０部の割合で構成される混合物
Ｅ−２：前記Ｅ−１において、非ラジカル重合性溶媒Ｓ−１をＳ−２とした混合物
Ｅ−３：前記Ｅ−１において、トルエンの量を３０部とした混合物
Ｅ−４：前記Ｅ−３において、非ラジカル重合性溶媒Ｓ−１をＳ−２とした混合物
【００５７】
【発明の効果】
既に明らかなように、以上説明した本発明の添加剤は紡糸油剤との相溶性に優れ、これを含有する紡糸油剤はその水性エマルジョンを高速走行下の繊維糸状に付着させた場合においても、繊維糸条からの油剤飛散を効果的に防止でき、飛散物による繊維糸状への障害を防止できるという効果がある。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an additive for a spinning oil agent (hereinafter simply referred to as a spinning oil agent) to be attached in the form of a fiber thread as an aqueous emulsion, and a spinning oil agent containing the same. 2. Description of the Related Art In recent years, the speed of manufacturing and processing of fibers has been increasing at a remarkable speed for labor saving or rationalization. For example, the spinning speed of synthetic fibers such as polyester and nylon is shifting to 5000 to 8000 m / min. Thus, when the running speed of the fiber yarn is increased, the scattering of the spinning oil adhered to the fiber yarn becomes noticeable, thereby deteriorating the working environment, reducing the use efficiency of the spinning oil, and the scattered matter. Various problems, such as running troubles due to, occur. Under such circumstances, an additive that does not form a solid obstacle on the running yarn path, has excellent compatibility with the spinning oil, has excellent anti-scattering properties that can cope with high-speed fiber yarns. Appearance is strongly requested. The present invention relates to an additive for a spinning oil that meets such a demand, and a spinning oil containing the same.
[0002]
[Prior art]
Conventionally, various polymer compounds have been proposed as additives used for preventing scattering of the spinning oil adhering to the fiber yarn under high-speed running. Examples thereof include 1) high molecular weight polyethylene oxide having a molecular weight of 100,000 to 6 million (Japanese Patent Laid-Open No. 2-68370), 2) high molecular weight polyacrylamide or acrylamide copolymer having a molecular weight of 50,000 to 20 million (Japanese Patent Laid-Open No. 59172), 3) a water-soluble polymer compound having a molecular weight of 100,000 to 500,000 derived from a polyoxyalkylene compound and an organic polyisocyanate compound (JP-A-4-119128), and 4) a polyalkylene glycol and an aliphatic carboxylic acid. A chain polymer compound having a lipophilic group at both ends (JP-A-5-44115), which is a reaction product of a diester or diepoxide and an oxyalkylene adduct of alcohol. However, these conventional additives are poorly compatible with the spinning oil, and therefore are insufficient in preventing the oil agent from scattering from the fiber yarn under high speed running, and the scattered matter is solid on the running yarn path. There is a disadvantage of forming an obstacle. When a solid obstacle is formed on the traveling yarn path, fluff and yarn breakage occur, which not only lowers the quality of the fiber yarn but also reduces operability.
[0003]
[Problems to be solved by the invention]
The problem to be solved by the present invention is that the conventional additive has poor compatibility with the spinning oil, so that the oil agent is not sufficiently prevented from scattering from the fiber yarn under high speed running, and the scattered matter travels. It is a point that forms a solid obstacle on the yarn path.
[0004]
[Means for Solving the Problems]
Accordingly, as a result of studies to solve the above problems, the present inventors have found that a specific amphiphilic vinyl copolymer is correctly suitable as an additive to be added to the spinning oil.
[0005]
That is, the present invention is an additive for a spinning oil agent that is attached to a fiber yarn as an aqueous emulsion, and includes a structural unit A represented by the following formula 1, a structural unit B represented by the following formula 2, and the following formula 3 The amphiphilic vinyl having a number average molecular weight of 30,000 to 30,000,000, comprising the structural unit C represented by the formula (1) as a main structural unit and having the structural unit A, the structural unit B, and the structural unit C in a proportion of 80% by weight or more in total. The present invention relates to an additive comprising a copolymer.
[0006]
[Formula 1]

[Formula 2]

[Formula 3]

[0007]
In Equation 1, Equation 2, and Equation 3,
R¹, R², R^Three: H or CH_Three
R^Four: Hydrocarbon group having 1 to 24 carbon atoms
X¹, X²: H, a hydroxyalkyl group having 1 to 3 carbon atoms or an aliphatic hydrocarbon group having 1 to 8 carbon atoms
M¹: Alkali metal, NH_FourOr quaternary ammonium cation
[0008]
The amphiphilic vinyl copolymer that is the additive of the present invention has a structural unit A represented by Formula 1, a structural unit B represented by Formula 2, and a structural unit C represented by Formula 3 as main structural units. However, those having a structural unit D represented by the following formula 4 as a structural unit other than these are preferable.
[0009]
[Formula 4]

[0010]
In Equation 4,
R^Five: H or CH_Three
R⁶: Hydrogen or an aliphatic hydrocarbon group having 1 to 6 carbon atoms
n: integer of 5-40
[0011]
Each of the structural units A to D is formed by copolymerizing a corresponding vinyl monomer. The vinyl monomer that forms the structural unit A is the vinyl monomer a represented by the following formula 5, and the vinyl monomer that forms the structural unit B is represented by the following formula 6. The vinyl monomer b which forms the structural unit C is a vinyl monomer c represented by the following formula 7. The vinyl monomer that forms the structural unit D is a vinyl monomer d represented by the following formula 8.
[0012]
[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[0013]
In Equation 5, Equation 6, Equation 7, and Equation 8,
R¹~ R⁶, X¹, X², M¹, N: Same as Formulas 1 to 4
[0014]
As vinyl monomer a which will form the structural unit A shown by Formula 1, 1) acrylamide, methacrylamide, 2) N-methylol acrylamide, N-2-hydroxyethyl acrylamide, N-3-hydroxypropyl Acrylamide, N, N-bis (2-hydroxyethyl) acrylamide, N, N-bis (3-hydroxypropyl) acrylamide, N-methylol methacrylamide, N-2-hydroxyethyl methacrylamide, N-3-hydroxypropyl methacryl N-substituted or N, substituted with a hydroxyalkyl group having 1 to 3 carbon atoms, such as amide, N, N-bis (2-hydroxyethyl) methacrylamide, N, N-bis (3-hydroxypropyl) methacrylamide N-substituted (meth) acrylamide, 3) N-methyla Rilamide, N-ethylacrylamide, N-propylacrylamide, N, N-diethylacrylamide, N, N-dipropylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N, N-diethyl Examples thereof include N-substituted or N, N-substituted (meth) acrylamide substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms such as methacrylamide, N, N-dipropylmethacrylamide, among others, acrylamide, methacryl Amides are preferred.
[0015]
Examples of the vinyl monomer b that will form the structural unit B represented by Formula 2 include 1) an alkali metal salt of acrylic acid, NH_FourSalts and quaternary ammonium salts, 2) alkali metal salts of methacrylic acid, NH_FourSalts and quaternary ammonium salts can be mentioned, and among them, alkali metal salts of acrylic acid and alkali metal salts of methacrylic acid are preferable.
[0016]
As the vinyl monomer c that will form the structural unit C represented by the formula 3, 1) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, acrylic acid Alkyl acrylate having 1 to 24 carbon atoms such as lauryl, stearyl acrylate, behenyl acrylate, etc. 2) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, methacrylic acid Examples thereof include alkyl methacrylates having an alkyl group having 1 to 24 carbon atoms such as octyl, lauryl methacrylate, stearyl methacrylate, behenyl methacrylate, etc. Among them, (meth) acrylic having an alkyl group having 1 to 8 carbon atoms Alkyl acids are preferred.
[0017]
The vinyl monomer d which will form the structural unit D represented by Formula 4 is a hydroxypolyethoxyethyl acrylate having a repeating number of ethoxy units of 5 to 40 and one terminal being hydrogen, Hydroxypolyethoxyethyl methacrylate, wherein one end is blocked with an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and one end blocked polyethoxyethyl acrylate and one end blocked polyethoxyethyl methacrylate are blocked. For example, 1) hydroxypolyethoxyethyl acrylate, 2) hydroxypolyethoxyethyl methacrylate, 3) methoxypolyethoxyethyl acrylate, ethoxypolyethoxyethyl acrylate, propoxypolyethoxyethyl acrylate, butoxypolyethoxyethyl acrylate, pentoxypoly One-end-capped polyethoxyethyl acrylate such as ethoxyethyl acrylate, hexoxypolyethoxyethyl acrylate, cyclohexyltochitopolyethoxyethyl acrylate, etc. 4) Methoxypolyethoxyethyl methacrylate, ethoxypolyethoxyethyl methacrylate, propoxypolyethoxyethyl methacrylate, Butoxypolyethoxyethyl methacrylate, pentoxypolyethoxyethyl methacrylate Rate, hexoxycarbonyl polyethoxy methacrylate, although the one-end-type polyethoxy methacrylate such cyclohexoxy polyethoxy methacrylate. Among them methoxy polyethoxy ethyl acrylate repeating number of ethoxy units is 6 to 30 is preferred.
[0018]
The amphiphilic vinyl copolymer that is the additive of the present invention has the structural unit A, the structural unit B, and the structural unit C as the main structural unit as described above, and the total of these is 80% by weight in all the structural units. Although it has the above, what is comprised by the structural unit A, the structural unit B, the structural unit C, and the structural unit D is preferable.
[0019]
The present invention does not particularly limit the proportion of each structural unit constituting the amphiphilic vinyl copolymer, but in the case where the structural units A to C are the main structural units, 10 to 50 in all the structural units. Those having 10% by weight of structural unit A, 10-50% by weight of structural unit B and 30-80% by weight of structural unit C (total of 80-100% by weight) are preferred, and 20-45% by weight in all the structural units More preferably, the structural unit A has 20 to 45% by weight of the structural unit B and 35 to 60% by weight of the structural unit C (total 80 to 100% by weight). Further, in the case of having the structural unit D as a structural unit other than the structural units A to C, the structural unit A of 8 to 40% by weight, the structural unit B of 8 to 40% by weight, the structural unit C of 24 to 64% by weight and 1 It is preferably composed of ˜20% by weight of structural unit D (total 100% by weight), 10 to 35% by weight of structural unit A, 10 to 35% by weight of structural unit B, and 30 to 35% by weight of structural unit. More preferably, it is composed of C and 3 to 15% by weight of the structural unit D (100% by weight in total).
[0020]
The amphiphilic vinyl copolymer that is the additive of the present invention has a number average molecular weight (GPC method, pullullan conversion, the same shall apply hereinafter) of 30000 to 3000000, preferably 100000 to 15000000.
[0021]
The amphiphilic vinyl copolymer that is the additive of the present invention can be obtained by the following synthesis method. For example, in non-radically polymerizable organic solvents such as mineral oil and kerosene, a nonionic surfactant having a molecular weight of less than 2000 and an HLB of 8 to 10, an oil-soluble nonionic surfactant having a molecular weight of 2000 or more, and a sorbitan fatty acid ester having an HLB of 3 to 5 To prepare an oil phase. Separately, a required amount of each vinyl monomer that will form each structural unit is dissolved in water to prepare an aqueous phase. The oil phase is put into a reaction vessel, and the water phase is slowly added thereto with high-speed stirring to prepare a water-in-oil emulsion. Thereafter, the number of stirring is suppressed, the internal temperature is adjusted to about 30 ° C., the inside of the reaction vessel is replaced with nitrogen, and then an oil-soluble radical initiator dissolved in a non-radically polymerizable organic solvent such as toluene is added to initiate polymerization, The vinyl monomer mixture is water-in-oil radical copolymerized for a predetermined time to obtain an amphiphilic vinyl copolymer as a water-in-oil emulsion.
[0022]
When synthesizing an amphiphilic vinyl copolymer by water-in-oil radical copolymer as described above, the total of the mixture of vinyl monomers and water that form each structural unit (water phase) / non- Radical polymerizable organic solvent = 20/80 to 80/20 (% by weight), preferably 30/70 to 70/30 (% by weight). In the case of synthesizing an amphiphilic vinyl copolymer having the structural units A to C as the main structural unit and having 80% by weight or more of all the structural units by water-in-oil radical copolymerization, for example, the structural unit Vinyl monomer a to form A / vinyl monomer b to form structural unit B / vinyl monomer c to form structural unit C = 10 to 50/10 to 50 / 30-80 (% by weight) and a total of 80% by weight or more of the vinyl monomer mixture containing the vinyl monomer mixture and water / non-radical polymerizability Water-in-oil radical copolymerization is performed in a reaction system in which the ratio of organic solvent is 20/80 to 80/20 (% by weight). When an amphiphilic vinyl copolymer composed of the structural units A to D is synthesized by water-in-oil radical copolymerization, for example, the vinyl monomer a / structural unit B that forms the structural unit A is used. The vinyl monomer b that forms the structural unit C / the vinyl monomer c that forms the structural unit C / the vinyl monomer d that forms the structural unit D = 8 to 40/8 to 40 / A vinyl monomer mixture having a ratio of 24 to 64/1 to 20 (wt%) is a total of the vinyl monomer mixture and water / non-radically polymerizable organic solvent = 20/80 to 80/20 (weight) %) In the reaction system, water-in-oil radical copolymerization.
[0023]
When the amphiphilic vinyl copolymer composed of the structural units A to D is synthesized by water-in-oil radical copolymerization, the amphiphilic vinyl copolymer may include the following first step, second step, and second step. What is obtained through three steps is particularly preferable.
First step: Vinyl monomer mixture comprising vinyl monomer a / vinyl monomer b / vinyl monomer c = 10-50 / 10-50 / 30-80 (wt%) The total reaction amount of the monomer mixture and water / non-radically polymerizable organic solvent = 20/80 to 80/20 (% by weight). In the reaction system in the presence of an oil-soluble radical initiator, After polymerization, the radical is stopped to obtain a radical-stopped copolymer
Second step: adding an oil-soluble radical initiator to a reaction system containing a radical-terminated copolymer to radically activate the copolymer
Third step: vinyl monomer d in the reaction system containing the radical activated copolymer, the sum of vinyl monomer a, vinyl monomer b and vinyl monomer c used in the first step / A step of obtaining an amphiphilic vinyl copolymer by adding a vinyl monomer d = 80/20 to 99/1 (wt%) and carrying out water-in-oil radical copolymerization.
[0024]
In the water-in-oil radical copolymerization of the vinyl monomers a to c in the first step, for example, a non-ionic surfactant having a molecular weight of less than 2000 and an HLB of 8 to 10 in a non-radically polymerizable organic solvent, and an oil solubility having a molecular weight of 2000 or more. An oil phase in which the nonionic surfactants and HLB 3 to 5 sorbitan fatty acid esters are dissolved is prepared, and an aqueous phase in which the vinyl monomers a to c are dissolved in water is prepared. The oil phase is put into a reaction vessel, and the aqueous phase is slowly added under high-speed stirring to prepare a water-in-oil emulsion. Thereafter, the number of stirring is suppressed, the internal temperature is adjusted to about 30 ° C., the inside of the reaction vessel is replaced with nitrogen, and then dissolved in a non-radically polymerizable organic solvent by itself adding a known oil-soluble radical initiator to a water-in-oil system. Perform radical copolymerization.
[0025]
In the first step, in the water-in-oil radical copolymerization of vinyl monomers a to c, radical termination of the reaction system is performed in a timely manner to obtain a radical-terminated copolymer. The radical termination method may be a method in which the reaction is continued until the radical completely disappears from the reaction system and the radical copolymerization reaction is substantially stopped. A method of adding a radical terminator to the reaction system is preferred. This is because the molecular weight of the resulting radical-terminated copolymer can be easily adjusted while smoothly shifting to the second step, which will be described later, and further to the third step.
[0026]
In the second step, a publicly known oil-soluble radical initiator is added to the reaction system containing the radical-terminated copolymer obtained in the first step to radically activate the copolymer.
[0027]
In the third step, a vinyl monomer d is added to the radical activated copolymer in the second step to further carry out water-in-oil radical copolymerization, and the copolymer having an alkoxypolyoxyethylene chain, that is, the parent of the present invention. A volatile vinyl copolymer is obtained. The amount of vinyl monomer d used in the third step is the sum of vinyl monomers a to c used in the first step / vinyl monomer d = 80/20 to 99/1 (% by weight), preferably The ratio is 85/15 to 97/3 (% by weight).
[0028]
The amphiphilic vinyl copolymer obtained by the first step, the second step and the third step is in the state of a water-in-oil emulsion. Such a water-in-oil emulsion can be used as an additive as it is because the present invention attaches the spinning oil to the fiber yarn as an aqueous emulsion, but for the convenience of preparing an aqueous emulsion of the spinning oil, the molecular weight is 2000. It is preferable to add a surfactant for phase inversion comprising a nonionic surfactant having an HLB of 8 to 10, a water-soluble polyoxyethylene polyoxypropylene derivative and a water-soluble nonionic surfactant having an HLB of 12 to 14 in advance. .
[0029]
This invention does not restrict | limit the usage method of the additive demonstrated above in particular. This includes, for example, 1) a method in which an additive is added to a spinning oil and then an aqueous emulsion, 2) a method in which the additive is added to an aqueous emulsion of the spinning oil, and 3) an aqueous emulsion of the spinning oil and an aqueous solution of the additive. Examples include a method of mixing with an emulsion.
[0030]
The spinning oil of the present invention contains 0.001 to 10% by weight, preferably 0.01 to 5% by weight of the additive described above.
[0031]
The spinning oil to which the additive is added is generally composed mainly of a lubricant component and a surfactant component. Although the present invention does not particularly limit the lubricant component or the surfactant component, the lubricant component has a viscosity of 5 × 10 5 at 30 ° C.^-6~ 2x10^-Fourm²/ S mineral oil, an ester compound having a total carbon number of 14 to 70, an ether ester compound having a total carbon number of 16 to 70, and a polyether compound having a weight average molecular weight of 500 to 15000 are one or more. Among these, linear fatty acid esters having a total carbon number of 24 to 47 such as butyl stearate, isooctyl palmitate, isooctyl stearate, lauryl oleate, isotridecyl stearate, and a viscosity at 30 ° C. of 1 × 10.^-Five~ 8x10^-Fivem²/ S mineral oil is more preferred. These lubricant components are preferably 20 to 90% by weight, more preferably 30 to 80% by weight in the spinning oil.
[0032]
As surfactant components, 1) any of polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylenes in which the oxyalkylene group is an oxyethylene group and / or oxypropylene group Nonionic surfactants having a polyoxyalkylene group, such as castor oil, polyoxyalkylene alkylamino ether, polyoxyalkylene fatty acid amide, etc., 2) sorbitan monolaurate, sorbitan trioleate, glycerin monolaurate, diglycerin dilaurate Nonionic surfactants of polyhydric alcohol partial ester type such as 3) Dialkyl monoalkanolamines, alkyl dialkanolamines, fatty acid monoalkanolamides, fatty acid dia Aliphatic nitrogen-containing nonionic surfactants such as fatty acid amides of cananolamides and polyalkylenepolyamines, 4) anionic surfactants such as alkylsulfonate salts and alkylphosphate ester salts, 5) alkyltrimethylammonium salts, alkyldimethylethyl Cationic surfactants such as ammonium salts and alkylimidazolinium salts, and 6) amphoteric surfactants such as alkyldimethylbetaine and alkylimidazoline betaine compounds are preferred. The surfactant component is preferably 5 to 75% by weight in the spinning oil, and more preferably 15 to 65% by weight.
[0033]
In adhering the spinning oil of the present invention to the fiber yarn, other components such as an antioxidant, an antiseptic, and a rust inhibitor can be used for the purpose, but the amount used is as much as possible. A small amount is preferable.
[0034]
The present invention does not particularly limit the method of adhering the spinning oil of the present invention to the fiber yarn, except that the spinning oil of the present invention is an aqueous emulsion. The method is applicable. For example, an aqueous emulsion of spinning oil is applied to unoriented yarn, partially oriented yarn, stretched oriented yarn, etc. in the spinning process of synthetic fiber, using a roller lubrication method, a guide lubrication method using a metering pump, an immersion lubrication method, a spray It is made to adhere 0.1 to 3 weight% as spinning oil agent by the oil supply method.
[0035]
As the fiber yarn to which the spinning oil of the present invention is attached, 1) polyester filament yarn having ethylene terephthalate as a main structural unit, 2) polyamide filament yarn such as nylon 6, nylon 66, etc., 3) polyacrylonitrile, modacrylic, etc. 4) Polyolefin filament yarns such as polyethylene and polypropylene, etc., but particularly effective when adhered to polyester filament yarns and polyamide filament yarns. Polyester partially drawn yarns and polyamide parts The effect is higher when adhering to drawn yarn and polyester direct spun drawn yarn.
[0036]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the additive according to the present invention include the following 1) to 3).
1) A vinyl monomer mixture having a ratio of acrylamide / sodium acrylate / ethyl methacrylate = 25/25/50 (wt%) is a total of the vinyl monomer mixture and water / non-radically polymerizable organic solvent. = Amphiphilic vinyl copolymer obtained by water-in-oil radical copolymerization in a reaction system with a ratio of 60/40 (% by weight), comprising 25% by weight of structural units formed from acrylamide and sodium acrylate An additive comprising an amphiphilic vinyl copolymer having a number average molecular weight of 10,000,000 having 25% by weight of structural units formed and 50% by weight of structural units formed from ethyl methacrylate.
[0037]
2) A vinyl monomer mixture having a ratio of acrylamide / sodium acrylate / ethyl methacrylate / methoxypolyethoxy (the number of repeating ethoxy units n = 22) ethyl acrylate = 30/20/40/10 (% by weight), An amphiphilic vinyl copolymer obtained by water-in-oil radical copolymerization in a reaction system having a ratio of the total of the vinyl monomer mixture and water / non-radically polymerizable organic solvent = 60/40 (wt%). 30% by weight of structural units formed from acrylamide, 20% by weight of structural units formed from sodium acrylate, 40% by weight of structural units formed from ethyl methacrylate, and methoxypolyethoxy (n = 22) Amphiphilic vinyl having a number average molecular weight of 15000000 having a unit of 10% by weight formed from ethyl acrylate Additives consisting of alcohol copolymer.
[0038]
3) An additive comprising an amphiphilic vinyl copolymer obtained through the following first step, second step and third step.
First step: A vinyl monomer mixture having a ratio of acrylamide / sodium acrylate / ethyl methacrylate = 17.6 / 35.3 / 47.1 (% by weight) is mixed with the vinyl monomer mixture and water. Total / non-radically polymerizable organic solvent = 60/40 (% by weight) of reaction system with 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile) as oil-soluble radical initiator In the presence of water-in-oil radical copolymerization, 3-mercapto-1,2-propanediol is added as a radical terminator to terminate the radical, thereby obtaining a radical-terminated copolymer.
Second step: 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile) is added as an oil-soluble radical initiator to the reaction system containing the radical-terminated copolymer, and the copolymer is radically activated. Process
Third step: To the radical-activated copolymer, methoxypolyethoxy (n = 22) ethyl acrylate is the total of acrylamide, sodium acrylate and ethyl methacrylate used in the first step / methoxy polyethoxy (n = 22) In addition to ethyl acrylate = 85/15 (% by weight), water-in-oil radical copolymerization was performed, and 15% by weight of the structural unit formed from acrylamide and the structural unit formed from sodium acrylate 30% by weight, 40% by weight of structural units formed from ethyl methacrylate and 15% by weight of structural units formed from methoxypolyethoxy (n = 22) ethyl acrylate. For obtaining a functional vinyl copolymer
[0039]
Moreover, as embodiment of the spinning oil agent which concerns on this invention, following 4) and 5) are mentioned.
4) 0.05% by weight of the additive of 1), lauryl octanoate as a lubricant component / viscosity at 30 ° C. of 1.3 × 10^-Fivem²/ S Mineral oil = 67/33 (weight ratio) 60% by weight of a mixture and polyoxyethylene oleyl ether (HLB9.0) / decylsulfonate potassium salt / potassium oleate = 98 / A spinning oil containing a mixture having a ratio of 1/1 (weight ratio) in a ratio of 39.84% by weight.
[0040]
5) 0.5% by weight of the additive for spinning oil of 3) above, polyether having a weight average molecular weight of 1000 / polyether having a weight average molecular weight of 10,000 / butoxypolyethoxyethyl laurate = 60/10/15 as a lubricant component. 85% by weight of the mixture (weight ratio) and polyoxyethylene oleyl ether (HLB11.4) / octanoic acid diethanolamide / lauryl phosphate diethanolamine salt = 40/35/25 (weight ratio) as a surfactant component A spinning oil containing a mixture of
[0041]
【Example】
Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to the examples. In the following examples and the like, parts means parts by weight, and% means% by weight.
[0042]
Test Category 1 (Synthesis of amphiphilic vinyl copolymers and preparation of water-in-oil emulsion)
Synthesis of amphiphilic vinyl copolymer P-1 (Example 1) and preparation of water-in-oil emulsion PE-1
A water phase was prepared by subjecting 400 g of ion-exchanged water, 125 g (1.75 mol) of acrylamide, 125 g (1.38 mol) of sodium acrylate and 250 g (2.25 mol) of ethyl methacrylate to a high-pressure homogenizer. Separately, the viscosity at 30 ° C. in the flask is 4 × 10^-6m²/ S liquid paraffin 600g and polyoxyethylene nonylphenyl ether (HLB9.2) 30g as a surfactant and poly (12-hydroxystearic acid) -polyoxyethylene-poly (12-hydroxystearic acid) copolymer (HLB5) .5) 15 g and 5 g of sorbitan oleate (HLB13.2) were charged and dissolved uniformly to prepare an oil phase. The aqueous phase was slowly added to the prepared oil phase with high-speed stirring, and stirring was continued for 10 minutes to prepare a water-in-oil emulsion. The atmosphere in the flask was replaced with nitrogen, and the temperature of the reaction system was adjusted to 30 ° C. with a warm water bath. Next, a solution of 1 g of 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile) dissolved in 15 g of toluene as a radical initiator was added to start radical polymerization, and the polymerization reaction was continued for 8 hours. Thus, the water-in-oil radical copolymerization reaction was completed, and a water-in-oil emulsion containing an amphiphilic vinyl copolymer was obtained. When the obtained amphiphilic vinyl copolymer was analyzed, the structural unit formed from acrylamide / the structural unit formed from sodium acrylate / the structural unit formed from methyl methacrylate = 25/25/50 (wt% ) And an amphiphilic vinyl copolymer P-1 having a number average molecular weight of 10,000,000. Furthermore, after adjusting the temperature of the water-in-oil emulsion containing the amphiphilic vinyl copolymer P-1 to 20 ° C., 30 g of polyoxyethylene nonylphenyl ether (HLB9.2) as a phase inversion surfactant, 30 g of polyoxyethylene nonylphenyl ether (HLB13.7) was added to obtain a water-in-oil emulsion PE-1 containing 30.8% of an amphiphilic vinyl copolymer P-1.
[0043]
Synthesis of amphiphilic vinyl copolymers P-2 to P-7 (Examples 2 to 7), vinyl copolymers R-1 to R-4 (Comparative Examples 1 to 4) and water-in-oil emulsion PE- Preparation of 2-PE-7, RE-1 to RE-4
In the same manner as the synthesis of the amphiphilic vinyl copolymer P-1 and the preparation of the water-in-oil emulsion PE-1, the amphiphilic vinyl copolymers P-2 to P-7, the vinyl copolymer R-1 to R-4 and corresponding water-in-oil emulsions PE-2 to PE-7, RE-1 to RE4 were obtained. These contents are summarized in Table 1.
[0044]
Synthesis of amphiphilic vinyl copolymer P-8 (Example 8) and preparation of water-in-oil emulsion PE-8
430 g of ion-exchanged water, 75 g (1.05 mol) of acrylamide, 150 g (1.65 mol) of sodium acrylate and 200 g (1.8 mol) of ethyl methacrylate were treated with a high pressure homogenizer to prepare an aqueous phase. Separately, the viscosity at 30 ° C. in the flask is 2 × 10^-6m²/ S liquid paraffin 570g and polyoxyethylene nonylphenyl ether (HLB9.2) 30g as a surfactant and poly (12-hydroxystearic acid) -polyoxyethylene-poly (12-hydroxystearic acid) copolymer (HLB5) .5) 15 g and 5 g of sorbitan oleate (HLB13.2) were charged and dissolved uniformly to prepare an oil phase. The aqueous phase was slowly added to the prepared oil phase with high-speed stirring, and stirring was continued for 10 minutes to prepare a water-in-oil emulsion. The atmosphere in the flask was replaced with nitrogen, and the temperature of the reaction system was adjusted to 30 ° C. with a warm water bath. Next, a solution of 1 g of 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile) dissolved in 15 g of toluene as a radical initiator was added to start radical polymerization, and the polymerization reaction was continued for 8 hours. (First step). Then, 2 g of a 20% aqueous solution of 3-mercapto-1,2-propanediol was added to terminate the radical (second step). Finally, a solution of 1 g of 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile) dissolved in 15 g of toluene was added to radically activate the radical-terminated copolymer, and then methoxy. In an oil containing amphiphilic vinyl copolymer, polyethoxy (n = 22) ethyl acrylate 75 g (0.075 mol) was added and the reaction was continued for 6 hours to complete the water-in-oil radical copolymerization reaction. An aqueous emulsion was obtained. When the obtained amphiphilic vinyl copolymer was analyzed, the structural unit formed from acrylamide / the structural unit formed from sodium acrylate / the structural unit formed from methyl methacrylate / methoxypolyethoxy (n = 22) It was an amphiphilic vinyl copolymer P-8 having a number average molecular weight of 8000000 and having a structural unit of 15/30/40/15 (% by weight) formed from ethyl methacrylate. Further, after adjusting the temperature of the water-in-oil emulsion containing the amphiphilic vinyl copolymer P-8 to 20 ° C., 30 g of polyoxyethylene nonylphenyl ether (HLB9.2) as a phase inversion surfactant and 30 g of polyoxyethylene nonylphenyl ether (HLB13.7) was added to obtain a water-in-oil emulsion PE-8 containing 30.4% of an amphiphilic vinyl copolymer P-8.
[0045]
Synthesis of amphiphilic vinyl copolymers P-9 and P-10 (Examples 9 and 10) and preparation of water-in-oil emulsions PE-9 and PE-10
Similar to the synthesis of the amphiphilic vinyl copolymer P-8 and the preparation of the water-in-oil emulsion PE-8, the amphiphilic vinyl copolymers P-9 and P-10 and the corresponding water-in-oil emulsion PE- 9, PE-10 was obtained. These contents are summarized in Table 1.
[0046]
[Table 1]

[0047]
In Table 1,
* 1: Non-radical polymerizable organic solvent used for water-in-oil radical copolymerization of each vinyl monomer
* 2: Total of vinyl monomer mixture and water / non-radically polymerizable organic solvent (% by weight) in a reaction system when each vinyl monomer is water-in-oil radical copolymerized, but Examples 8 to 10 Is their proportion in the first step (% by weight)
A-1: A structural unit formed from acrylamide
A-2: A structural unit formed from methacrylamide
B-1: A structural unit formed from sodium acrylate
B-2: Methacrylic acid NH_FourBuilding blocks formed from salt
C-1: a structural unit formed from ethyl metalylate
C-2: A structural unit formed from 2-ethylhexyl acrylate
D-1: a structural unit formed from methoxypolyethoxy (n = 22) ethyl acrylate
D-2: A structural unit formed from hydroxypolyethoxy (n = 12) ethyl methacrylate
S-1: viscosity at 30 ° C. is 4 × 10^-6m²/ S liquid paraffin
S-2: viscosity at 30 ° C. is 2 × 10^-6m²/ S mineral oil
[0048]
Test Category 2 (Preparation of aqueous emulsion of spinning oil)
-Preparation of aqueous emulsion of spinning oil (Examples 11-20, Comparative Examples 5-8)
0.16 parts of a water-in-oil emulsion PE-1 containing 30.8% of the amphiphilic vinyl copolymer P-1 prepared in Test Category 1 (0.002 as the amphiphilic vinyl copolymer P-1). 05 parts), lubricant component L-1 {lauryl octanoate / viscosity at 30 ° C. is 1.3 × 10^-Fivem²/ S mineral oil = mixture comprising 67/33 (weight ratio)} and surfactant component DT-2 {Polyoxyethylene oleyl ether (HLB9.0) / decylsulfonate potassium salt / potassium oleate 39.84 parts of salt = 98/1/1 (weight ratio) and 3.1 parts of water were weighed into a beaker and stirred to prepare a 97% aqueous emulsion of the spinning oil (Example 11). did. In the same manner as in the case of the spinning oil (Example 11), a 97% aqueous emulsion of the spinning oil (Examples 12 to 20) and (Comparative Examples 5 to 8) was prepared. These contents are summarized in Table 2.
[0049]
-Preparation of aqueous emulsion of spinning oil (Comparative Examples 9-12)
60 parts of the lubricant component L-1, 39.5 parts of the surfactant component DT-1 and 3.1 parts of water were weighed in a beaker and stirred to obtain an aqueous emulsion. Separately, high molecular weight polyethylene oxide (molecular weight 2000000) was diluted with water to give a 1% aqueous solution. Then, the aqueous emulsion, a 1% aqueous solution of high molecular weight polyethylene oxide and water are mixed, and the total of the lubricant component L-1 and the surfactant component DT-1 / high molecular weight polyethylene oxide (molecular weight 2000000) = 99.5. A 10% aqueous emulsion of a spinning oil (Comparative Example 9) adjusted to be /0.5 (weight ratio) was prepared. In the same manner as in the case of the spinning oil (Comparative Example 9), a 10% aqueous emulsion of the spinning oil (Comparative Examples 10 to 12) was prepared. These contents are summarized in Table 2.
[0050]
Test category 3 (Evaluation of additives and spinning oils containing them)
・ Compatibility evaluation of additives in aqueous emulsion of spinning oil
・ Compatibility test (compatibility evaluation 1)
The aqueous emulsion of the spinning oil of each example prepared in Test Category 2 was allowed to stand at 30 ° C. for 30 days, and its appearance was observed with the naked eye and evaluated according to the following criteria. However, about Comparative Examples 9-12, what water-evaporated until the water | moisture content of the water-based emulsion prepared by the test division 2 became 3% was used for the test.
○: Generation of solid or gel-like material is not observed, and compatibility is good.
Δ: Slight generation of solid or gel-like material was observed, and the compatibility was slightly poor.
X: Generation | occurrence | production of a solid substance or a gel-like substance was recognized notably, and compatibility was poor.
[0051]
・ Compatibility test (compatibility evaluation 2)
The aqueous emulsion of the spinning oil of each example prepared in Test Category 2 was diluted with water to obtain a 10% aqueous emulsion. 1 g of this 10% aqueous emulsion was placed in a petri dish having a diameter of 100 mm, subjected to hot air drying at 110 ° C. for 2 hours, and then evaluated according to the following criteria. However, Comparative Examples 9 to 12 were used for the test as they were. The above results are summarized in Table 2.
○: Generation of solid or gel-like material is not recognized, and compatibility is good.
Δ: Slight generation of solid or gel-like material was observed, and the compatibility was slightly poor.
X: Generation | occurrence | production of a solid substance or a gel-like substance was recognized notably, and compatibility was poor.
[0052]
・ Evaluation of scattering prevention from running yarn and appearance of scattered objects
A polyethylene terephthalate chip having an intrinsic viscosity of 0.64 and a titanium oxide content of 0.2% was dried by a conventional method, and then spun at 295 ° C. using an extruder. A 10% aqueous emulsion obtained by further diluting the aqueous emulsion of the spinning oil of each example prepared in Test Category 2 into the running yarn after being discharged from the die and cooled and solidified (in Test Category 2 for Comparative Examples 9 to 12) The prepared spinning oil (10% aqueous emulsion as it is) was adhered by a guide oiling method using a metering pump so that the amount of adhesion was 1.1%, and subsequently focused by a guide, and the surface speed was 4000 m / After stretching with a first gotted roller with a surface temperature of 90 ° C. and a second gotted roller with a surface speed of 5000 m / min and a surface temperature of 130 ° C., it is wound up at a speed of 4900 m / min and stretched by 75 denier 36 filaments I got a thread. Here, when the drawn yarn 50000m is manufactured, the lower part of the oiling guide, the interlacer part located between the oiling guide and the first goted roller, and the emulsion of the spinning oil scattered on the lower part of the first goted roller are collected with filter paper. did. The recovered filter paper was heat-treated at 60 ° C. for 24 hours to remove moisture, then weighed, the weight of the recovered spinning oil was calculated, and the scattering prevention property was evaluated according to the following criteria. In addition, the evaluation of the appearance of the flying object was carried out by depositing solid objects on the oiling guide and the first goted roller according to the following criteria by visual observation. The results are summarized in Table 2.
[0053]
Scattering prevention
A: The weight of the recovered spinning oil is less than 10 mg, which is excellent.
○: The weight of the recovered spinning oil is 10 mg or more and less than 30 mg, which is good.
Δ: The weight of the recovered spinning oil is 30 mg or more and less than 100 mg, which is somewhat problematic.
X: The weight of the recovered spinning oil is 100 mg or more, which is problematic.
[0054]
Scattered object appearance
A: Almost no solid deposits are observed.
○: Slight accumulation of solid matter is observed.
Δ: Solid matter accumulation is observed to some extent.
X: Accumulation of solid matter is remarkably observed.
[0055]
[Table 2]

[0056]
In Table 2,
P-1 to P-10, R-1 to R-4: amphiphilic vinyl copolymers described in Table 1, etc. PE-1 to PE-10, RE-1 to RE-4: prepared in test category 1 Water-in-oil emulsion containing a modified amphiphilic vinyl copolymer
R-5: High molecular weight polyethylene (molecular weight 2 million)
R-6: Polyacrylamide (molecular weight 10 million)
R-7: Polyurethane (molecular weight: 400,000) consisting of polyoxyalkylene glycol (compound with an average molecular weight of 2000 obtained by random addition of ethylene oxide and propylene oxide to ethylene glycol) and 4,4'-diphenylmethane diisocyanate
R-8: PEG2000 Zika plate
L-1: Lauryl octanoate / viscosity at 30 ° C. is 1.3 × 10^-Fivem²/ S mineral oil = mixture of 67/33 (weight ratio)
L-2: A mixture having a weight average molecular weight of 1000 polyether / weight average molecular weight of 10000 polyether / butoxypolyethoxyethyl laurate = 60/10/15 (weight ratio).
DT-1: Mixture of polyoxyethylene oleyl ether (HLB11.4) / octanoic acid diethanolamide / lauryl phosphate diethanolamine salt = 40/35/25 (weight ratio)
DT-2: Mixture of polyoxyethylene oleyl ether (HLB9.0) / decylsulfonate potassium salt / potassium oleate = 98/1/1 (weight ratio)
E-1 to E-4: Raw materials used for water-in-oil radical polymerization, which are raw materials having the following constitution excluding the raw material vinyl monomer, radical initiator and radical stopper
E-1: Water (400 parts), non-radically polymerizable solvent S-1 (600 parts), surfactant for water-in-oil radical polymerization {polyoxyethylene nonylphenyl ether (HLB9.2) / poly (12-hydroxy) Stearic acid) -polyoxyethylene-poly (12-hydroxystearic acid) copolymer (HLB5.5) / sorbitan oleate (HLB13.2) = 60/30/10 (weight ratio)} 50 parts , 15 parts of toluene and surfactant for phase inversion {mixture of polyoxyethylene nonylphenyl ether (HLB9.2) / polyoxyethylene nonylphenyl ether (HLB13.7) = 50/50 (weight ratio)} Mixture composed of proportion
E-2: A mixture in which the non-radically polymerizable solvent S-1 is S-2 in E-1
E-3: A mixture in which the amount of toluene in E-1 is 30 parts
E-4: A mixture in which the non-radically polymerizable solvent S-1 is S-2 in E-3
[0057]
【The invention's effect】
As is clear from the above, the additive of the present invention described above is excellent in compatibility with the spinning oil, and the spinning oil containing the fiber can be used even when the aqueous emulsion is adhered to the fiber yarn under high-speed running. The oil agent from the yarn can be effectively prevented from being scattered, and the fibers can be prevented from being damaged by the scattered material.

Claims (9)

An additive for a spinning oil to be attached to a fiber yarn as an aqueous emulsion, which is a structural unit A represented by the following formula 1, a structural unit B represented by the following formula 2, and a structural unit represented by the following formula 3. It is composed of an amphiphilic vinyl copolymer having a number average molecular weight of 30,000 to 30,000,000 having C as a main structural unit and having structural units A, B and C in a total proportion of 80% by weight or more in all the structural units. An additive characterized by that.
[Formula 1]

[Formula 2]

[Formula 3]

(In Formula 1, Formula 2, and Formula 3,
R ¹ , R ² , R ³ : H or CH ₃
R ⁴ : C 1-24 hydrocarbon group X ¹ , X ² : H, C 1-3 hydroxyalkyl group or C 1-8 aliphatic hydrocarbon group M ¹ : alkali metal, NH ₄ or Quaternary ammonium cation) The additive according to claim 1, wherein the amphiphilic vinyl copolymer is composed of a structural unit A, a structural unit B, a structural unit C, and further a structural unit D represented by the following formula 4.
[Formula 4]

(In Equation 4,
R ⁵ : H or CH ₃
R ⁶ : hydrogen or an aliphatic hydrocarbon group having 1 to 6 carbon atoms n: an integer of 5 to 40) The amphiphilic vinyl copolymer has 10 to 50% by weight of the structural unit A, 10 to 50% by weight of the structural unit B and 30 to 80% by weight of the structural unit C in all the structural units. The additive according to 1. The amphiphilic vinyl copolymer is composed of 8 to 40% by weight of structural unit A, 8 to 40% by weight of structural unit B, 24 to 64% by weight of structural unit C, and 1 to 20% by weight of structural unit D. The additive according to claim 2. The amphiphilic vinyl copolymer forms a vinyl monomer a that will form the structural unit A / vinyl monomer b that will form the structural unit B / vinyl unit that will form the structural unit C. A vinyl monomer mixture containing a monomer c = 10 to 50/10 to 50/30 to 80 (wt%) and a total of 80 wt% or more thereof is used as the vinyl monomer. The additive according to claim 3, wherein the mixture is a water-in-oil radical copolymer in a reaction system with a ratio of the total of the mixture and water / non-radically polymerizable organic solvent = 20/80 to 80/20 (wt%). . The amphiphilic vinyl copolymer forms a vinyl monomer a that will form the structural unit A / vinyl monomer b that will form the structural unit B / vinyl unit that will form the structural unit C. A vinyl monomer mixture having a ratio of the monomer c / the vinyl monomer d to form the structural unit D = 8 to 40/8 to 40/24 to 64/1 to 20 (% by weight), 5. A water-in-oil radical copolymerization in a reaction system in which the total of the vinyl monomer mixture and water / non-radically polymerizable organic solvent = 20/80 to 80/20 (wt%). The additive as described. The additive according to claim 2, wherein the amphiphilic vinyl copolymer is obtained through the following first step, second step and third step.
First step: Vinyl monomer mixture comprising vinyl monomer a / vinyl monomer b / vinyl monomer c = 10-50 / 10-50 / 30-80 (wt%) The total reaction amount of the monomer mixture and water / non-radically polymerizable organic solvent = 20/80 to 80/20 (% by weight). In the reaction system in the presence of an oil-soluble radical initiator, Step of obtaining radical-terminated copolymer after polymerization Second step: Step of radically activating the copolymer by adding an oil-soluble radical initiator to the reaction system containing the radical-terminated copolymer Third step: vinyl monomer d in the reaction system containing the radical activated copolymer, the sum of vinyl monomer a, vinyl monomer b and vinyl monomer c used in the first step / The ratio of vinyl monomer d = 80/20 to 99/1 (% by weight) In addition to so that, oil is aqueous radical copolymerization, to obtain an amphiphilic vinyl copolymer A spinning oil that adheres to a fiber yarn as an aqueous emulsion, wherein the additive according to claim 1, 2, 3, 4, 5, 6, or 7 is contained in a proportion of 0.001 to 10% by weight. Spinning oil. The spinning oil according to claim 8, further comprising the following lubricant component and surfactant component.
Lubricant component: mineral oil having a viscosity at 30 ° C. of 5 × 10 ⁻⁶ to 2 × 10 ⁻⁴ m ² / s, an ester compound having a total carbon number of 14 to 70, and an ether ester compound having a total carbon number of 16 to 70 And one or more selected from polyether compounds having a weight average molecular weight of 500 to 15000