JP4229411B2 - Processing agent and processing method of polyolefin fiber for manufacturing nonwoven fabric by dry method - Google Patents

Description

【００４３】
式２において、
Ｙ¹，Ｙ²，Ｙ³：メチル基又はＲ⁴−Ａ²−Ｏ−Ｒ⁵で示されるポリオキシアルキレン変性基であって、少なくともいずれか一つが該ポリオキシアルキレン変性基（Ｒ⁴：炭素数２〜５のアルキレン基，Ｒ⁵：水素又は炭素数１〜１２のアルキル基，Ａ²：炭素数２又は３のオキシアルキレン単位の繰り返しで構成されたポリオキシアルキレン基であって、該オキシアルキレン単位の繰り返し数が１０〜１００であり且つ該オキシアルキレン単位としてオキシエチレン単位を５０モル％以上有するポリオキシアルキレン基）
Ｒ³：炭素数２〜５のアルキル基又はフェニル基
ｐ，ｑ：ｐが７〜１５０、ｑが０〜２０の整数であって、且つ７≦ｐ＋ｑ≦１５０を満足する整数
ｒ：０〜１０の整数
【００４４】
式２で示されるポリオキシアルキレン変性ポリオルガノシロキサンは、必須の構成単位としてジメチルシロキサン単位とポリオキシアルキレン変性基を有するシロキサン単位とを含む線状ポリオルガノシロキサンである。ポリオキシアルキレン変性基を有するシロキサン単位としては、式２においてポリオルガノシロキサン鎖中に存在するｒで括られた２価のメチル・ポリオキシアルキレン変性シロキサン単位、末端基としての１価のジメチル・ポリオキシアルキレン変性シロキサン単位が挙げられるが、かかるポリオキシアルキレン変性シロキサン単位としてｒで括られた２価のメチル・ポリオキシアルキレン変性シロキサン単位を有するものが好ましい。このようにポリオキシアルキレン変性基を末端でなくポリオルガノシロキサン鎖中に有する場合、これを含むシロキサン単位としては１個又は２〜１０個の繰り返し単位とする。この場合、末端基としては式２中のＹ¹，Ｙ²がメチル基に相当するトリメチルシロキサン単位であっても又はＹ¹，Ｙ²がポリオキシアルキレン変性基であるジメチル・ポリオキシアルキレン変性シロキサン単位であっても支障はないが、トリメチルシロキサン単位が好ましい。
【００４５】
式２で示されるポリオキシアルキレン変性ポリオルガノシロキサンにおいて、ポリオルガノシロキサン主鎖を形成することとなるポリオキシアルキレン変性基を有しないシロキサン単位としてはｐで括られたジメチルシロキサン単位に加えてｑで括られた２価のオルガノシロキサン単位を含むことができる。ｑで括られた２価のオルガノシロキサン単位としては、メチルエチルシロキサン単位、メチルプロピルシロキサン単位、メチルヘキシルシロキサン単位、メチルフェニルシロキサン単位等が挙げられる。ポリオキシアルキレン変性基を有しないシロキサン単位の繰り返し数は、ｐが７〜１５０、ｑが０〜２０であって、且つｐとｑとの合計が７〜１５０とするが、ジメチルシロキサン単位のみから成り（式２中のｑが０の場合）、且つその繰り返し数が１０〜７０のものが好ましい。
【００４６】
式２中のＲ⁴−Ａ²−Ｏ−Ｒ⁵で示されるポリオキシアルキレン変性基において、Ｒ⁴はシロキサン単位のケイ素原子とポリオキシアルキレン基とを連結するアルキレン基であり、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基等の炭素数２〜５のアルキレン基であるが、エチレン基、トリメチレン基が好ましい。またＲ⁵はポリオキシアルキレン基の末端基であって、水素、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基等であるが、水素又はメチル基が好ましい。更にＡ²を構成するオキシアルキレン単位は、オキシエチレン単位或はオキシエチレン単位とオキシプロピレン単位とであるが、該オキシアルキレン単位としてオキシエチレン単位を５０モル％以上、好ましくは７０モル％以上有するものである。かかるポリオキシアルキレン基には、１）オキシエチレン単位のみから成るもの、２）５０モル％以上のオキシエチレン単位と５０モル％以下のオキシプロピレン単位とがブロック状及び／又はランダム状に結合したものから成るものが包含される。かかるポリオキシアルキレン基を構成するオキシアルキレン単位の繰り返し数は１０〜１００とするが、２０〜７０とするのが好ましい。
【００４７】
以上説明したポリオキシアルキレン変性ポリオルガノシロキサンは公知の合成方法、例えば米国再発行特許第２５７２７号明細書に記載されている合成方法で合成できる。かかるポリオキシアルキレン変性ポリオルガノシロキサンを併用する場合、本発明の処理剤は、前記した式１で示されるポリエーテル化合物とポリグリセリン脂肪酸エステルとポリエーテルポリエステルブロック共重合体との合計量に対して、該ポリエーテル化合物と該ポリグリセリン脂肪酸エステルと該ポリエーテルポリエステルブロック共重合体との合計量／該ポリオキシアルキレン変性ポリオルガノシロキサン＝４０／６０〜９５／５（重量比）の割合で含有するものが好ましく、６０／４０〜９０／１０（重量比）の割合で含有するものが更に好ましい。
【００４８】
本発明の処理剤には、以上説明した式１で示されるポリエーテル化合物、ポリグリセリン脂肪酸エステル、ポリエーテルエステルブロック共重合体及びポリオキシアルキレン変性ポリオルガノシロキサン以外に、合目的的に他の界面活性剤を併用することができる。かかる界面活性剤としては公知のものが適用できる。これには例えば、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アルキルエステル、ポリオキシアルキレンヒマシ油、ポリオキシアルキレン硬化ヒマシ油等の、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）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、長鎖アルキル基含有ポリオキシアルキレンアルキルアミノエーテル、２〜４個のポリオキシアルキレンアミノエーテル部位を有するポリエーテルポリアミン、ポリオキシアルキレン基を有する脂肪酸アミド化合物等の、ポリオキシアルキレン基を有する含窒素非イオン性界面活性剤、４）脂肪族サルフェート塩、脂肪族スルフォネート塩、脂肪族フォスフェート塩、脂肪族カルボン酸塩、ポリオキシアルキレン基を有する脂肪族サルフェート塩、ポリオキシアルキレン基を有する脂肪族スルフォネート塩、ポリオキシアルキレン基を有する脂肪族フォスフェート塩等のアニオン性界面活性剤、５）長鎖アルキルアミンの酸中和物、ポリオキシアルキレンアルキルアミノエーテルの酸中和物、ポリオキシアルキレン基を有する脂肪酸アミド化合物の酸中和物、ポリオキシアルキレンポリアミンポリアミド架橋物の酸中和物等のアミン塩部位を有するカチオン性界面活性剤、６）ポリオキシアルキレン基を有する脂肪酸アミド化合物の４級化物、テトラアルキルアンモニウム塩、アルキルイミダゾリニウム塩、テトラアルキルホスホニウム塩等の４級化部位を有するカチオン性界面活性剤、７）長鎖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、長鎖アルキルアミノ酸等の両性界面活性剤等が挙げられる。
【００４９】
本発明の処理剤を乾式法による不織布製造用ポリオレフィン系繊維へ付着させる場合、該処理剤を、該ポリオレフィン系繊維の紡糸工程、延伸工程、更には延伸後の各工程において、浸漬法、スプレー法、ローラー給油法、計量ポンプを用いたガイド給油法等の給油法により付着させることができるが、浸漬法で付着させるのが好ましい。処理剤の付着量は、ポリオレフィン系繊維に対し０．０５〜５重量％とするが、０．１〜２．５重量％とするのが好ましい。ポリオレフィン系繊維に所望通りの優れたカード通過性を付与し、また得られるカードウェッブに優れた地合の均一性、透水性、耐久親水性及びウェットバック防止性を付与するためである。
【００５０】
本発明の処理剤はその水性液としてポリオレフィン系繊維に付着させるのが好ましい。かかる水性液の調製にはホモミキサーやホモジナイザー等を用いた公知の機械的乳化方法が適用できる。調製される水性液の処理剤濃度は通常１〜３０重量％とするが、５〜１５重量％とするのが有利である。
【００５１】
本発明の処理剤を適用するポリオレフィン系繊維としては、ポリエチレン繊維、ポリプロピレン繊維、ポリブテン繊維、芯鞘構造の複合繊維であって鞘部がポリオレフィン系繊維である複合繊維、例えば鞘部がポリエチレン繊維であるポリエチレン／ポリプロピレン複合繊維、ポリエチレン／ポリエステル複合繊維等が挙げられる。
【００５２】
【発明の実施の形態】
本発明に係る処理剤の実施形態としては、次の１）〜２２）が挙げられる。
１）下記のポリエーテル化合物（Ｈ−１）５０重量％、及び下記のポリグリセリン脂肪酸エステル（Ｊ−１）５０重量％を含有して成る処理剤。
ポリエーテル化合物（Ｈ−１）：式１中のＲ¹がトリアコンチル基、Ｒ²が水素、Ａ¹が１０モルのオキシエチレン単位の繰り返しからなるポリオキシエチレン基である場合のポリエーテル化合物
ポリグリセリン脂肪酸エステル（Ｊ−１）：縮合度が４のテトラグリセリンとステアリン酸とをエステル化反応させ、該テトラグリセリンの水酸基の１６．７モル％をエステル化したポリグリセリン脂肪酸エステル
【００５３】
２）下記のポリエーテル化合物（Ｈ−２）７０重量％、及び下記のポリグリセリン脂肪酸エステル（Ｊ−２）３０重量％を含有して成る処理剤。
ポリエーテル化合物（Ｈ−２）：式１中のＲ¹がテトラコンチル基、Ｒ²が水素、Ａ¹が３０モルのオキシエチレン単位の繰り返しからなるポリオキシエチレン基である場合のポリエーテル化合物
ポリグリセリン脂肪酸エステル（Ｊ−２）：縮合度が６のヘキサグリセリンとミリスチン酸とをエステル化反応させ、該ヘキサグリセリンの水酸基の１２．５モル％をエステル化したポリグリセリン脂肪酸エステル
【００５４】
３）下記のポリエーテル化合物（Ｈ−３）８０重量％、及び下記のポリグリセリン脂肪酸エステル（Ｊ−３）２０重量％を含有して成る処理剤。
ポリエーテル化合物（Ｈ−３）：式１中のＲ¹がトリアコンタノイル基、Ｒ²が水素、Ａ¹が２４モルのオキシエチレン単位と１６モルのオキシプロピレン単位との繰り返しからなるポリオキシエチレンポリオキシプロピレン基である場合のポリエーテル化合物
ポリグリセリン脂肪酸エステル（Ｊ−３）：縮合度が４のテトラグリセリンとステアリン酸とをエステル化反応させ、該テトラグリセリンの水酸基の３３．３モル％をエステル化したポリグリセリン脂肪酸エステル
【００５５】
４）下記のポリエーテル化合物（Ｈ−４）３０重量％、及び下記のとポリグリセリン脂肪酸エステル（Ｊ−４）７０重量％を含有して成る処理剤。
ポリエーテル化合物（Ｈ−４）：式１中のＲ¹がテトラコンタノイル基、Ｒ²が水素、Ａ¹が２５モルのオキシエチレン単位の繰り返しからなるポリオキシエチレン基である場合のポリエーテル化合物
ポリグリセリン脂肪酸エステル（Ｊ−４）：縮合度が１０のデカグリセリンとステアリン酸とをエステル化反応させ、該デカグリセリンの水酸基の２５．０モル％をエステル化したポリグリセリン脂肪酸エステル
【００５６】
５）下記のポリエーテル化合物（Ｈ−５）６０重量％、及び下記のポリグリセリン脂肪酸エステル（Ｊ−５）４０重量％を含有して成る処理剤。
ポリエーテル化合物（Ｈ−５）：式１中のＲ¹がペンタコンチル基、Ｒ²がメチル基、Ａ¹が３０モルのオキシエチレン単位の繰り返しからなるポリオキシエチレン基である場合のポリエーテル化合物
ポリグリセリン脂肪酸エステル（Ｊ−５）：縮合度が４のテトラグリセリンとミリスチン酸とをエステル化反応させ、該テトラグリセリンの水酸基の１６．７モル％をエステル化したポリグリセリン脂肪酸エステル
【００５７】
６）下記のポリエーテル化合物（Ｈ−６）６０重量％、及び下記のポリグリセリン脂肪酸エステル（Ｊ−６）４０重量％を含有して成る処理剤。
ポリエーテル化合物（Ｈ−６）：式１中のＲ¹がトリアコンチル基、Ｒ²がアセチル基、Ａ¹が２０モルのオキシエチレン単位の繰り返しからなるポリオキシエチレン基である場合のポリエーテル化合物
ポリグリセリン脂肪酸エステル（Ｊ−６）：縮合度が６のヘキサグリセリンとオレイン酸とをエステル化反応させ、該ヘキサグリセリンの水酸基の５０．０モル％をエステル化したポリグリセリン脂肪酸エステル
【００５８】
７）前記のポリエーテル化合物（Ｈ−１）３０重量％、前記のポリグリセリン脂肪酸エステル（Ｊ−１）３０重量％、及び下記のポリエーテルポリエステルブロック共重合体（Ｋ−１）４０重量％を含有して成る処理剤。
ポリエーテルポリエステルブロック共重合体（Ｋ−１）：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との混合物を開環重合してポリエーテルブロックを形成させ、次いでε−カプロラクトンを開環重合してポリエステルブロックを形成させた、ポリエーテルブロックがエチレングリコールの水酸基１個当たり７５モルのオキシアルキレン単位を有すると共にオキシアルキレン単位としてオキシエチレン単位を６７モル％有し、且つオキシカプロイル単位の全繰り返し数／オキシアルキレン単位の全繰り返し数＝１／３（モル比）の割合で有するポリエーテルポリエステルブロック共重合体
【００５９】
８）前記のポリエーテル化合物（Ｈ−１）４９重量％、前記のポリグリセリン脂肪酸エステル（Ｊ−１）２１重量％、及び下記のポリエーテルポリエステルブロック共重合体（Ｋ−２）３０重量％を含有して成る処理剤。
ポリエーテルポリエステルブロック共重合体（Ｋ−２）：エチレングリコールにエチレンオキサイドを開環重合してポリエーテルブロックを形成させ、次いでε−カプロラクトンを開環重合してポリエステルブロックを形成させた、ポリエーテルブロックがエチレングリコールの水酸基１個当たり７５モルのオキシアルキレン単位を有すると共にオキシアルキレン単位としてオキシエチレン単位を１００モル％有し、且つオキシカプロイル単位の全繰り返し数／オキシアルキレン単位の全繰り返し数＝１／３（モル比）の割合で有するポリエーテルポリエステルブロック共重合体
【００６０】
９）前記のポリエーテル化合物（Ｈ−２）３５重量％、前記のポリグリセリン脂肪酸エステル（Ｊ−２）３５重量％、及び下記のポリエーテルポリエステルブロック共重合体（Ｋ−３）３０重量％を含有して成る処理剤。
ポリエーテルポリエステルブロック共重合体（Ｋ−３）：グリセリンにプロピレンオキサイドを開環重合し、更にエチレンオキサイドを開環重合してポリエーテルブロックを形成させ、次いでε−カプロラクトンを開環重合してポリエステルブロックを形成させた、ポリエーテルブロックがグリセリンの水酸基１個当たり７５モルのオキシアルキレン単位を有すると共にオキシアルキレン単位としてオキシエチレン単位を８０モル％有し、且つオキシカプロイル単位の全繰り返し数／オキシアルキレン単位の全繰り返し数＝１／２．５（モル比）の割合で有するポリエーテルポリエステルブロック共重合体
【００６１】
１０）前記のポリエーテル化合物（Ｈ−２）４２重量％、前記のポリグリセリン脂肪酸エステル（Ｊ−１）１８重量％、及び下記のポリエーテルポリエステルブロック共重合体（Ｋ−４）４０重量％を含有して成る処理剤。
ポリエーテルポリエステルブロック共重合体（Ｋ−４）：グリセリンにエチレンオキサイドを開環重合してポリエーテルブロックを形成させ、次いでε−カプロラクトンを開環重合してポリエステルブロックを形成させた、ポリエーテルブロックがグリセリンの水酸基１個当たり７５モルのオキシアルキレン単位を有すると共にオキシアルキレン単位としてオキシエチレン単位を１００モル％有し、且つオキシカプロイル単位の全繰り返し数／オキシアルキレン単位の全繰り返し数＝１／２．５（モル比）の割合で有するポリエーテルポリエステルブロック共重合体
【００６２】
１１）前記のポリエーテル化合物（Ｈ−２）４２重量％、前記のポリグリセリン脂肪酸エステル（Ｊ−１）１８重量％、及び下記のポリエーテルポリエステルブロック共重合体（Ｋ−５）４０重量％を含有して成る処理剤。
ポリエーテルポリエステルブロック共重合体（Ｋ−５）：ペンタエリスリトールにエチレンオキサイド及びプロピレンオキサイドの混合物を開環重合してポリエーテルブロックを形成させ、次いでε−カプロラクトンを開環重合してポリエステルブロックを形成させた、ポリエーテルブロックがペンタエリスリトールの水酸基１個当たり６０モルのオキシアルキレン単位を有すると共にオキシアルキレン単位としてオキシエチレン単位を７５モル％有し、且つオキシカプロイル単位の全繰り返し数／オキシアルキレン単位の全繰り返し数＝１／２（モル比）の割合で有するポリエーテルポリエステルブロック共重合体
【００６３】
１２）前記のポリエーテル化合物（Ｈ−２）４２重量％、前記のポリグリセリン脂肪酸エステル（Ｊ−１）１８重量％、及び下記のポリエーテルポリエステルブロック共重合体（Ｋ−６）４０重量％を含有して成る処理剤。
ポリエーテルポリエステルブロック共重合体（Ｋ−６）：ソルビタンモノステアレートにエチレンオキサイドを開環重合してポリエーテルブロックを形成させ、次いでε−カプロラクトンを開環重合してポリエステルブロックを形成させた、ポリエーテルブロックがソルビタンモノステアレートの水酸基１個当たり６０モルのオキシアルキレン単位を有すると共にオキシアルキレン単位としてオキシエチレン単位を１００モル％有し、且つオキシカプロイル単位の全繰り返し数／オキシアルキレン単位の全繰り返し数＝１／１．５（モル比）の割合で有するポリエーテルポリエステルブロック共重合体
【００６４】
１３）前記のポリエーテル化合物（Ｈ−１）４２重量％、前記のポリグリセリン脂肪酸エステル（Ｊ−２）１８重量％、及び下記のポリエーテルポリエステルブロック共重合体（Ｋ−７）４０重量％を含有して成る処理剤。
ポリエーテルポリエステルブロック共重合体（Ｋ−７）：前記のポリエーテルポリエステルブロック共重合体（Ｋ−３）をステアリン酸でアシル化したアシル化ポリエーテルポリエステルブロック共重合体
【００６５】
１４）前記のポリエーテル化合物（Ｈ−２）４２重量％、前記のポリグリセリン脂肪酸エステル（Ｊ−１）１８重量％、及び下記のポリエーテルポリエステルブロック共重合体（Ｋ−８）４０重量％を含有して成る処理剤。
ポリエーテルポリエステルブロック共重合体（Ｋ−８）：前記のポリエーテルポリエステルブロック共重合体（Ｋ−５）をステアリン酸でアシル化したアシル化ポリエーテルポリエステルブロック共重合体
【００６６】
１５）前記のポリエーテル化合物（Ｈ−１）４２重量％、前記のポリグリセリン脂肪酸エステル（Ｊ−２）１８重量％、及び下記のポリエーテルポリエステルブロック共重合体（Ｋ−９）４０重量％を含有して成る処理剤。
ポリエーテルポリエステルブロック共重合体（Ｋ−９）：グリセリンにε−カプロラクトンを開環重合してポリエステルブロックを形成させ、次いでエチレンオキサイドを開環重合してポリエーテルブロックを形成させた、ポリエーテルブロックがグリセリンの水酸基１個当たり７５モルのオキシアルキレン単位を有すると共にオキシアルキレン単位としてオキシエチレン単位を１００モル％有し、且つオキシカプロイル単位の全繰り返し数／オキシアルキレン単位の全繰り返し数＝１／２．５（モル比）の割合で有するポリエーテルポリエステルブロック共重合体
【００６７】
１６）前記のポリエーテル化合物（Ｈ−２）４２重量％、前記のポリグリセリン脂肪酸エステル（Ｊ−１）１８重量％、及び下記のポリエーテルポリエステルブロック共重合体（Ｋ−１０）４０重量％を含有して成る処理剤。
ポリエーテルポリエステルブロック共重合体（Ｋ−１０）：グルコン酸にエチレンオキサイドを開環重合してポリエーテルブロックを形成させ、次いでε−カプロラクトンを開環重合してポリエステルブロックを形成させた、ポリエーテルブロックがグルコン酸の水酸基１個当たり４０モルのオキシアルキレン単位を有すると共にオキシアルキレン単位としてオキシエチレン単位を１００モル％有し、且つオキシカプロイル単位の全繰り返し数／オキシアルキレン単位の全繰り返し数＝１／１（モル比）の割合で有するポリエーテルポリエステルブロック共重合体
【００６８】
１７）前記のポリエーテル化合物（Ｈ−１）４２重量％、前記のポリグリセリン脂肪酸エステル（Ｊ−２）１８重量％、及び下記のポリエーテルポリエステルブロック共重合体（Ｋ−１１）４０重量％を含有して成る処理剤。
ポリエーテルポリエステルブロック共重合体（Ｋ−１１）：トリエタノールアミンにエチレンオキサイドを開環重合してポリエーテルブロックを形成させ、次いでε−カプロラクトンを開環重合してポリエステルブロックを形成させた、ポリエーテルブロックがトリエタノールアミンの水酸基１個当たり４０モルのオキシアルキレン単位を有すると共にオキシアルキレン単位としてオキシエチレン単位を１００モル％有し、且つオキシカプロイル単位の全繰り返し数／オキシアルキレン単位の全繰り返し数＝１／１（モル比）の割合で有するポリエーテルポリエステルブロック共重合体
【００６９】
１８）前記のポリエーテル化合物（Ｈ−２）４２重量％、前記のポリグリセリン脂肪酸エステル（Ｊ−１）１８重量％、及び下記のポリエーテルポリエステルブロック共重合体（Ｋ−１２）４０重量％を含有して成る処理剤。
ポリエーテルポリエステルブロック共重合体（Ｋ−１２）：Ｎ，Ｎ，Ｎ’，Ｎ’−テトラ（２−ヒドロキシプロピル）−エチレンジアミンにエチレンオキサイドを開環重合してポリエーテルブロックを形成させ、次いでε−カプロラクトンを開環重合してポリエステルブロックを形成させた、ポリエーテルブロックがＮ，Ｎ，Ｎ’，Ｎ’−テトラ（２−ヒドロキシプロピル）−エチレンジアミンの水酸基１個当たり４０モルのオキシアルキレン単位を有すると共にオキシアルキレン単位としてオキシエチレン単位を１００モル％有し、且つオキシカプロイル単位の全繰り返し数／オキシアルキレン単位の全繰り返し数＝１／１（モル比）の割合で有するポリエーテルポリエステルブロック共重合体
【００７０】
１９）前記のポリエーテル化合物（Ｈ−１）２７重量％、前記のポリグリセリン脂肪酸エステル（Ｊ−２）２７重量％、前記のポリエーテルポリエステルブロック共重合体（Ｋ−１）２３重量％、下記のポリオキシアルキレン変性ポリオルガノシロキサン（Ｌ−１）１９重量％、及び下記の界面活性剤混合物（Ｅ−１）４重量％を含有して成る処理剤。
ポリオキシアルキレン変性ポリオルガノシロキサン（Ｌ−１）：式２中のＹ¹，Ｙ²がメチル基、ｐが１２０、ｑが０、ｒが２、Ｙ³がＲ⁴−Ａ²−Ｏ−Ｒ⁵で示されるポリオキシアルキレン変性基であって、Ｒ⁴がトリメチレン基、Ｒ⁵がメチル基、Ａ²が４５モルのオキシエチレン単位の繰り返しからなるポリオキシエチレン基である場合のポリオキシアルキレン変性ポリオルガノシロキサン
界面活性剤混合物（Ｅ−１）：グリセリンモノラウリン酸エステル／ポリオキシエチレン（１５モル）ソルビタンモノステアリン酸エステル／ラウリルスルホン酸ナトリウム＝３０／３０／４０（重量比）の割合の混合物
【００７１】
２０）前記のポリエーテル化合物（Ｈ−２）２７重量％、前記のポリグリセリン脂肪酸エステル（Ｊ−１）２７重量％、前記のポリエーテルポリエステルブロック共重合体（Ｋ−３）２３重量％、下記のポリオキシアルキレン変性ポリオルガノシロキサン（Ｌ−２）１９重量％、及び下記の界面活性剤混合物（Ｅ−２）４重量％を含有して成る処理剤。
ポリオキシアルキレン変性ポリオルガノシロキサン（Ｌ−２）：式２中のＹ¹，Ｙ²がメチル基、ｐが８０、ｑが０、ｒが２、Ｙ³がＲ⁴−Ａ²−Ｏ−Ｒ⁵で示されるポリオキシアルキレン変性基であって、Ｒ⁴がトリメチレン基、Ｒ⁵が水素、Ａ²が２５モルのオキシエチレン単位の繰り返しからなるポリオキシエチレン基である場合のポリオキシアルキレン変性ポリオルガノシロキサン
界面活性剤混合物（Ｅ−２）：グリセリンモノラウリン酸エステル／ポリオキシエチレン（１５モル）ソルビタンモノステアリン酸エステル／ポリオキシエチレン（５モル）ラウリルエーテル硫酸エステルナトリウム＝３０／３０／４０（重量比）の割合の混合物
【００７２】
２１）前記のポリエーテル化合物（Ｈ−１）３８重量％、前記のポリグリセリン脂肪酸エステル（Ｊ−２）１６重量％、前記のポリエーテルポリエステルブロック共重合体（Ｋ−５）２３重量％、下記のポリオキシアルキレン変性ポリオルガノシロキサン（Ｌ−３）１９重量％、及び下記の界面活性剤混合物（Ｅ−３）４重量％を含有して成る処理剤。
ポリオキシアルキレン変性ポリオルガノシロキサン（Ｌ−３）：式２中のｐが１００、ｑが１０、ｒが０、Ｒ³がフェニル基、Ｙ¹，Ｙ²がＲ⁴−Ａ²−Ｏ−Ｒ⁵で示されるポリオキシアルキレン変性基であって、Ｒ⁴がトリメチレン基、Ｒ⁵が水素、Ａ²が３０モルのオキシエチレン単位と２０モルのオキシプロピレン単位の繰り返しからなるポリオキシエチレン基である場合のポリオキシアルキレン変性ポリオルガノシロキサン
界面活性剤混合物（Ｅ−３）：グリセリンモノラウリン酸エステル／ポリオキシエチレン（１５モル）ソルビタンモノステアリン酸エステル／ポリオキシエチレン（８モル）セチルエーテルリン酸エステルカリウム＝３０／３０／４０（重量比）の割合の混合物
【００７３】
２２）前記のポリエーテル化合物（Ｈ−２）３８重量％、前記のポリグリセリン脂肪酸エステル（Ｊ−１）１６重量％、前記のポリエーテルポリエステルブロック共重合体（Ｋ−１）２３重量％、前記のポリオキシアルキレン変性ポリオルガノシロキサン（Ｌ−１）１９重量％、及び下記の界面活性剤混合物（Ｅ−４）４重量％を含有して成る処理剤。
界面活性剤混合物（Ｅ−４）：グリセリンモノラウリン酸エステル／ステアリン酸ジエタノールアミド／ベヘニン酸アミドプロピルジメチルエチルアンモニウムエトサルフェート＝４０／３０／３０（重量比）の割合の混合物
【００７４】
また本発明に係る処理方法の実施形態としては、次の２３）が挙げられる。
２３）前記した１）〜２２）のいずれかの処理剤１００ｇと水９００ｇとを激しく撹拌して分散液とし、更にホモジナイザーにより乳化して処理剤の１０重量％水性液とした後、これを水で希釈した１重量％水性液を用いて、乾式法による不織布製造に供する２．０デニール×５１mmカットのポリエチレン／ポリエステル複合繊維綿に対し処理剤として０．３５重量％となるよう浸漬法で付着させる方法。
【００７５】
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、本発明がこれらの実施例に限定されるものではない。
【００７６】
【実施例】
試験区分１（ポリエーテル化合物の合成）
・ポリエーテル化合物（Ｈ−１）の合成
トリアコンチルアルコール４３８ｇ（１モル）及び水酸化カリウム２ｇをオートクレーブに仕込み、窒素ガスでパージ後、１２０℃に加温し、エチレンオキサイド４５０ｇ（１０．２モル）を圧入して、反応させた。１時間の熟成反応後、触媒を吸着剤処理により除去し、反応物を得た。得られた反応物を分析したところ、オキシエチレン単位の繰り返し数が１０であり、水酸基価６３、数平均分子量９２０（ＧＰＣ法、ポリスチレン換算、以下同じ）のポリエーテル化合物（Ｈ−１）であった。
【００７７】
ポリエーテル化合物（Ｈ−２）〜（Ｈ−４）及び（ｈ−１）〜（ｈ−４）の合成
ポリエーテル化合物（Ｈ−１）の場合と同様にして、ポリエーテル化合物（Ｈ−２）〜（Ｈ−４）及び（ｈ−１）〜（ｈ−４）を合成した。
【００７８】
ポリエーテル化合物（Ｈ−５）の合成
ペンタコンチルアルコール７１８ｇ（１モル）をオートクレーブに仕込み、触媒として水酸化カリウム粉末５ｇを加えた後、オートクレーブ内を充分に窒素で置換した。撹拌しながら反応温度を１１０℃〜１２０℃に維持してエチレンオキサイド１３６４ｇ（３１モル）を圧入し、付加重合反応を行った。その後、同温度で１時間熟成して反応を終了した。反応物をフラスコに移し、触媒の水酸化カリウムをリン酸で中和した。中和物からリン酸塩を濾別してポリオキシアルキレンモノペンタコンチルエーテル２０８０ｇを得た。ここで得られたポリオキシアルキレンモノペンタコンチルエーテル２９１８ｇ（１モル）と４８％水酸化カリウム水溶液１１７ｇをオートクレーブに仕込み、撹拌しながら７０〜１００℃で減圧下に脱水を行った。その後、反応温度を１００〜１２０℃に維持して、塩化メチル５３ｇ（１．０５モル）をオートクレーブ内の圧力低下が認められなくなるまで圧入し、エーテル化反応を行った。反応生成物から副生した塩化カリウムを濾別して、ポリエーテル化合物（Ｈ−５）を得た。これを分析したところ、ポリオキシアルキレン基がオキシエチレン単位の繰り返し数３０で構成されたポリオキシアルキレンペンタコンチルメチルエーテルであった。
【００７９】
ポリエーテル化合物（ｈ−５）の合成
ポリエーテル化合物（Ｈ−５）の場合と同様にして、ポリエーテル化合物（ｈ−５）を合成した。
【００８０】
・ポリエーテル化合物（Ｈ−６）の合成
ポリエーテル化合物（Ｈ−１）の合成の場合と同様にして得た中間体としてのポリオキシアルキレンモノトリアコンチルエーテル１３１８ｇ（１モル）、氷酢酸７２ｇ（１．２モル）及び触媒として濃硫酸６ｇをフラスコに仕込み、撹拌しながら反応温度を１００〜１１０℃とし、減圧下に脱水してエステル化反応を行った。反応終了後、冷却しながら、濃硫酸と未反応酢酸とを４８％水酸化カリウム３５ｇで中和した。次いで生成水を減圧下に留去した。副生した無機塩を濾別してポリエーテル化合物（Ｈ−６）を得た。これを分析したところ、ポリオキシアルキレン基がオキシエチレン単位の繰り返し数２０で構成されたポリオキシアルキレンモノトリアコンチルエーテルの酢酸エステルであった。以上で合成した各ポリエーテル化合物の内容を表１にまとめて示した。
【００８１】
【表１】

【００８２】
表１において、
ＥＯ：オキシエチレン単位
ＰＯ：オキシプロピレン単位
【００８３】
試験区分２（ポリエーテルポリエステルブロック共重合体等の合成）
・ポリエーテルポリエステルブロック共重合体（Ｋ−１）の合成
エチレングリコール６２ｇ（１モル）及び水酸化カリウム２０ｇをオートクレーブに仕込み、窒素ガスでパージ後、１２０℃に加温し、エチレンオキサイド４５３２ｇ（１０３．０モル）とプロピレンオキサイド２９９２．８ｇ（５１．６モル）との混合物を圧入して、反応させた。１時間の熟成反応後、触媒を吸着剤処理により除去し、反応物を得た。得られた反応物を分析したところ、オキシエチレン単位／オキシプロピレン単位＝５０／２５（モル比、ＮＭＲ分析法、以下同じ）の共重合比率であり、水酸基価１５．２、数平均分子量７５００（ＧＰＣ法、ポリスチレン換算、以下同じ）のポリエーテル化合物であった。得られたポリエーテル化合物７５０ｇ（０．１モル）及びテトラブチルチタネート２．５ｇをフラスコに仕込み、窒素ガス気流下で撹拌しながら１５０℃に加温した。１４０〜１５０℃に温度を保ち、ε−カプロラクトン５９２．８ｇ（５．２モル）を２０分かけて滴下した。滴下終了後、１５０℃で３時間反応を続けて合成を終了し、反応物を得た。得られた反応物を分析したところ、オキシエチレン単位／オキシプロピレン単位／オキシカプロイル単位＝５０／２５／２５（モル％）の共重合比率であり、数平均分子量１３２００のポリエーテルポリエステルブロック共重合体（Ｋ−１）であった。
【００８４】
・ポリエーテルポリエステルブロック共重合体（Ｋ−５）の合成
ポリエーテルポリエステルブロック共重合体（Ｋ−１）の場合と同様にして、ポリエーテルポリエステルブロック共重合体（Ｋ−５）を得た。
【００８５】
・ポリエーテルポリエステルブロック共重合体（Ｋ−２）の合成
エチレングリコール６２ｇ（１モル）及び水酸化カリウム１７ｇをオートクレーブに仕込み、窒素ガスでパージ後、１２０℃に加温し、エチレンオキサイド６７９８ｇ（１５４．５モル）を圧入して、反応させた。１時間の熟成反応後、触媒を吸着剤処理により除去し、反応物を得た。得られた反応物を分析したところ、エチレングリコール１モルに対してオキシエチレン単位が１５０モル付加しており、水酸基価１６．８、数平均分子量６８００のポリエーテル化合物であった。得られたポリエーテル化合物６８０ｇ（０．１モル）及びテトラブチルチタネート４．２ｇをフラスコに仕込み、窒素ガス気流下で撹拌しながら１５０℃に加温した。１４０〜１５０℃に温度を保ち、ε−カプロラクトン５９２．８ｇ（５．２モル）を４０分かけて滴下した。滴下終了後、１５０℃で３時間反応を続けて合成を終了し、反応物を得た。得られた反応物を分析したところ、オキシエチレン単位／オキシカプロイル単位＝７５／２５（モル％）の共重合比率であり、数平均分子量１２５００のポリエーテルポリエステルブロック共重合体（Ｋ−２）であった。
【００８６】
・ポリエーテルポリエステルブロック共重合体（Ｋ−４）及び（Ｋ−６）の合成
ポリエーテルポリエステルブロック共重合体（Ｋ−２）の場合と同様にして、ポリエーテルポリエステルブロック共重合体（Ｋ−４）及び（Ｋ−６）を得た。
【００８７】
・ポリエーテルポリエステルブロック共重合体（Ｋ−３）の合成
グリセリン９２ｇ（１モル）及び水酸化カリウム２７ｇをオートクレーブに仕込み、窒素ガスでパージ後、１２０〜１４０℃に温度を保ちながらプロピレンオキサイド２６９１．２ｇ（４６．４モル）を圧入して、反応させた。同温度で１時間の熟成反応後、更にエチレンオキサイド８１５７．６ｇ（１８５．４モル）を圧入して、反応させた。同温度で１時間の熟成反応後、触媒を吸着剤処理により除去し、反応物を得た。得られた反応物を分析したところ、オキシエチレン単位／オキシプロピレン単位＝６０／１５（モル比）の共重合比率であり、水酸基価１５．８、数平均分子量１０８００のポリエーテル化合物であった。得られたポリエーテル化合物１０８０ｇ（０．１モル）及びテトラブチルチタネート３．８ｇをフラスコに仕込み、窒素ガス気流下で撹拌しながら１５０℃に加温した。１４０〜１５０℃に温度を保ち、ε−カプロラクトン１０６０．２ｇ（９．３モル）を４０分かけて滴下した。滴下終了後、１５０℃で３時間反応を続けて合成を終了し、反応物を得た。得られた反応物を分析したところ、オキシエチレン単位／オキシプロピレン単位／オキシカプロイル単位＝６０／１５／３０（モル％）の共重合比率であり、数平均分子量２１１００のポリエーテルポリエステルブロック共重合体（Ｋ−３）であった。
【００８８】
・ポリエーテルポリエステルブロック共重合体（Ｋ−９）の合成
グリセリン９２ｇ（１モル）及びテトラブチルチタネート７．６ｇをフラスコに仕込み、窒素ガス気流下で撹拌しながら１５０℃に加温した。１４０〜１５０℃に温度を保ち、ε−カプロラクトン１０５６７．８ｇ（９２．７モル）を４０分かけて滴下した。滴下終了後、１５０℃で３時間反応を続けて合成を終了し、触媒を吸着剤処理により除去して、反応物を得た。得られた反応物を分析したところ、グリセリン１モルにオキシカプロイル単位が９０モル付加しており、数平均分子量１０３００のポリエステル重合体であった。得られたポリエステル重合体１０３０ｇ（０．１モル）及び水酸化カリウム８ｇをオートクレーブに仕込み、窒素ガスでパージ後、１２０℃に加温し、エチレンオキサイド１０２０．８ｇ（２３．２モル）を圧入して、反応させた。１時間の熟成反応後、触媒を吸着剤処理により除去し、反応物を得た。得られた反応物を分析したところ、オキシエチレン単位／オキシカプロイル単位＝７５／３０（モル％）の共重合比率であり、数平均分子量２０３００のポリエーテルポリエステルブロック共重合体（Ｋ−９）であった。
【００８９】
・アシル化ポリエーテルポリエステルブロック共重合体（Ｋ−７）の合成
前記のポリエーテルポリエステルブロック共重合体（Ｋ−３）２１１０ｇ（０．１モル）、ステアリン酸８８．０ｇ（０．３１モル）及びパラトルエンスルホン酸１水和物８ｇをフラスコに仕込み、窒素ガス気流下で温度を１２０〜１３０℃にし、同温度で２時間反応させた後、減圧下に１２０℃で副生する水を除去して、生成物を得た。得られた生成物は、ポリエーテルポリエステルブロック共重合体（Ｋ−３）の１分子にステアロイル基が３個導入された、数平均分子量２１９００のアシル化ポリエーテルポリエステルブロック共重合体（Ｋ−７）であった。
【００９０】
・アシル化ポリエーテルポリエステルブロック共重合体（Ｋ−８）の合成
アシル化ポリエーテルポリエステルブロック共重合体（Ｋ−７）の場合と同様にして、アシル化ポリエーテルポリエステルブロック共重合体（Ｋ−８）を得た。
【００９１】
・ポリエーテルポリエステルブロック共重合体（Ｋ−１０）の合成
４０重量％グルコン酸水溶液４９０ｇ（１モル）及び水酸化カリウム２８ｇをオートクレーブに仕込み、窒素ガスでパージ後、８５℃に加温し、エチレンオキサイド１１０００ｇ（２５０モル）を圧入して、反応させた。１時間の熟成反応後、触媒を吸着剤処理により除去し、水を減圧留去して、反応物を得た。得られた反応物を分析したところ、グルコン酸１モルに対してオキシエチレン単位が２４０モル付加した、水酸基価３１．９、数平均分子量１１０００のポリエーテル化合物であった。得られたポリエーテル化合物１１００ｇ（０．１モル）及びテトラブチルチタネート２．５ｇをフラスコに仕込み、窒素ガス気流下で撹拌しながら１５０℃に加温した。１４０〜１５０℃に温度を保ち、ε−カプロラクトン２７９０ｇ（２４．５モル）を２０分かけて滴下した。滴下終了後、１５０℃で３時間反応を続けて合成を終了し、反応物を得た。得られた反応物を分析したところ、オキシエチレン単位／オキシカプロイル単位＝４０／４０（モル％）の共重合比率であり、数平均分子量３８３００のポリエーテルポリエステルブロック共重合体（Ｋ−１０）であった。
【００９２】
・ポリエーテルポリエステルブロック共重合体（Ｋ−１１）の合成
トリエタノールアミン１４９ｇ（１モル）及び水酸化カリウム１３ｇをオートクレーブに仕込み、窒素ガスでパージ後、１２０℃に加温し、エチレンオキサイド５３８６ｇ（１２２．４モル）を圧入して、反応させた。１時間の熟成反応後、触媒を吸着剤処理により除去し、反応物を得た。得られた反応物を分析したところ、トリエタノールアミン１モルに対してオキシエチレン単位が１２０モル付加した、水酸基価３１．５、数平均分子量５５００のポリエーテル化合物であった。得られたポリエーテル化合物５５０ｇ（０．１モル）及びテトラブチルチタネート２．５ｇをフラスコに仕込み、窒素ガス気流下で撹拌しながら１５０℃に加温した。１４０〜１５０℃に温度を保ち、ε−カプロラクトン１３８０ｇ（１２．１モル）を２０分かけて滴下した。滴下終了後、１５０℃で３時間反応を続けて合成を終了し、反応物を得た。得られた反応物を分析したところ、オキシエチレン単位／オキシカプロイル単位＝４０／４０（モル％）の共重合比率であり、数平均分子量１９２００のポリエーテルポリエステルブロック共重合体（Ｋ−１１）であった。
【００９３】
・ポリエーテルポリエステルブロック共重合体（Ｋ−１２）の合成
Ｎ，Ｎ，Ｎ’，Ｎ’−テトラ（２−ヒドロキシプロピル）−エチレンジアミン２９２ｇ（１モル）及び水酸化カリウム１３ｇをオートクレーブに仕込み、窒素ガスでパージ後、１２０℃に加温し、エチレンオキサイド７１８０ｇ（１６３．２モル）を圧入して、反応させた。１時間の熟成反応後、触媒を吸着剤処理により除去し、反応物を得た。得られた反応物を分析したところ、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラ（２−ヒドロキシプロピル）−エチレンジアミン１モルに対してオキシエチレン単位が１６０モル付加した、水酸基価３１．０、数平均分子量７５００のポリエーテル化合物であった。得られたポリエーテル化合物７５０ｇ（０．１モル）及びテトラブチルチタネート５．２ｇをフラスコに仕込み、窒素ガス気流下で撹拌しながら１５０℃に加温した。１４０〜１５０℃に温度を保ち、ε−カプロラクトン１８５０ｇ（１６．２モル）を２０分かけて滴下した。滴下終了後、１５０℃で３時間反応を続けて合成を終了し、反応物を得た。得られた反応物を分析したところ、オキシエチレン単位／オキシカプロイル単位＝４０／４０（モル％）の共重合比率であり、数平均分子量２６１００のポリエーテルポリエステルブロック共重合体（Ｋ−１２）であった。以上で合成した各ポリエーテルポリエステル共重合体等の内容を表２にまとめて示した。
【００９４】
【表２】

【００９５】
表２において、
ポリエーテルブロックを構成するオキシアルキレン単位の繰り返し数：脂肪族ヒドロキシ化合物の水酸基１個当たりの繰り返し数
ＥＯ：オキシエチレン単位
ＰＯ：オキシプロピレン単位
＊１：Ｎ，Ｎ，Ｎ’，Ｎ’−テトラ（２−ヒドロキシプロピル）−エチレンジアミン
＊２：ステアロイル基／Ｈ＝３／０
＊３：ステアロイル基／Ｈ＝３／１
【００９６】
試験区分３（処理剤の水性液の調製）
・処理剤（Ｔ−１）の１０重量％水性液の調製
試験区分１で合成したポリエーテル化合物（Ｈ−１）５０ｇとポリグリセリン脂肪酸エステル（Ｊ−１）５０ｇとを混合、融解した後、これに９０℃の熱水９００ｇを加え、激しく撹拌して分散液とし、更に２５０kg/cm²の圧力でホモジナイザー処理して、処理剤（Ｔ−１）の１０重量％水性液を得た。
【００９７】
・処理剤（Ｔ−２）〜（Ｔ−６）及び（Ｒ−１）〜（Ｒ−１３）の１０重量％水性液の調製
処理剤（Ｔ−１）の１０重量％水性液の場合と同様にして、処理剤（Ｔ−２）〜（Ｔ−６）及び（Ｒ−１）〜（Ｒ−１３）の１０重量％水性液を得た。
【００９８】
・処理剤（Ｔ−７）の１０重量％水性液の調製
試験区分１で合成したポリエーテル化合物（Ｈ−１）３０ｇとポリグリセリン脂肪酸エステル（Ｊ−１）３０ｇと試験区分２で合成したポリエーテルポリエステルブロック共重合体（Ｋ−１）４０ｇとを混合、融解した後、これに９０℃の熱水９００ｇを加え、激しく撹拌して分散液とし、更に２５０kg/cm²の圧力でホモジナイザー処理して、処理剤（Ｔ−７）の１０重量％水性液を得た。
【００９９】
・処理剤（Ｔ−８）〜（Ｔ−１８）の１０重量％水性液の調製
処理剤（Ｔ−７）の１０重量％水性液の場合と同様にして、処理剤（Ｔ−８）〜（Ｔ−１８）の１０重量％水性液を得た。
【０１００】
・処理剤（Ｔ−１９）の１０重量％水性液の調製
試験区分１で合成したポリエーテル化合物（Ｈ−１）２７ｇとポリグリセリン脂肪酸エステル（Ｊ−２）２７ｇと試験区分２で合成したポリエーテルポリエステルブロック共重合体（Ｋ−１）２３ｇとポリオキシアルキレン変性ポリオルガノシロキサン（Ｌ−１）１９ｇと界面活性剤混合物（Ｅ−１）｛グリセリンモノラウリン酸エステル／ポリオキシエチレン（オキシエチレン単位の数が２０、ｎ＝２０とする）ソルビタンモノステアリン酸エステル／ラウリルスルホン酸ナトリウム＝３０／３０／４０（重量比）の混合物｝４ｇを混合、融解した後、これに９０℃の熱水９４５ｇを加え、激しく撹拌して分散液とし、更に２５０kg/cm²の圧力でホモジナイザー処理して、処理剤（Ｔ−１９）の１０重量％水性液を得た。
【０１０１】
・処理剤（Ｔ−２０）〜（Ｔ−２２）の１０重量％水性液の調製
処理剤（Ｔ−１９）の１０重量％水性液の場合と同様にして、処理剤（Ｔ−２０）〜（Ｔ−２２）の１０重量％水性液を得た。
【０１０２】
各処理剤の水性液の調製に用いたポリグリセリン脂肪酸エステルの内容を表３にまとめて示し、またポリオキシアルキレン変性ポリオルガノシロキサンの内容を表４にまとめて示した。そして、調製した各水性液において、水を除いた各処理剤の内容を表５及び表６にまとめて示した。
【０１０３】
【表３】

【０１０４】
表３において、
エステル化率：ポリグリセリンの全水酸基のうちでエステル化した水酸基の割合（モル％）
【０１０５】
【表４】

【０１０６】
表４において、
＊４：ポリオキシアルキレン変性基の含有割合（重量％）
ＰＯＡ−１：Ｒ⁴−Ａ²−Ｏ−Ｒ⁵で示されるポリオキシアルキレン変性基において、Ｒ⁴がトリメチレン基、Ｒ⁵がメチル基、Ａ²がオキシエチレン単位の繰り返し数が４５のポリオキシアルキレン基である場合のポリオキシアルキレン変性基
ＰＯＡ−２：Ｒ⁴−Ａ²−Ｏ−Ｒ⁵で示されるポリオキシアルキレン変性基において、Ｒ⁴がトリメチレン基、Ｒ⁵が水素、Ａ²がオキシエチレン単位の繰り返し数が２５のポリオキシアルキレン基である場合のポリオキシアルキレン変性基
ＰＯＡ−３：Ｒ⁴−Ａ²−Ｏ−Ｒ⁵で示されるポリオキシアルキレン変性基において、Ｒ⁴がトリメチレン基、Ｒ⁵が水素、Ａ²がオキシエチレン単位の繰り返し数が３０及びオキシプロピレン単位の繰り返し数が２０から成るポリオキシアルキレン基である場合のポリオキシアルキレン変性基
【０１０７】
【表５】

【０１０８】
【表６】

【０１０９】
表５及び表６において、
Ｅ−１：グリセリンモノラウリン酸エステル／ポリオキシエチレン（１５モル）ソルビタンモノステアリン酸エステル／ラウリルスルホン酸ナトリウム＝３０／３０／４０（重量比）の割合の界面活性剤混合物
Ｅ−２：グリセリンモノラウリン酸エステル／ポリオキシエチレン（１５モル）ソルビタンモノステアリン酸エステル／ポリオキシエチレン（５モル）ラウリルエーテル硫酸エステルナトリウム＝３０／３０／４０（重量比）の割合の界面活性剤混合物
Ｅ−３：グリセリンモノラウリン酸エステル／ポリオキシエチレン（１５モル）ソルビタンモノステアリン酸エステル／ポリオキシエチレン（８モル）セチルエーテルリン酸エステルカリウム＝３０／３０／４０（重量比）の割合の界面活性剤混合物
Ｅ−４：グリセリンモノラウリン酸エステル／ステアリン酸ジエタノールアミド／ベヘニン酸アミドプロピルジメチルエチルアンモニウムエトサルフェート＝４０／３０／３０（重量比）の割合の界面活性剤混合物
割合：重量％
比：重量比
【０１１０】
試験区分４（乾式法による不織布製造用ポリオレフィン系繊維への処理剤の付着とその評価）
・乾式法による不織布製造用ポリオレフィン系繊維への処理剤の付着
表５又は表６に記載した水性液を水で希釈して浴濃度を目標付着量となるようにした処理浴（浴温２５℃、浴比１：３０）を準備し、この処理浴に、鞘部がポリエチレンであり、芯部がポリエステルであるポリオレフィン系複合繊維綿（２．０デニール×５１mmカット長）を５分間浸漬して、絞り率５０重量％で遠心脱水した後、６０℃×６０分間送風乾燥して下記評価用の処理綿とした。尚、処理綿への処理剤付着量は、該処理綿をソックスレー抽出器を用いてメタノール／ベンゼン（５０／５０容量比）混合溶剤で抽出することにより測定した。評価結果及び測定結果を表７及び表８にまとめて示した。
【０１１１】
・スカム及びフライの評価
上記で得た処理綿２０００ｇを２５℃×６０％ＲＨの温湿度で２４時間調湿し、同条件下に、開繊機で開繊した後、小型ローラーカード（１山タイプ）を通してカードウェッブを調製した。スカムをフライコムの汚れについて下記の評価基準で評価し、またフライを小型ローラーカードの側面に黒色のスクリーンを立て下記の評価基準で評価した。尚、スカム及びフライが少ない程、カード通過性が良く、操業性が良い。
【０１１２】
・・スカムの評価基準
◎：針布にスカムが全く認められない
○：針布に僅かにスカムが認められる
△：針布にやや多くのスカムが認められる
×：針布にスカムが堆積し、掃除をする必要がある
【０１１３】
・・フライの評価基準
◎：フライが全く認められない
○：フライが僅かに認められる
△：フライがやや多く認められる
×：フライが多く認められ、掃除をする必要がある
【０１１４】
・カードウェッブの地合いの均一性の評価
スカム及びフライの評価の場合と同じ条件で目付２４ｇ／ｍ²のカードウェッブを調製した。これを用いて下記の評価基準でカードウェッブの地合いの均一性を評価した。
・・カードウェッブの地合いの均一性の評価基準
◎：斑が全くなく、均一である
○：僅かな斑が認められるが、問題にならない
△：斑が少し確認でき、やや問題である
×：広範囲にはっきりと斑が確認でき、製品とならない
【０１１５】
・透水性の評価
上記で得られたカードウェッブから１０cm×１０cmの小片を裁断し、１３０℃のヒータープレートで３０秒間熱処理して透水性評価の試料とした。この試料を２０℃×６０％ＲＨの恒温室内で２４時間調湿した後、水平板上におき、ビューレットを用いて１０mmの高さから０．４mlの水滴を落下させ、その水滴が完全に吸収されてしまうまでに要する時間を測定し、下記の評価基準で評価した。
・・透水性の評価基準
◎：透水までに要する時間が０．５秒未満
○：透水までに要する時間が０．５秒以上〜１秒未満
△：透水までに要する時間が１秒以上〜２秒未満
×：透水までに要する時間が２秒以上
【０１１６】
耐久親水性の評価
上記の透水性評価試料の上に８０mlのイオン交換水を全面に振りかけて吸引、通過させた後、４０℃×９０分間送風乾燥して、再度上記の透水性の評価を行なうという操作を繰り返して、透水性の評価が△になるまでの繰り返し回数を求め、下記の評価基準で評価した。
・・耐久親水性の評価基準
◎：繰り返し回数が１５回以上
○：繰り返し回数が１０〜１４回
△：繰り返し回数が５〜９回
×：繰り返し回数が４回以下
【０１１７】
ウエットバック防止性の評価
市販紙おむつの最外部の不織布素材から１０cm×１０cmの不織布片を切除し、その切除部に上記の透水性評価試料と同様に作製した１０cm×１０cmの小片を取り付けて、ウエットバック防止性評価試料とした。取り付けた小片が上向きになるようにウエットバック防止性評価試料を水平に置き、該小片の中央に両端が開放された内径６cmの円筒を垂直に立て、この円筒に水８０mlを注入し、５分間静置して、紙おむつ内部に水を吸収させた。次に取り付けた小片上に１０cm×１０cmのろ紙を１５枚重ねたものを載せ、更にその上に１０cm×１０cmで２．８kgの錘板を載せて、２分間荷重した後、１５枚重ねたろ紙の総重量を測量し、その重量の増加率を算出して、下記の評価基準で評価した。
・・ウエットバック防止性の評価基準
◎：重量増加率が１％未満
○：重量増加率が１％以上１．３％未満
△：重量増加率が１．３％以上２％未満
×：重量増加率が２％以上
【０１１８】
【表７】

【０１１９】
【表８】

【０１２０】
表７及び表８において、
付着量：ポリオレフィン系複合繊維に対する処理剤の付着量（重量％）
【０１２１】
【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、乾式法による不織布製造用ポリオレフィン系繊維に、そのウエッブ製造工程におけるスカムやフライの発生を抑えて優れたカード通過性を付与し、同時に得られるカードウェッブに優れた地合の均一性、透水性、耐久親水性及びウェットバック防止性を付与することができるという効果がある。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a treatment agent and a treatment method for polyolefin fibers for producing nonwoven fabrics by a dry method. A nonwoven fabric is produced from a polyolefin fiber by a wet method or a dry method. Of these, the present invention particularly relates to an improvement of a treatment agent and a treatment method for polyolefin fibers for producing nonwoven fabrics by a dry method.
[0002]
[Prior art]
Conventionally, as treatment agents for polyolefin fibers for producing nonwoven fabrics by wet or dry methods, 1) polyoxyalkylene-modified organosiloxane (JP-A-1-148879), 2) alkylolamide type compound and polyoxyalkylene-modified organosiloxane 3) Polyglycerin fatty acid ester or a blend thereof with polyoxyalkylene-modified organosiloxane (Japanese Patent Laid-Open No. 2-216265), 4) Polyether polyester block copolymer or Is a blend of this and a polyoxyalkylene-modified organosiloxane (Japanese Patent Laid-Open No. 8-226082), 5) a blend of a polyoxyalkylene-modified organosiloxane and a surfactant having a hydrocarbon group having 28 or more carbon atoms as a hydrophobic group (Japanese Patent Publication 4-1868) has been proposed .
[0003]
However, some of the conventional treatment agents as described above are correspondingly effective when used as treatment agents for polyolefin fibers for producing nonwoven fabrics by a wet method, but they are used for producing nonwoven fabrics by a dry method. When used as a processing agent for polyolefin fibers, it is necessary to suppress the occurrence of scum and fly in the dry nonwoven fabric manufacturing process, especially the web manufacturing process, and to ensure good operability. There is a problem that the effect is insufficient in providing uniformity, water permeability, durable hydrophilicity, and wetback prevention.
[0004]
[Problems to be solved by the invention]
The problem to be solved by the present invention is that, in the case of conventional treatment agents, when they are used as treatment agents for polyolefin fibers for producing nonwoven fabrics by a dry method, scum and fly in the dry nonwoven fabric production process, especially the web production process. Insufficient expression of effects to suppress generation and secure good operability, and to impart good texture uniformity, water permeability, durable hydrophilicity, and wetback prevention to the resulting card web That is the point.
[0005]
[Means for Solving the Problems]
Therefore, the present inventors have studied to solve the above problems, and as a treatment agent for polyolefin fibers for producing nonwoven fabrics by a dry method, a treatment agent containing a specific polyether compound and a specific polyglycerin fatty acid ester is used. Has been found to be correct and suitable.
[0006]
That is, the present invention provides a treatment agent for polyolefin fibers for producing nonwoven fabrics by a dry process characterized by comprising a polyether compound represented by the following formula 1 and the following polyglycerin fatty acid ester (hereinafter simply referred to as treatment). And a treatment method of the polyolefin fiber for producing nonwoven fabric by a dry method (hereinafter simply referred to as a treatment method), characterized in that a predetermined amount of the treatment agent is adhered to a polyolefin fiber for nonwoven fabric production by a dry method.
[0007]
[Formula 1]
R¹-A¹-O-R²
[0008]
In Equation 1,
R¹: An alkyl group having 28 to 60 carbon atoms or an alkanoyl group having 28 to 60 carbon atoms
R²: Hydrogen, alkyl group having 1 to 4 carbon atoms or alkanoyl group having 1 to 4 carbon atoms
A¹: A polyoxyalkylene group composed of repeating oxyalkylene units having 2 or 3 carbon atoms, wherein the number of repeating oxyalkylene units is 5 to 100, and 50 mol% of oxyethylene units as the oxyalkylene units Polyoxyalkylene group having
[0009]
Polyglycerin fatty acid ester: Polyglycerin fatty acid ester obtained by esterification of polyglycerin and fatty acid and / or an ester-forming compound of fatty acid, the degree of condensation of the polyglycerin is 2 to 14, and the fatty acid is Polyglycerin fatty acid ester, which is an aliphatic monocarboxylic acid having 6 to 24 carbon atoms, wherein the ester forming compound of the fatty acid is an ester forming compound of an aliphatic monocarboxylic acid having 6 to 24 carbon atoms
[0010]
The present invention also provides a treatment agent comprising the following polyether polyester block copolymer in addition to the polyether compound and polyglycerin fatty acid ester, and a polyolefin fiber for nonwoven fabric production by a dry method. The present invention relates to a processing method for attaching a predetermined amount.
[0011]
Polyether polyester block copolymer: It is constituted by repeating oxyalkylene units in the molecule by ring-opening polymerization of alkylene oxide having 2 to 4 carbon atoms and ε-caprolactone to 1 to 6-valent aliphatic hydroxy compounds. A polyether polyester block copolymer in which a polyoxyalkylene group and a polyester group composed of repeating oxycaproyl units are formed, wherein the polyoxyalkylene group is 5 to 5 per hydroxyl group of the aliphatic hydroxy compound. It has 200 moles of oxyalkylene units and 40 mole% or more of oxyethylene units as the oxyalkylene units, and the total number of repeats of the oxycaproyl units / the total number of repeats of the oxyalkylene units = 1/1 to 1 / 10 (molar ratio) of poly Chromatography ether polyester block copolymer
[0012]
Furthermore, the present invention provides a polyoxyalkylene group in the molecule in an amount of 5 to 38% by weight in addition to the polyether compound and polyglycerin fatty acid ester, or in addition to these and the polyether polyester block copolymer. And a treatment method comprising adhering a predetermined amount of this treatment agent to a polyolefin fiber for producing nonwoven fabrics by a dry method.
[0013]
In the polyether compound represented by Formula 1, 1) a polyether compound in which one end of a polyoxyalkylene group is blocked with an alkyl group having 28 to 60 carbon atoms and the other end is a hydroxyl group, 2) one end of a polyoxyalkylene group Is a polyether compound blocked with an alkanoyl group having 28 to 60 carbon atoms and the other end is a hydroxyl group, 3) one end of a polyoxyalkylene group is blocked with an alkyl group having 28 to 60 carbon atoms, and the other end has a carbon number of 1 Polyether compound blocked with ˜4 alkyl groups, 4) Poly with one end of a polyoxyalkylene group blocked with an alkanoyl group having 28 to 60 carbon atoms and the other end blocked with an alkyl group having 1 to 4 carbon atoms Ether compound, 5) One end of a polyoxyalkylene group is blocked with an alkyl group having 28 to 60 carbon atoms, and the other end is blocked with an alkanoyl group having 1 to 4 carbon atoms The polyether compound, 6) polyether compounds having one end and other end is blocked with an alkanoyl group having 28 to 60 carbon atoms are blocked by an alkanoyl group having 1-4 carbon atoms of the polyoxyalkylene group and the like.
[0014]
In the polyether compound represented by the formula 1, R that blocks one end of the polyoxyalkylene group¹As: 1) an alkyl group having 28 to 60 carbon atoms such as octacosyl group, triacontyl group, dotriacontyl group, tetratriacontyl group, tetracontyl group, dotetracontyl group, hexatetracontyl group, pentacontyl group, hexacontyl group, etc. 2) Octacosanoyl group, triacontanoyl group, dotriacontanoyl group, tetratriacontanoyl group, tetracontanoyl group, dotetracontanoyl group, hexatetracontanoyl group, pentacontanoyl group, hexacontanoyl group, etc. Examples thereof include an alkanoyl group having 28 to 60 carbon atoms, and an alkyl group having 30 to 40 carbon atoms is particularly preferable.
[0015]
In the polyether compound represented by Formula 1, R constituting the other end of the polyoxyalkylene group²1) hydrogen, 2) methyl group, ethyl group, propyl group, isopropyl group, butyl group and other alkyl groups having 1 to 4 carbon atoms, 3) formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group Examples of the alkanoyl group having 1 to 4 carbon atoms such as hydrogen are preferable.
[0016]
In the polyether compound represented by the formula 1, the oxyalkylene unit constituting the polyoxyalkylene group is an oxyethylene unit or an oxyethylene unit and an oxypropylene unit. % Or more, preferably 70 mol% or more. Such polyoxyalkylene groups include 1) those composed solely of oxyethylene units, and 2) those in which 50 mol% or more of oxyethylene units and 50 mol% or less of oxypropylene units are combined in block form and / or random form. Is comprised of. The number of repeating oxyalkylene units constituting the polyoxyalkylene group is 5 to 100, and preferably 10 to 50.
[0017]
The polyether compound represented by the formula 1 described above can be synthesized by a known synthesis method, for example, a synthesis method described in JP-B-49-14841.
[0018]
The polyglycerin fatty acid ester used together with the polyether compound represented by Formula 1 is a polyglycerin fatty acid ester obtained by esterifying polyglycerin and a fatty acid and / or an ester-forming compound of the fatty acid. Examples of such polyglycerin fatty acid esters include 1) a complete ester in which all hydroxyl groups in polyglycerin are completely esterified, and 2) a partial ester partially esterified among all hydroxyl groups in polyglycerol. The partial ester in which 10 to 85 mol% of the hydroxyl group of the polyglycerol is esterified is preferable, and the partial ester in which 10 to 60 mol% is esterified is more preferable.
[0019]
In the polyglycerin fatty acid ester, the starting polyglycerin can be obtained by a dehydration condensation reaction of glycerin in the presence of a catalyst or a ring-opening addition reaction between glycerin and glycidol. When dehydrating condensation of glycerin in the presence of a catalyst, the resulting polyglycerin contains some cyclic polyglycerin as a by-product. In the present invention, polyglycerin partially containing such cyclic polyglycerin is also a raw material. Can be used as In the present invention, those having a condensation degree of 2 to 14 are used as the above polyglycerol, but those having 3 to 12 are preferably used.
[0020]
In the polyglycerin fatty acid ester, the raw material fatty acid is 1) saturated fat having 6 to 24 carbon atoms such as caproic acid, caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, etc. Group monocarboxylic acids, 2) caproleic acid, myristoleic acid, palmitoleic acid, 9-icosenoic acid, 11-docosenoic acid, erucic acid, etc. Of these, saturated aliphatic monocarboxylic acids having 12 to 22 carbon atoms such as lauric acid, palmitic acid, stearic acid, arachidic acid and behenic acid are preferred.
[0021]
In the polyglycerin fatty acid ester, the ester-forming compound of the starting fatty acid is 1) methyl caproate, methyl caprylate, methyl caprate, methyl laurate, ethyl laurate, methyl palmitate, methyl stearate, ethyl stearate C6-24 saturated aliphatic monocarboxylic acid lower alkyl esters such as methyl arachidate, methyl behenate, and lignocerate, 2) methyl caproleate, methyl myristoleate, methyl palmitate, methyl 9-icosenoate , Lower alkyl esters of unsaturated aliphatic monocarboxylic acids having 6 to 24 carbon atoms such as methyl 11-docosenoate and ethyl erucate, among which methyl laurate, ethyl laurate, methyl palmitate, stearic acid Methyl, steer Ethyl phosphate, methyl arachidic acid, saturated aliphatic monocarboxylic acid lower alkyl esters having a carbon number of 12 to 22 such as methyl behenic acid.
[0022]
The polyglycerol fatty acid ester described above can be synthesized by a known synthesis method, for example, a synthesis method described in JP-A-5-140037 or JP-A-5-140038. Specific examples of such polyglycerol fatty acid esters include diglycerol monolaurate, diglycerol monooleate, tetraglycerol monolaurate, tetraglycerol monostearate, tetraglycerol distearate, hexaglycerol monolaurate, Examples include hexaglycerin monomyristic acid ester, hexaglycerin monostearic acid ester, hexaglyceryl distearic acid ester, hexaglycerin dioleic acid ester, and decaglycerin tristearic acid ester.
[0023]
The treatment agent of the present invention contains the polyether compound represented by the formula 1 as described above and a polyglycerin fatty acid ester. The total content of the polyether compound and the polyglycerin fatty acid ester in the treating agent is usually 30% by weight or more, preferably 40% by weight or more, and more preferably 50% by weight or more. . Although this invention does not specifically limit the content rate of this polyether compound and this polyglycerin fatty acid ester, Inclusion of this polyether compound / this polyglycerin fatty acid ester = 20 / 80-90 / 10 (weight ratio) It is preferable to set it as a ratio, and it is more preferable to set it as a content ratio of 40/60 to 80/20 (weight ratio).
[0024]
For the purpose of further improving the effects of the present invention, it is preferable to use a specific polyether polyester block copolymer in combination with the treatment agent of the present invention. Such a polyether polyester block copolymer includes 1) ring-opening polymerization of alkylene oxide to a 1 to 6-valent aliphatic hydroxy compound to form a polyether block, and then ε-caprolactone at the terminal hydroxyl group of the polyether block A polyether polyester block copolymer in which a polyester block is formed by ring-opening polymerization of 2), and a polyester block is formed by ring-opening polymerization of ε-caprolactone to a 1-6 hexavalent aliphatic hydroxy compound, and then the polyester block Polyether polyester block copolymer in which a polyether block is formed by ring-opening polymerization of alkylene oxide at the terminal hydroxyl group of the block, 3) Polyether block by ring-opening polymerization of alkylene oxide on 1 to 6-valent aliphatic hydroxy compounds And ε-caprolact Polyether polyester block copolymer is formed by connecting alternately and polyester block according to the ring-opening polymerization of are included.
[0025]
Examples of the 1-6 valent aliphatic hydroxy compounds include: a) 1-6 valent aliphatic alcohols, b) 2-6 valent aliphatic alcohols and aliphatic monocarboxylic acids having 6-18 carbon atoms. A partial alcohol ester, c) a hydroxycarboxylic acid having 1 to 5 hydroxyl groups in the molecule, d) an alkanolamine having 1 to 3 hydroxyl groups in the molecule, e) an alkyl having 1 to 18 carbon atoms in the alkyl group Examples include dialkanolamines or dialkyllucanolamines, f) alkoxylated polyamines having 1 to 5 hydroxyl groups in the molecule, and among these, the above-mentioned a) aliphatic alcohols and b) polyhydric alcohol partial esters. preferable.
[0026]
Examples of the 1-6 hexavalent aliphatic alcohols of a) include 1) monovalent aliphatic alcohols such as methanol, ethanol, butanol, 2-ethylhexanol, lauryl alcohol, stearyl alcohol, and benzyl alcohol, 2) ethylene glycol, Examples include 2- to 6-valent aliphatic alcohols such as propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, sorbitol, and pentaerythritol. Aliphatic alcohols are preferred.
[0027]
Examples of the polyhydric alcohol partial ester of b) include 1) a fatty acid monoester of a divalent aliphatic alcohol obtained from, for example, 1 mol of ethylene glycol or butanediol and 1 mol of an aliphatic monocarboxylic acid, and 2) Fatty acid mono- or diester of trihydric aliphatic alcohol or mixed ester thereof obtained from 1 mol of glycerin or trimethylolpropane and 1-2 mol of aliphatic monocarboxylic acid, 3) For example, 1 mol of pentaerythritol and aliphatic Obtained from 1 to 3 mol of monocarboxylic acid, fatty acid mono to triester of tetravalent aliphatic alcohol or mixed ester thereof, 4) For example, obtained from 1 mol of sorbitol and 1 to 5 mol of aliphatic monocarboxylic acid , Fatty acid mono-pentaesters of hexavalent aliphatic alcohols, or mixtures thereof Ether, 5) further include an aliphatic monocarboxylic acid partial esters of sorbitan or sorbite is.
[0028]
The aliphatic monocarboxylic acid used to obtain the polyhydric alcohol partial ester of b) is 1) saturated aliphatic monocarboxylic acid such as hexanoic acid, octanoic acid, lauric acid, stearic acid, and 2) palmitooleic acid. And those having 6 to 18 carbon atoms such as unsaturated aliphatic monocarboxylic acids such as oleic acid.
[0029]
Examples of the hydroxycarboxylic acid having 1 to 5 hydroxyl groups in the molecule c) include 1) monohydroxycarboxylic acids such as glycolic acid, lactic acid, malic acid, hydroxybutyric acid, hydroxystearic acid, and 2) tartaric acid, tetrahydroxyl Examples thereof include di-pentahydroxycarboxylic acid such as acid and gluconic acid.
[0030]
Examples of the alkanolamine having 1 to 3 hydroxyl groups in the molecule d) include 1) monoalkanolamines such as monoethanolamine and monoisopropanolamine, 2) dialkanolamines such as diethanolamine and dipropanolamine, 3) Examples include trialkanolamines such as ethanolamine and triisopropanolamine.
[0031]
Examples of the alkyl dialkanolamine or dialkylalkanolamine having 1 to 18 carbon atoms in e) include 1) dialkylalkanolamines such as diethylethanolamine and dibutylethanolamine, 2) ethyldiethanolamine, butyldiethanolamine, stearyl Examples thereof include alkyl dialkanolamines such as diisopropanolamine.
[0032]
Examples of the alkoxylated polyamine having 1 to 5 hydroxyl groups in the molecule f) include N-2-hydroxyethylaminoethylamine, N, N-di (2-hydroxyethyl) aminopropylamine, N, N, N ′. , N′-tetra (2-hydroxypropyl) -ethylenediamine, N, N-di (2-hydroxypropyl) -N′-2-hydroxypropyl-N ″, N ″ -di (2-hydroxypropyl)- Examples include diethylenetriamine.
[0033]
In the present invention, the oxyalkylene unit forming the polyether block in the polyether polyester block copolymer is an oxyalkylene unit having 2 to 4 carbon atoms such as an oxyethylene group, an oxypropylene group, and an oxybutylene group. The oxyalkylene unit has an oxyethylene unit of 40 mol% or more, preferably 50 mol% or more. Such a polyether block has 1) only composed of oxyethylene units, and 2) 40 mol% or more of oxyethylene units and 60 mol% or less of other oxyalkylene units bonded in a block form and / or a random form. What consists of things is included.
[0034]
In the polyether polyester block copolymer, the number of repeating oxyalkylene units forming the polyether block is 5 to 200 per hydroxyl group contained in the 1 to 6-valent aliphatic hydroxy compound. Is preferable. This is for imparting excellent durability and hydrophilicity to the polyolefin fiber for producing a nonwoven fabric by a dry method.
[0035]
In the present invention, the number of repeating oxycaproyl units forming the polyester block in the polyether polyester block copolymer is the total number of repeating oxycaproyl units / the total number of repeating oxyalkylene units = 1/1 to 1/10 ( Molar ratio), preferably a ratio of 1 / 1.5-1 to 1/4 (molar ratio). This is for imparting excellent durability and hydrophilicity to the polyolefin fiber for producing a nonwoven fabric by a dry method.
[0036]
The polyether polyester block copolymer described above can be synthesized by a known synthesis method. Examples of a method for forming a polyether block in a polyether polyester block copolymer include ethylene oxide, propylene oxide, butylene oxide in a hydroxy compound in the presence of a basic catalyst such as sodium hydroxide or potassium hydroxide as a catalyst. And a method of successively ring-opening polymerization of an alkylene oxide having 2 to 4 carbon atoms such as the above. In addition, as a method for forming a polyester block in a polyether polyester block copolymer, for example, ε-caprolactone is successively opened in a hydroxy compound in the presence of an anion polymerization catalyst, a coordination anion polymerization catalyst, a cation polymerization catalyst, or the like as a catalyst. The method of ring polymerization is mentioned.
[0037]
The polyether polyester block copolymer used in the present invention has a 1 to 6-valent aliphatic hydroxy compound as a starting material, and a polyether block and a polyester block bonded to each other through the hydroxyl group. According to the present invention, as a bonding form of the polyether block and the polyester block, the polyether block is bonded to the hydroxyl group of 1 to 6-valent aliphatic hydroxy compound, and then the polyester block is bonded to the terminal hydroxyl group of the polyether block. Bonded ones are preferred. In this case, the 1-6 valent aliphatic hydroxy compound used as a starting material is a 1-6 valent aliphatic alcohol, or a 2-6 valent aliphatic alcohol and an aliphatic monocarboxylic acid having 6-18 carbon atoms. And polyhydric alcohol partial esters are preferred, and among those described above, those having 2 to 4 valences are more preferred.
[0038]
In the above case, the polyether polyester block copolymer has a hydroxyl group based on the polyoxycaproyl group constituting the polyester block as a terminal group. In the present invention, an acylated polyether polyester block copolymer obtained by reacting an acylating agent with a terminal hydroxyl group of such a polyether polyester block copolymer may be used together with or in place of the polyether polyester block copolymer. it can.
[0039]
The acylated polyether polyester block copolymer includes 1) a fully acylated product in which all of the terminal hydroxyl groups of the polyether polyester block copolymer are acylated with an acylating agent, and 2) the end of the polyether polyester block copolymer. A partially acylated product obtained by acylating a part of the hydroxyl group with an acylating agent is included. Acyl groups formed by acylation include 1) carbon number such as acetyl group, propanoyl group, butanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, hexadecanoyl group and octadecanoyl group Examples thereof include alkanoyl groups having 2 to 18 carbon atoms, 2) alkenoyl groups having 16 to 22 carbon atoms such as hexadecenoyl group, eicosenoyl group, and octadecenoyl group.
[0040]
When the polyether polyester block copolymer as described above is used in combination, the treating agent of the present invention is the polyether based on the total amount of the polyether compound represented by formula 1 and the polyglycerin fatty acid ester. What is contained in a ratio of the total amount of the compound and the polyglycerol fatty acid ester / the polyether polyester block copolymer = 40/60 to 90/10 (weight ratio), preferably 50/50 to 80/20 (weight ratio) ) Is more preferable.
[0041]
For the purpose of further improving the effects of the present invention, it is preferable to use a polyoxyalkylene-modified polyorganosiloxane having a polyoxyalkylene group in the molecule in a proportion of 5 to 38% by weight in the treatment agent of the present invention. Among these, it is more preferable to use a polyoxyalkylene-modified polyorganosiloxane represented by the following formula 2 together.
[0042]
[Formula 2]

[0043]
In Equation 2,
Y¹, Y², Y^Three: Methyl group or R^Four-A²-O-R^FiveAt least one of the polyoxyalkylene-modified groups (R)^Four: C2-C5 alkylene group, R^Five: Hydrogen or alkyl group having 1 to 12 carbon atoms, A²: A polyoxyalkylene group composed of repeating oxyalkylene units having 2 or 3 carbon atoms, wherein the number of repeating oxyalkylene units is 10 to 100, and 50 mol% of oxyethylene units as the oxyalkylene units Polyoxyalkylene group having
R^Three: C2-C5 alkyl group or phenyl group
p, q: p is an integer of 7 to 150, q is an integer of 0 to 20, and 7 ≦ p + q ≦ 150
r: integer from 0 to 10
[0044]
The polyoxyalkylene-modified polyorganosiloxane represented by Formula 2 is a linear polyorganosiloxane containing dimethylsiloxane units and siloxane units having a polyoxyalkylene-modified group as essential structural units. Examples of the siloxane unit having a polyoxyalkylene-modified group include a divalent methyl-polyoxyalkylene-modified siloxane unit surrounded by r present in the polyorganosiloxane chain in Formula 2, and a monovalent dimethyl-polysiloxane as a terminal group. Examples of the polyoxyalkylene-modified siloxane unit include those having a divalent methyl polyoxyalkylene-modified siloxane unit surrounded by r. Thus, when it has a polyoxyalkylene modified group in a polyorganosiloxane chain instead of a terminal, it is set as 1 or 2-10 repeating units as a siloxane unit containing this. In this case, Y in Formula 2 is used as the end group.¹, Y²Is a trimethylsiloxane unit corresponding to a methyl group or Y¹, Y²There is no problem even if the dimethyl / polyoxyalkylene-modified siloxane unit is a polyoxyalkylene-modified group, but a trimethylsiloxane unit is preferred.
[0045]
In the polyoxyalkylene-modified polyorganosiloxane represented by the formula 2, the siloxane unit having no polyoxyalkylene-modified group that forms the polyorganosiloxane main chain is represented by q in addition to the dimethylsiloxane unit surrounded by p. It can contain divalent organosiloxane units. Examples of the divalent organosiloxane unit enclosed by q include a methylethylsiloxane unit, a methylpropylsiloxane unit, a methylhexylsiloxane unit, and a methylphenylsiloxane unit. The number of repeating siloxane units having no polyoxyalkylene modifying group is such that p is 7 to 150, q is 0 to 20, and the sum of p and q is 7 to 150, but only from dimethylsiloxane units. Preferably (when q in Formula 2 is 0) and having 10 to 70 repetitions.
[0046]
R in Formula 2^Four-A²-O-R^FiveIn the polyoxyalkylene-modified group represented by^FourIs an alkylene group linking a silicon atom of a siloxane unit and a polyoxyalkylene group, and is an alkylene group having 2 to 5 carbon atoms such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, An ethylene group and a trimethylene group are preferable. Also R^FiveIs a terminal group of a polyoxyalkylene group, such as hydrogen, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. preferable. A²The oxyalkylene unit constituting is an oxyethylene unit or an oxyethylene unit and an oxypropylene unit, and the oxyalkylene unit has an oxyethylene unit of 50 mol% or more, preferably 70 mol% or more. Such polyoxyalkylene groups include 1) those composed solely of oxyethylene units, and 2) those in which 50 mol% or more of oxyethylene units and 50 mol% or less of oxypropylene units are combined in block form and / or random form. Is comprised of. The number of repeating oxyalkylene units constituting the polyoxyalkylene group is 10 to 100, but preferably 20 to 70.
[0047]
The polyoxyalkylene-modified polyorganosiloxane described above can be synthesized by a known synthesis method, for example, a synthesis method described in US Reissue Patent No. 25727. When the polyoxyalkylene-modified polyorganosiloxane is used in combination, the treating agent of the present invention is based on the total amount of the polyether compound, polyglycerin fatty acid ester and polyether polyester block copolymer represented by the above-described formula 1. The total amount of the polyether compound, the polyglycerin fatty acid ester and the polyether polyester block copolymer / the polyoxyalkylene-modified polyorganosiloxane = 40/60 to 95/5 (weight ratio) What contains is preferable, and what is contained in the ratio of 60 / 40-90 / 10 (weight ratio) is still more preferable.
[0048]
In addition to the polyether compound, polyglycerin fatty acid ester, polyether ester block copolymer, and polyoxyalkylene-modified polyorganosiloxane represented by the formula 1 described above, the treating agent of the present invention is suitably used for other interfaces. An activator can be used in combination. Known surfactants can be used as such surfactants. Examples thereof include 1) polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene alkyl esters, polyoxyalkylene castor oils in which all oxyalkylene groups consist of oxyethylene groups and / or oxypropylene groups, Nonionic surfactant having polyoxyalkylene group such as polyoxyalkylene hydrogenated castor oil, 2) Polyhydric alcohol partial ester type such as sorbitan monolaurate, sorbitan trioleate, glycerin monolaurate, diglycerin dilaurate 3) All of the nonionic surfactants, 3) long-chain alkyl group-containing polyoxyalkylene alkylamino ethers, wherein the oxyalkylene group comprises an oxyethylene group and / or an oxypropylene group, Nitrogen-containing nonionic surfactant having a polyoxyalkylene group, such as a polyether polyamine having an oxyalkylene amino ether moiety and a fatty acid amide compound having a polyoxyalkylene group, 4) an aliphatic sulfate salt, an aliphatic sulfonate salt, Anionic interfaces such as aliphatic phosphate salt, aliphatic carboxylate salt, aliphatic sulfate salt having polyoxyalkylene group, aliphatic sulfonate salt having polyoxyalkylene group, aliphatic phosphate salt having polyoxyalkylene group Activating agent, 5) acid neutralized product of long chain alkylamine, acid neutralized product of polyoxyalkylene alkylamino ether, acid neutralized product of fatty acid amide compound having polyoxyalkylene group, cross-linked polyoxyalkylene polyamine polyamide Acid neutralized products, etc. 6) Cationic surfactants having a min salt moiety, 6) Quaternized moieties of fatty acid amide compounds having a polyoxyalkylene group, tetraalkyl ammonium salts, alkyl imidazolinium salts, tetraalkyl phosphonium salts, etc. And cationic surfactants, 7) amphoteric surfactants such as long-chain alkyldimethylbetaines, alkylimidazoline betaine compounds, and long-chain alkylamino acids.
[0049]
When the treatment agent of the present invention is attached to polyolefin fibers for producing nonwoven fabrics by a dry method, the treatment agent is immersed in the spinning process, stretching process, and further in each process after stretching. It can be attached by an oil supply method such as a roller oil supply method or a guide oil supply method using a metering pump, but it is preferably attached by an immersion method. Although the adhesion amount of a processing agent shall be 0.05-5 weight% with respect to polyolefin fiber, it is preferable to set it as 0.1-2.5 weight%. This is for imparting excellent card passability as desired to the polyolefin-based fiber and imparting excellent uniformity of formation, water permeability, durable hydrophilicity and wetback prevention to the resulting card web.
[0050]
The treatment agent of the present invention is preferably attached to the polyolefin fiber as the aqueous liquid. A known mechanical emulsification method using a homomixer or a homogenizer can be applied to the preparation of such an aqueous liquid. The concentration of the treatment agent in the prepared aqueous liquid is usually 1 to 30% by weight, but is preferably 5 to 15% by weight.
[0051]
Polyolefin fibers to which the treatment agent of the present invention is applied include polyethylene fibers, polypropylene fibers, polybutene fibers, core-sheath composite fibers, and sheath fibers made of polyolefin fibers, for example, the sheath portions are polyethylene fibers. A certain polyethylene / polypropylene composite fiber, polyethylene / polyester composite fiber, etc. are mentioned.
[0052]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the processing agent according to the present invention include the following 1) to 22).
1) A treating agent comprising 50% by weight of the following polyether compound (H-1) and 50% by weight of the following polyglycerol fatty acid ester (J-1).
Polyether compound (H-1): R in formula 1¹Is a triacontyl group, R²Is hydrogen, A¹Polyether compound in which is a polyoxyethylene group consisting of repeating 10 moles of oxyethylene units
Polyglycerin fatty acid ester (J-1): polyglycerin fatty acid ester obtained by esterification of tetraglycerin having a condensation degree of 4 and stearic acid to esterify 16.7 mol% of the hydroxyl group of the tetraglycerin
[0053]
2) A treating agent comprising 70% by weight of the following polyether compound (H-2) and 30% by weight of the following polyglycerol fatty acid ester (J-2).
Polyether compound (H-2): R in formula 1¹Is tetracontyl group, R²Is hydrogen, A¹Is a polyoxyethylene group consisting of repeating 30 moles of oxyethylene units
Polyglycerin fatty acid ester (J-2): polyglycerin fatty acid ester obtained by esterifying hexaglycerin having a condensation degree of 6 and myristic acid and esterifying 12.5 mol% of the hydroxyl group of the hexaglycerin
[0054]
3) A treating agent comprising 80% by weight of the following polyether compound (H-3) and 20% by weight of the following polyglycerol fatty acid ester (J-3).
Polyether compound (H-3): R in formula 1¹Is triacontanoyl group, R²Is hydrogen, A¹Compound in which is a polyoxyethylene polyoxypropylene group consisting of a repetition of 24 mol oxyethylene units and 16 mol oxypropylene units
Polyglycerin fatty acid ester (J-3): polyglycerin fatty acid ester obtained by esterification of tetraglycerin having a condensation degree of 4 and stearic acid to esterify 33.3 mol% of the hydroxyl group of the tetraglycerin
[0055]
4) A treating agent comprising 30% by weight of the following polyether compound (H-4) and 70% by weight of the following polyglycerol fatty acid ester (J-4).
Polyether compound (H-4): R in formula 1¹Is tetracontanoyl group, R²Is hydrogen, A¹Is a polyether compound in which is a polyoxyethylene group consisting of repeating 25 mol oxyethylene units
Polyglycerin fatty acid ester (J-4): polyglycerin fatty acid ester obtained by esterifying decaglycerin having a condensation degree of 10 and stearic acid to esterify 25.0 mol% of the hydroxyl group of the decaglycerin
[0056]
5) A treating agent comprising 60% by weight of the following polyether compound (H-5) and 40% by weight of the following polyglycerol fatty acid ester (J-5).
Polyether compound (H-5): R in formula 1¹Is a pentacontyl group, R²Is a methyl group, A¹Is a polyoxyethylene group consisting of repeating 30 moles of oxyethylene units
Polyglycerin fatty acid ester (J-5): polyglycerin fatty acid ester obtained by esterification of tetraglycerin having a degree of condensation of 4 and myristic acid to esterify 16.7 mol% of the hydroxyl group of the tetraglycerin
[0057]
6) A treating agent comprising 60% by weight of the following polyether compound (H-6) and 40% by weight of the following polyglycerol fatty acid ester (J-6).
Polyether compound (H-6): R in formula 1¹Is a triacontyl group, R²Is an acetyl group, A¹Is a polyoxyethylene group consisting of repeating 20 moles of oxyethylene units
Polyglycerin fatty acid ester (J-6): polyglycerin fatty acid ester obtained by esterifying hexaglycerin having a condensation degree of 6 and oleic acid to esterify 50.0 mol% of the hydroxyl group of the hexaglycerin
[0058]
7) 30% by weight of the polyether compound (H-1), 30% by weight of the polyglycerol fatty acid ester (J-1), and 40% by weight of the following polyether polyester block copolymer (K-1) A treating agent comprising.
Polyether polyester block copolymer (K-1): A mixture of ethylene oxide and propylene oxide is subjected to ring opening polymerization to ethylene glycol to form a polyether block, and then ε-caprolactone is subjected to ring opening polymerization to form a polyester block. The formed polyether block has 75 moles of oxyalkylene units per hydroxyl group of ethylene glycol, 67 mole% of oxyethylene units as oxyalkylene units, and the total number of repeating oxycaproyl units / oxyalkylene units Polyether polyester block copolymer having a total number of repetitions of 1/3 (molar ratio)
[0059]
8) 49% by weight of the polyether compound (H-1), 21% by weight of the polyglycerol fatty acid ester (J-1), and 30% by weight of the following polyether polyester block copolymer (K-2) A treating agent comprising.
Polyether polyester block copolymer (K-2): Polyether obtained by ring-opening polymerization of ethylene oxide to ethylene glycol to form a polyether block and then ring-opening polymerization of ε-caprolactone to form a polyester block The block has 75 moles of oxyalkylene units per hydroxyl group of ethylene glycol and 100 mole% of oxyethylene units as oxyalkylene units, and the total number of repeating oxycaproyl units / the total number of repeating oxyalkylene units = 1 / Polyether polyester block copolymer having a ratio of 3 (molar ratio)
[0060]
9) 35% by weight of the polyether compound (H-2), 35% by weight of the polyglycerol fatty acid ester (J-2), and 30% by weight of the following polyether polyester block copolymer (K-3) A treating agent comprising.
Polyether polyester block copolymer (K-3): ring-opening polymerization of propylene oxide on glycerin, ring-opening polymerization of ethylene oxide to form a polyether block, and then ring-opening polymerization of ε-caprolactone to form a polyester The polyether block in which the block is formed has 75 moles of oxyalkylene units per hydroxyl group of glycerin and 80 mole% of oxyethylene units as oxyalkylene units, and the total number of repeating oxycaproyl units / oxyalkylene units Polyether polyester block copolymer having a total number of repetitions of 1 / 2.5 (molar ratio)
[0061]
10) 42% by weight of the polyether compound (H-2), 18% by weight of the polyglycerol fatty acid ester (J-1), and 40% by weight of the following polyether polyester block copolymer (K-4) A treating agent comprising.
Polyether polyester block copolymer (K-4): Polyether block in which ethylene oxide is ring-opened and polymerized into glycerin to form a polyether block, and then ε-caprolactone is ring-opened and polymerized to form a polyester block. Has 75 moles of oxyalkylene units per hydroxyl group of glycerin and 100 mole% of oxyethylene units as oxyalkylene units, and the total number of repeating oxycaproyl units / the total number of repeating oxyalkylene units = 1/2. Polyether polyester block copolymer having a ratio of 5 (molar ratio)
[0062]
11) 42% by weight of the polyether compound (H-2), 18% by weight of the polyglycerol fatty acid ester (J-1), and 40% by weight of the following polyether polyester block copolymer (K-5) A treating agent comprising.
Polyether polyester block copolymer (K-5): Pentaerythritol is subjected to ring-opening polymerization of a mixture of ethylene oxide and propylene oxide to form a polyether block, and then ε-caprolactone is subjected to ring-opening polymerization to form a polyester block. The polyether block has 60 moles of oxyalkylene units per hydroxyl group of pentaerythritol, 75 mole% of oxyethylene units as oxyalkylene units, and the total number of repeating oxycaproyl units / total number of oxyalkylene units. Polyether polyester block copolymer having a repeating number of 1/2 (molar ratio)
[0063]
12) 42% by weight of the polyether compound (H-2), 18% by weight of the polyglycerol fatty acid ester (J-1), and 40% by weight of the following polyether polyester block copolymer (K-6) A treating agent comprising.
Polyether polyester block copolymer (K-6): ring-opening polymerization of ethylene oxide to sorbitan monostearate to form a polyether block, and then ring-opening polymerization of ε-caprolactone to form a polyester block. The polyether block has 60 moles of oxyalkylene units per hydroxyl group of sorbitan monostearate and 100 mole% of oxyethylene units as oxyalkylene units, and the total number of repeating oxycaproyl units / all repeating oxyalkylene units Polyether polyester block copolymer having a ratio of number = 1 / 1.5 (molar ratio)
[0064]
13) 42% by weight of the polyether compound (H-1), 18% by weight of the polyglycerol fatty acid ester (J-2), and 40% by weight of the following polyether polyester block copolymer (K-7) A treating agent comprising.
Polyether polyester block copolymer (K-7): Acylated polyether polyester block copolymer obtained by acylating the above polyether polyester block copolymer (K-3) with stearic acid
[0065]
14) 42% by weight of the polyether compound (H-2), 18% by weight of the polyglycerol fatty acid ester (J-1), and 40% by weight of the following polyether polyester block copolymer (K-8) A treating agent comprising.
Polyether polyester block copolymer (K-8): acylated polyether polyester block copolymer obtained by acylating the above polyether polyester block copolymer (K-5) with stearic acid
[0066]
15) 42 wt% of the polyether compound (H-1), 18 wt% of the polyglycerol fatty acid ester (J-2), and 40 wt% of the following polyether polyester block copolymer (K-9) A treating agent comprising.
Polyether polyester block copolymer (K-9): Polyether block formed by ring-opening polymerization of ε-caprolactone to glycerin to form a polyester block, and then ring-opening polymerization of ethylene oxide to form a polyether block Has 75 moles of oxyalkylene units per hydroxyl group of glycerin and 100 mole% of oxyethylene units as oxyalkylene units, and the total number of repeating oxycaproyl units / the total number of repeating oxyalkylene units = 1/2. Polyether polyester block copolymer having a ratio of 5 (molar ratio)
[0067]
16) 42% by weight of the polyether compound (H-2), 18% by weight of the polyglycerol fatty acid ester (J-1), and 40% by weight of the following polyether polyester block copolymer (K-10) A treating agent comprising.
Polyether polyester block copolymer (K-10): polyether obtained by ring-opening polymerization of ethylene oxide to gluconic acid to form a polyether block, and then ring-opening polymerization of ε-caprolactone to form a polyester block The block has 40 moles of oxyalkylene units per hydroxyl group of gluconic acid, 100 mole% of oxyethylene units as oxyalkylene units, and the total number of repeating oxycaproyl units / the total number of repeating oxyalkylene units = 1 / Polyether polyester block copolymer having a ratio of 1 (molar ratio)
[0068]
17) 42% by weight of the polyether compound (H-1), 18% by weight of the polyglycerol fatty acid ester (J-2), and 40% by weight of the following polyether polyester block copolymer (K-11) A treating agent comprising.
Polyether polyester block copolymer (K-11): Polyethanol obtained by ring-opening polymerization of ethylene oxide to triethanolamine to form a polyether block and then ring-opening polymerization of ε-caprolactone to form a polyester block. The ether block has 40 moles of oxyalkylene units per hydroxyl group of triethanolamine and 100 mole% of oxyethylene units as oxyalkylene units, and the total number of repeating oxycaproyl units / the total number of repeating oxyalkylene units = Polyether polyester block copolymer having a 1/1 (molar ratio) ratio
[0069]
18) 42% by weight of the polyether compound (H-2), 18% by weight of the polyglycerol fatty acid ester (J-1), and 40% by weight of the following polyether polyester block copolymer (K-12) A treating agent comprising.
Polyether polyester block copolymer (K-12): N, N, N ′, N′-tetra (2-hydroxypropyl) -ethylenediamine is subjected to ring-opening polymerization of ethylene oxide to form a polyether block, and then ε A ring-opening polymerization of caprolactone to form a polyester block, the polyether block contains 40 moles of oxyalkylene units per hydroxyl group of N, N, N ′, N′-tetra (2-hydroxypropyl) -ethylenediamine Polyether polyester block copolymer having 100 mol% of oxyethylene units as oxyalkylene units and having a total number of repeating oxycaproyl units / total number of repeating oxyalkylene units = 1/1 (molar ratio)
[0070]
19) 27% by weight of the polyether compound (H-1), 27% by weight of the polyglycerol fatty acid ester (J-2), 23% by weight of the polyether polyester block copolymer (K-1), A processing agent comprising 19% by weight of polyoxyalkylene-modified polyorganosiloxane (L-1) and 4% by weight of the following surfactant mixture (E-1).
Polyoxyalkylene-modified polyorganosiloxane (L-1): Y in formula 2¹, Y²Is a methyl group, p is 120, q is 0, r is 2, Y^ThreeIs R^Four-A²-O-R^FiveA polyoxyalkylene-modified group represented by:^FourIs a trimethylene group, R^FiveIs a methyl group, A²Polyoxyalkylene-modified polyorganosiloxane in which is a polyoxyethylene group consisting of repeating 45 moles of oxyethylene units
Surfactant mixture (E-1): Mixture of glycerin monolaurate / polyoxyethylene (15 mol) sorbitan monostearate / sodium lauryl sulfonate = 30/30/40 (weight ratio)
[0071]
20) 27% by weight of the polyether compound (H-2), 27% by weight of the polyglycerol fatty acid ester (J-1), 23% by weight of the polyether polyester block copolymer (K-3), A treating agent comprising 19% by weight of polyoxyalkylene-modified polyorganosiloxane (L-2) and 4% by weight of the following surfactant mixture (E-2).
Polyoxyalkylene-modified polyorganosiloxane (L-2): Y in formula 2¹, Y²Is a methyl group, p is 80, q is 0, r is 2, Y^ThreeIs R^Four-A²-O-R^FiveA polyoxyalkylene-modified group represented by:^FourIs a trimethylene group, R^FiveIs hydrogen, A²Polyoxyalkylene modified polyorganosiloxane in which is a polyoxyethylene group consisting of repeating 25 moles of oxyethylene units
Surfactant mixture (E-2): glycerin monolaurate / polyoxyethylene (15 mol) sorbitan monostearate / polyoxyethylene (5 mol) sodium lauryl ether sulfate = 30/30/40 (weight ratio) Mixture of proportions
[0072]
21) 38% by weight of the polyether compound (H-1), 16% by weight of the polyglycerol fatty acid ester (J-2), 23% by weight of the polyether polyester block copolymer (K-5), A treating agent comprising 19% by weight of polyoxyalkylene-modified polyorganosiloxane (L-3) and 4% by weight of the following surfactant mixture (E-3).
Polyoxyalkylene-modified polyorganosiloxane (L-3): p in formula 2 is 100, q is 10, r is 0, R^ThreeIs a phenyl group, Y¹, Y²Is R^Four-A²-O-R^FiveA polyoxyalkylene-modified group represented by:^FourIs a trimethylene group, R^FiveIs hydrogen, A²Polyoxyalkylene-modified polyorganosiloxane in which is a polyoxyethylene group composed of repeating 30 mol oxyethylene units and 20 mol oxypropylene units
Surfactant mixture (E-3): glycerin monolaurate / polyoxyethylene (15 mol) sorbitan monostearate / polyoxyethylene (8 mol) potassium cetyl ether phosphate = 30/30/40 (weight ratio) ) Proportion mixture
[0073]
22) 38% by weight of the polyether compound (H-2), 16% by weight of the polyglycerol fatty acid ester (J-1), 23% by weight of the polyether polyester block copolymer (K-1), A treating agent comprising 19% by weight of polyoxyalkylene-modified polyorganosiloxane (L-1) and 4% by weight of the following surfactant mixture (E-4).
Surfactant mixture (E-4): Mixture of glycerin monolaurate / stearic acid diethanolamide / behenic acid amidopropyldimethylethylammonium ethosulphate = 40/30/30 (weight ratio)
[0074]
Moreover, the following 23) is mentioned as embodiment of the processing method which concerns on this invention.
23) 100 g of the treatment agent of any one of 1) to 22) and 900 g of water are vigorously stirred to form a dispersion, and further emulsified by a homogenizer to obtain a 10% by weight aqueous solution of the treatment agent. 1% by weight aqueous solution diluted in 1) is attached by dipping method to 0.35% by weight as a treatment agent for 2.0 denier x 51mm cut polyethylene / polyester composite fiber cotton used for non-woven fabric production by dry method How to make.
[0075]
Hereinafter, examples and the like will be given to make the configuration and effects of the present invention more specific, but the present invention is not limited to these examples.
[0076]
【Example】
Test Category 1 (Synthesis of polyether compounds)
・ Synthesis of polyether compound (H-1)
438 g (1 mol) of triacontyl alcohol and 2 g of potassium hydroxide were charged into an autoclave, purged with nitrogen gas, heated to 120 ° C., and 450 g (10.2 mol) of ethylene oxide was injected to react. After an aging reaction for 1 hour, the catalyst was removed by adsorbent treatment to obtain a reaction product. When the obtained reaction product was analyzed, it was a polyether compound (H-1) having a repeating number of oxyethylene units of 10, a hydroxyl value of 63, and a number average molecular weight of 920 (GPC method, polystyrene conversion, the same applies hereinafter). It was.
[0077]
Synthesis of polyether compounds (H-2) to (H-4) and (h-1) to (h-4)
In the same manner as in the case of the polyether compound (H-1), polyether compounds (H-2) to (H-4) and (h-1) to (h-4) were synthesized.
[0078]
Synthesis of polyether compound (H-5)
After adding 718 g (1 mol) of pentacontyl alcohol to the autoclave and adding 5 g of potassium hydroxide powder as a catalyst, the inside of the autoclave was sufficiently substituted with nitrogen. While stirring, the reaction temperature was maintained at 110 ° C. to 120 ° C., and 1364 g (31 mol) of ethylene oxide was injected to carry out an addition polymerization reaction. Thereafter, the reaction was terminated by aging for 1 hour at the same temperature. The reaction was transferred to a flask and the catalytic potassium hydroxide was neutralized with phosphoric acid. The phosphate was filtered off from the neutralized product to obtain 2080 g of polyoxyalkylene monopentacontyl ether. 2918 g (1 mol) of polyoxyalkylene monopentacontyl ether obtained here and 117 g of 48% potassium hydroxide aqueous solution were charged into an autoclave and dehydrated under reduced pressure at 70 to 100 ° C. with stirring. Thereafter, the reaction temperature was maintained at 100 to 120 ° C., and 53 g (1.05 mol) of methyl chloride was injected until no pressure drop in the autoclave was observed, and an etherification reaction was performed. The potassium chloride by-produced from the reaction product was filtered off to obtain a polyether compound (H-5). When this was analyzed, it was polyoxyalkylene pentacontyl methyl ether in which the polyoxyalkylene group was composed of 30 repeating oxyethylene units.
[0079]
Synthesis of polyether compound (h-5)
A polyether compound (h-5) was synthesized in the same manner as in the case of the polyether compound (H-5).
[0080]
・ Synthesis of polyether compound (H-6)
1318 g (1 mol) of polyoxyalkylene monotriacontyl ether as an intermediate obtained in the same manner as in the synthesis of the polyether compound (H-1), 72 g (1.2 mol) of glacial acetic acid and 6 g of concentrated sulfuric acid as a catalyst. The reaction temperature was adjusted to 100 to 110 ° C. while stirring and dehydration was performed under reduced pressure to carry out an esterification reaction. After completion of the reaction, concentrated sulfuric acid and unreacted acetic acid were neutralized with 35 g of 48% potassium hydroxide while cooling. The product water was then distilled off under reduced pressure. The inorganic salt formed as a by-product was separated by filtration to obtain a polyether compound (H-6). When this was analyzed, it was an acetic ester of polyoxyalkylene monotriacontyl ether in which the polyoxyalkylene group was composed of 20 repeating oxyethylene units. The contents of each polyether compound synthesized above are summarized in Table 1.
[0081]
[Table 1]

[0082]
In Table 1,
EO: Oxyethylene unit
PO: Oxypropylene unit
[0083]
Test category 2 (Synthesis of polyether polyester block copolymer, etc.)
・ Synthesis of polyether polyester block copolymer (K-1)
An autoclave was charged with 62 g (1 mol) of ethylene glycol and 20 g of potassium hydroxide, purged with nitrogen gas and heated to 120 ° C., and 4532 g (103.0 mol) of ethylene oxide and 2992.8 g (51.6 mol) of propylene oxide were heated. ) And the mixture were reacted. After an aging reaction for 1 hour, the catalyst was removed by adsorbent treatment to obtain a reaction product. When the obtained reaction product was analyzed, it was a copolymerization ratio of oxyethylene unit / oxypropylene unit = 50/25 (molar ratio, NMR analysis method, hereinafter the same), hydroxyl value 15.2 and number average molecular weight 7500 ( It was a polyether compound of GPC method, polystyrene conversion, and the same below. 750 g (0.1 mol) of the obtained polyether compound and 2.5 g of tetrabutyl titanate were charged into a flask and heated to 150 ° C. while stirring under a nitrogen gas stream. While maintaining the temperature at 140 to 150 ° C., 592.8 g (5.2 mol) of ε-caprolactone was added dropwise over 20 minutes. After completion of the dropping, the reaction was continued at 150 ° C. for 3 hours to complete the synthesis, and a reaction product was obtained. When the obtained reaction product was analyzed, it was a copolymer ratio of oxyethylene unit / oxypropylene unit / oxycaproyl unit = 50/25/25 (mol%), and a polyether polyester block copolymer having a number average molecular weight of 13200 ( K-1).
[0084]
・ Synthesis of polyether polyester block copolymer (K-5)
In the same manner as in the case of the polyether polyester block copolymer (K-1), a polyether polyester block copolymer (K-5) was obtained.
[0085]
-Synthesis of polyether polyester block copolymer (K-2)
An autoclave was charged with 62 g (1 mol) of ethylene glycol and 17 g of potassium hydroxide, purged with nitrogen gas, heated to 120 ° C., and 6798 g (154.5 mol) of ethylene oxide was injected and reacted. After an aging reaction for 1 hour, the catalyst was removed by adsorbent treatment to obtain a reaction product. When the obtained reaction product was analyzed, 150 mol of an oxyethylene unit was added to 1 mol of ethylene glycol, and it was a polyether compound having a hydroxyl value of 16.8 and a number average molecular weight of 6800. 680 g (0.1 mol) of the obtained polyether compound and 4.2 g of tetrabutyl titanate were charged into a flask and heated to 150 ° C. while stirring under a nitrogen gas stream. While maintaining the temperature at 140 to 150 ° C., 592.8 g (5.2 mol) of ε-caprolactone was added dropwise over 40 minutes. After completion of the dropping, the reaction was continued at 150 ° C. for 3 hours to complete the synthesis, and a reaction product was obtained. When the obtained reaction product was analyzed, it was a copolymer ratio of oxyethylene unit / oxycaproyl unit = 75/25 (mol%), and it was a polyether polyester block copolymer (K-2) having a number average molecular weight of 12,500. It was.
[0086]
Synthesis of polyether polyester block copolymers (K-4) and (K-6)
In the same manner as in the case of the polyether polyester block copolymer (K-2), polyether polyester block copolymers (K-4) and (K-6) were obtained.
[0087]
・ Synthesis of polyether polyester block copolymer (K-3)
After charging 92 g (1 mol) of glycerin and 27 g of potassium hydroxide in an autoclave and purging with nitrogen gas, 2691.2 g (46.4 mol) of propylene oxide was injected and reacted while maintaining the temperature at 120 to 140 ° C. . After an aging reaction at the same temperature for 1 hour, 8157.6 g (185.4 mol) of ethylene oxide was further injected and reacted. After aging reaction for 1 hour at the same temperature, the catalyst was removed by adsorbent treatment to obtain a reaction product. When the obtained reactant was analyzed, it was a polyether compound having a copolymerization ratio of oxyethylene unit / oxypropylene unit = 60/15 (molar ratio), a hydroxyl value of 15.8, and a number average molecular weight of 10800. 1080 g (0.1 mol) of the obtained polyether compound and 3.8 g of tetrabutyl titanate were charged into a flask and heated to 150 ° C. while stirring under a nitrogen gas stream. While maintaining the temperature at 140 to 150 ° C., 1060.2 g (9.3 mol) of ε-caprolactone was added dropwise over 40 minutes. After completion of the dropping, the reaction was continued at 150 ° C. for 3 hours to complete the synthesis, and a reaction product was obtained. When the obtained reaction product was analyzed, it was a copolymerization ratio of oxyethylene unit / oxypropylene unit / oxycaproyl unit = 60/15/30 (mol%), and a polyether polyester block copolymer having a number average molecular weight of 21,100 ( K-3).
[0088]
・ Synthesis of polyether polyester block copolymer (K-9)
The flask was charged with 92 g (1 mol) of glycerin and 7.6 g of tetrabutyl titanate and heated to 150 ° C. with stirring under a nitrogen gas stream. While maintaining the temperature at 140 to 150 ° C., 10567.8 g (92.7 mol) of ε-caprolactone was added dropwise over 40 minutes. After completion of the dropping, the reaction was continued at 150 ° C. for 3 hours to complete the synthesis, and the catalyst was removed by adsorbent treatment to obtain a reaction product. When the obtained reaction product was analyzed, 90 mol of an oxycaproyl unit was added to 1 mol of glycerin, and it was a polyester polymer having a number average molecular weight of 10300. 1030 g (0.1 mol) of the obtained polyester polymer and 8 g of potassium hydroxide were charged into an autoclave, purged with nitrogen gas, heated to 120 ° C., and 1020.8 g (23.2 mol) of ethylene oxide was injected. And reacted. After an aging reaction for 1 hour, the catalyst was removed by adsorbent treatment to obtain a reaction product. When the obtained reaction product was analyzed, it was a copolymer ratio of oxyethylene unit / oxycaproyl unit = 75/30 (mol%), and it was a polyether polyester block copolymer (K-9) having a number average molecular weight of 20,300. It was.
[0089]
Synthesis of acylated polyether polyester block copolymer (K-7)
The above-mentioned polyether polyester block copolymer (K-3) 2110 g (0.1 mol), stearic acid 88.0 g (0.31 mol) and paratoluenesulfonic acid monohydrate 8 g were charged into a flask, and nitrogen gas was added. The temperature was adjusted to 120 to 130 ° C. under an air stream, and the reaction was performed at the same temperature for 2 hours. Then, water produced as a by-product at 120 ° C. was removed under reduced pressure to obtain a product. The obtained product was an acylated polyether polyester block copolymer (K-7) having a number average molecular weight of 21,900, in which three stearoyl groups were introduced into one molecule of the polyether polyester block copolymer (K-3). )Met.
[0090]
Synthesis of acylated polyether polyester block copolymer (K-8)
In the same manner as in the case of the acylated polyether polyester block copolymer (K-7), an acylated polyether polyester block copolymer (K-8) was obtained.
[0091]
・ Synthesis of polyether polyester block copolymer (K-10)
An autoclave was charged with 490 g (1 mol) of 40 wt% gluconic acid aqueous solution and 28 g of potassium hydroxide, purged with nitrogen gas, heated to 85 ° C., and 11000 g (250 mol) of ethylene oxide was injected and reacted. After an aging reaction for 1 hour, the catalyst was removed by adsorbent treatment, and water was distilled off under reduced pressure to obtain a reaction product. When the obtained reaction product was analyzed, it was a polyether compound having a hydroxyl value of 31.9 and a number average molecular weight of 11,000, in which 240 mol of oxyethylene units was added to 1 mol of gluconic acid. 1100 g (0.1 mol) of the obtained polyether compound and 2.5 g of tetrabutyl titanate were charged into a flask and heated to 150 ° C. with stirring under a nitrogen gas stream. While maintaining the temperature at 140 to 150 ° C., 2790 g (24.5 mol) of ε-caprolactone was added dropwise over 20 minutes. After completion of the dropping, the reaction was continued at 150 ° C. for 3 hours to complete the synthesis, and a reaction product was obtained. When the obtained reaction product was analyzed, it was a copolymer ratio of oxyethylene unit / oxycaproyl unit = 40/40 (mol%), and it was a polyether polyester block copolymer (K-10) having a number average molecular weight of 38,300. It was.
[0092]
・ Synthesis of polyether polyester block copolymer (K-11)
149 g (1 mol) of triethanolamine and 13 g of potassium hydroxide were charged into an autoclave, purged with nitrogen gas, heated to 120 ° C., and 5386 g (122.4 mol) of ethylene oxide was injected to react. After an aging reaction for 1 hour, the catalyst was removed by adsorbent treatment to obtain a reaction product. When the obtained reaction product was analyzed, it was a polyether compound having a hydroxyl value of 31.5 and a number average molecular weight of 5,500, in which 120 moles of oxyethylene units were added to 1 mole of triethanolamine. 550 g (0.1 mol) of the obtained polyether compound and 2.5 g of tetrabutyl titanate were charged into a flask and heated to 150 ° C. while stirring under a nitrogen gas stream. While maintaining the temperature at 140 to 150 ° C., 1380 g (12.1 mol) of ε-caprolactone was added dropwise over 20 minutes. After completion of the dropping, the reaction was continued at 150 ° C. for 3 hours to complete the synthesis, and a reaction product was obtained. When the obtained reaction product was analyzed, it was a copolymer ratio of oxyethylene unit / oxycaproyl unit = 40/40 (mol%), and it was a polyether polyester block copolymer (K-11) having a number average molecular weight of 19,200. It was.
[0093]
・ Synthesis of polyether polyester block copolymer (K-12)
292 g (1 mol) of N, N, N ′, N′-tetra (2-hydroxypropyl) -ethylenediamine and 13 g of potassium hydroxide were charged into an autoclave, purged with nitrogen gas, heated to 120 ° C., and 7180 g of ethylene oxide. (163.2 mol) was injected and allowed to react. After an aging reaction for 1 hour, the catalyst was removed by adsorbent treatment to obtain a reaction product. When the obtained reaction product was analyzed, 160 mol of an oxyethylene unit was added to 1 mol of N, N, N ′, N′-tetra (2-hydroxypropyl) -ethylenediamine, and the hydroxyl value was 31.0. It was a polyether compound having an average molecular weight of 7,500. 750 g (0.1 mol) of the obtained polyether compound and 5.2 g of tetrabutyl titanate were charged into a flask and heated to 150 ° C. while stirring under a nitrogen gas stream. While maintaining the temperature at 140 to 150 ° C., 1850 g (16.2 mol) of ε-caprolactone was added dropwise over 20 minutes. After completion of the dropping, the reaction was continued at 150 ° C. for 3 hours to complete the synthesis, and a reaction product was obtained. When the obtained reaction product was analyzed, it was a copolymer ratio of oxyethylene unit / oxycaproyl unit = 40/40 (mol%), and it was a polyether polyester block copolymer (K-12) having a number average molecular weight of 26100. It was. The contents of each of the polyether polyester copolymers synthesized above are summarized in Table 2.
[0094]
[Table 2]

[0095]
In Table 2,
Number of repeating oxyalkylene units constituting the polyether block: Number of repeating units per hydroxyl group of the aliphatic hydroxy compound
EO: Oxyethylene unit
PO: Oxypropylene unit
* 1: N, N, N ′, N′-tetra (2-hydroxypropyl) -ethylenediamine
* 2: Stearoyl group / H = 3/0
* 3: Stearoyl group / H = 3/1
[0096]
Test category 3 (Preparation of aqueous treatment solution)
-Preparation of 10 wt% aqueous solution of treating agent (T-1)
After mixing and melting 50 g of the polyether compound (H-1) synthesized in Test Category 1 and 50 g of the polyglycerol fatty acid ester (J-1), 900 g of hot water at 90 ° C. was added thereto, and the mixture was vigorously stirred and dispersed. Liquid, 250 kg / cm²The 10% by weight aqueous solution of the treating agent (T-1) was obtained by homogenizer treatment at a pressure of 5 ° C.
[0097]
-Preparation of 10 wt% aqueous solutions of treatment agents (T-2) to (T-6) and (R-1) to (R-13)
10% by weight aqueous solution of the treating agents (T-2) to (T-6) and (R-1) to (R-13) in the same manner as in the case of the 10% by weight aqueous solution of the treating agent (T-1). A liquid was obtained.
[0098]
-Preparation of 10 wt% aqueous solution of treating agent (T-7)
30 g of the polyether compound (H-1) synthesized in Test Category 1, 30 g of the polyglycerol fatty acid ester (J-1) and 40 g of the polyether polyester block copolymer (K-1) synthesized in Test Category 2, After melting, add 900 g of hot water at 90 ° C. and stir vigorously to make a dispersion. Further, 250 kg / cm²The 10% by weight aqueous solution of the treating agent (T-7) was obtained by homogenizer treatment at
[0099]
-Preparation of 10 wt% aqueous solution of treatment agents (T-8) to (T-18)
In the same manner as in the case of the 10 wt% aqueous liquid of the treating agent (T-7), 10 wt% aqueous liquids of the treating agents (T-8) to (T-18) were obtained.
[0100]
-Preparation of 10 wt% aqueous solution of treating agent (T-19)
27 g of the polyether compound (H-1) synthesized in Test Category 1 and 27 g of the polyglycerol fatty acid ester (J-2), 23 g of the polyether polyester block copolymer (K-1) synthesized in Test Category 2 and polyoxyalkylene 19 g of modified polyorganosiloxane (L-1) and surfactant mixture (E-1) {glycerin monolaurate / polyoxyethylene (the number of oxyethylene units is 20 and n = 20) sorbitan monostearate / 4 g of a mixture of sodium lauryl sulfonate = 30/30/40 (weight ratio)} was mixed and melted, and then 945 g of hot water at 90 ° C. was added thereto, stirred vigorously to obtain a dispersion, and further 250 kg / cm²The 10% by weight aqueous solution of the treating agent (T-19) was obtained by homogenizer treatment at a pressure of 5 ° C.
[0101]
-Preparation of 10 wt% aqueous solution of treatment agents (T-20) to (T-22)
In the same manner as in the case of the 10 wt% aqueous solution of the treatment agent (T-19), 10 wt% aqueous solutions of the treatment agents (T-20) to (T-22) were obtained.
[0102]
The contents of the polyglycerin fatty acid ester used for the preparation of the aqueous solution of each treatment agent are summarized in Table 3, and the contents of the polyoxyalkylene-modified polyorganosiloxane are summarized in Table 4. And in each prepared aqueous liquid, the content of each processing agent except water was shown in Table 5 and Table 6 collectively.
[0103]
[Table 3]

[0104]
In Table 3,
Esterification rate: Ratio of hydroxyl groups esterified out of all hydroxyl groups of polyglycerol (mol%)
[0105]
[Table 4]

[0106]
In Table 4,
* 4: Content of polyoxyalkylene-modified groups (% by weight)
POA-1: R^Four-A²-O-R^FiveIn the polyoxyalkylene-modified group represented by^FourIs a trimethylene group, R^FiveIs a methyl group, A²A polyoxyalkylene-modified group in which is a polyoxyalkylene group having 45 repeating oxyethylene units
POA-2: R^Four-A²-O-R^FiveIn the polyoxyalkylene-modified group represented by^FourIs a trimethylene group, R^FiveIs hydrogen, A²Is a polyoxyalkylene group in which the number of repeating oxyethylene units is 25
POA-3: R^Four-A²-O-R^FiveIn the polyoxyalkylene-modified group represented by^FourIs a trimethylene group, R^FiveIs hydrogen, A²Is a polyoxyalkylene group in which the number of repeating oxyethylene units is 30 and the number of repeating oxypropylene units is 20
[0107]
[Table 5]

[0108]
[Table 6]

[0109]
In Table 5 and Table 6,
E-1: Surfactant mixture in a ratio of glycerol monolaurate / polyoxyethylene (15 mol) sorbitan monostearate / sodium lauryl sulfonate = 30/30/40 (weight ratio)
E-2: Surfactant with a ratio of glycerin monolaurate / polyoxyethylene (15 mol) sorbitan monostearate / polyoxyethylene (5 mol) sodium lauryl ether sulfate = 30/30/40 (weight ratio) blend
E-3: Surface activity of glycerol monolaurate / polyoxyethylene (15 mol) sorbitan monostearate / polyoxyethylene (8 mol) potassium cetyl ether phosphate = 30/30/40 (weight ratio) Agent mixture
E-4: Surfactant mixture at a ratio of glycerin monolaurate / stearic acid diethanolamide / behenic acid amidopropyldimethylethylammonium ethosulphate = 40/30/30 (weight ratio)
Proportion:% by weight
Ratio: Weight ratio
[0110]
Test Category 4 (Attachment and Evaluation of Treatment Agent to Polyolefin Fibers for Fabricating Nonwoven Fabrics by Dry Method)
・ Attachment of treatment agent to polyolefin fiber for non-woven fabric production by dry method
A treatment bath (bath temperature 25 ° C., bath ratio 1:30) was prepared by diluting the aqueous liquid described in Table 5 or Table 6 with water so that the bath concentration reached the target adhesion amount. A polyolefin composite fiber cotton (2.0 denier × 51 mm cut length) whose sheath is polyethylene and whose core is polyester is immersed for 5 minutes and centrifuged at 50% by weight, then 60 ° C. × 60 It was blown and dried for a minute to obtain treated cotton for evaluation below. In addition, the treatment agent adhesion amount to the treated cotton was measured by extracting the treated cotton with a methanol / benzene (50/50 volume ratio) mixed solvent using a Soxhlet extractor. The evaluation results and measurement results are summarized in Tables 7 and 8.
[0111]
・ Scum and fly evaluation
The treated cotton 2000g obtained above was conditioned at 25 ° C x 60% RH for 24 hours, opened under the same conditions with a spreader, and then prepared a card web through a small roller card (one pile type). did. The scum was evaluated for foul-com stains according to the following evaluation criteria, and the fly was evaluated according to the following evaluation criteria with a black screen on the side of a small roller card. The smaller the scum and fly, the better the card passing property and the better the operability.
[0112]
..Evaluation criteria for scum
A: No scum is observed on the needle cloth
○: Slight scum is observed on the needle cloth
Δ: Slightly more scum is observed on the cloth
×: Scum accumulates on the cloth and needs to be cleaned
[0113]
..Fly evaluation criteria
A: Fly is not recognized at all
○: Slight fly is recognized
Δ: Slightly more flies
×: Many flies are recognized and needs to be cleaned
[0114]
・ Evaluation of card web texture uniformity
24g / m per unit area under the same conditions as scum and fly evaluation²A card web was prepared. Using this, the uniformity of the texture of the card web was evaluated according to the following evaluation criteria.
..Evaluation criteria for uniformity of card web texture
A: No spots at all and uniform
○: Slight spots are observed, but this is not a problem
△: Slightly visible spots are a problem
×: Spots can be clearly observed in a wide range, and the product does not become
[0115]
・ Evaluation of water permeability
A small piece of 10 cm × 10 cm was cut from the card web obtained above, and heat-treated with a heater plate at 130 ° C. for 30 seconds to obtain a sample for water permeability evaluation. The sample was conditioned for 24 hours in a constant temperature room at 20 ° C. × 60% RH, placed on a horizontal plate, and 0.4 ml of water droplets were dropped from a height of 10 mm using a burette. The time required for absorption was measured and evaluated according to the following evaluation criteria.
..Evaluation criteria for water permeability
A: Time required for water permeation is less than 0.5 seconds
○: Time required for water permeation is 0.5 seconds or more to less than 1 second
Δ: Time required for water permeation is 1 second or more to less than 2 seconds
×: Time required for water permeation is 2 seconds or more
[0116]
Evaluation of durable hydrophilicity
The operation of repeating the above water permeability evaluation is repeated after 80 ml of ion-exchanged water is sprinkled over the entire surface of the water permeability evaluation sample and sucked and passed, and then blown and dried at 40 ° C. for 90 minutes. The number of repetitions until the water permeability evaluation becomes Δ was evaluated according to the following evaluation criteria.
..Evaluation criteria for durable hydrophilicity
◎: Repeat count 15 times or more
○: 10 to 14 repetitions
△: 5-9 repetitions
×: The number of repetitions is 4 times or less
[0117]
Evaluation of wetback prevention
A 10 cm × 10 cm non-woven piece is cut from the outermost non-woven fabric material of a commercially available paper diaper, and a small piece of 10 cm × 10 cm prepared in the same manner as the above-mentioned water permeability evaluation sample is attached to the cut portion, did. Place the sample to evaluate the wetback prevention horizontally so that the attached piece is facing upward, and set up a 6 cm inner diameter cylinder open at both ends at the center of the piece, and inject 80 ml of water into this cylinder for 5 minutes. The water was absorbed inside the disposable diaper. Next, 15 sheets of 10 cm × 10 cm filter paper stacked on top of the attached small piece are placed, and further, a 2.8 kg weight plate of 10 cm × 10 cm is placed thereon, and after loading for 2 minutes, 15 sheets of filter paper are stacked. The total weight was measured and the rate of increase in the weight was calculated and evaluated according to the following evaluation criteria.
..Evaluation criteria for wetback prevention
A: Weight increase rate is less than 1%
○: Weight increase rate is 1% or more and less than 1.3%
Δ: Weight increase rate is 1.3% or more and less than 2%
X: Weight increase rate is 2% or more
[0118]
[Table 7]

[0119]
[Table 8]

[0120]
In Table 7 and Table 8,
Adhesion amount: Amount of treatment agent attached to polyolefin-based composite fiber (wt%)
[0121]
【The invention's effect】
As is clear from the above, the present invention described above can be obtained by simultaneously imparting excellent card passage properties to polyolefin fibers for producing nonwoven fabrics by a dry process while suppressing the occurrence of scum and fly in the web production process. The card web has the effect of providing excellent formation uniformity, water permeability, durable hydrophilicity and wetback prevention.

Claims (14)

A treating agent for polyolefin fibers for producing nonwoven fabrics by a dry process, comprising a polyether compound represented by the following formula 1 and the following polyglycerin fatty acid ester.
[Formula 1]

(In Equation 1,
R ¹ : an alkyl group having 28 to 60 carbon atoms or an alkanoyl group having 28 to 60 carbon atoms R ² : hydrogen, an alkyl group having 1 to 4 carbon atoms or an alkanoyl group having 1 to 4 carbon atoms A ¹ : 2 or 3 carbon atoms A polyoxyalkylene group composed of repeating oxyalkylene units, wherein the number of repeating oxyalkylene units is 5 to 100, and the oxyalkylene units have 50 mol% or more of oxyethylene units )
Polyglycerin fatty acid ester: Polyglycerin fatty acid ester obtained by esterification of polyglycerin and fatty acid and / or an ester-forming compound of fatty acid, the degree of condensation of the polyglycerin is 2 to 14, and the fatty acid is Polyglycerin fatty acid ester, which is an aliphatic monocarboxylic acid having 6 to 24 carbon atoms, wherein the ester forming compound of the fatty acid is an ester forming compound of an aliphatic monocarboxylic acid having 6 to 24 carbon atoms The treatment of polyolefin fibers for producing nonwoven fabrics by a dry method according to claim 1, wherein the polyether compound is one in which R ^{1 in} formula 1 is an alkyl group having 30 to 40 carbon atoms and R ² is hydrogen. Agent. Polyglycerin fatty acid ester esterifies polyglycerin having a condensation degree of 3 to 12, saturated aliphatic monocarboxylic acid having 12 to 22 carbon atoms and / or saturated aliphatic monocarboxylic acid lower alkyl ester having 12 to 22 carbon atoms The processing agent for polyolefin fibers for producing nonwoven fabrics according to the dry method according to claim 1 or 2, which is obtained by reacting and esterifying 10 to 85 mol% of the hydroxyl groups of the polyglycerol. Furthermore, the processing agent of the polyolefin fiber for nonwoven fabric manufacture by the dry process of Claim 1, 2, or 3 formed by containing the following polyether polyester block copolymer.
Polyether polyester block copolymer: It is constituted by repeating oxyalkylene units in the molecule by ring-opening polymerization of alkylene oxide having 2 to 4 carbon atoms and ε-caprolactone to 1 to 6-valent aliphatic hydroxy compounds. A polyether polyester block copolymer in which a polyoxyalkylene group and a polyester group composed of repeating oxycaproyl units are formed, wherein the polyoxyalkylene group is 5 to 5 per hydroxyl group of the aliphatic hydroxy compound. It has 200 moles of oxyalkylene units and 40 mole% or more of oxyethylene units as the oxyalkylene units, and the total number of repeats of the oxycaproyl units / the total number of repeats of the oxyalkylene units = 1/1 to 1 / 10 (molar ratio) of poly Chromatography ether polyester block copolymer The polyether polyester block copolymer is a 1-6 valent aliphatic hydroxy compound, a 1-6 valent aliphatic alcohol, or a 2-6 valent aliphatic alcohol and an aliphatic monocarboxylic acid having 6-18 carbon atoms. The processing agent of the polyolefin-type fiber for nonwoven fabric manufacture by the dry method of Claim 4 which uses the polyhydric alcohol partial ester. Polyether polyester block copolymer forms a polyether block by ring-opening polymerization of alkylene oxide to 1 to 6-valent aliphatic hydroxy compound, and then ring-opening polymerization of ε-caprolactone at the terminal hydroxyl group of the polyether block A treatment agent for polyolefin-based fibers for producing nonwoven fabrics according to the dry method according to claim 4 or 5, wherein a polyester block is formed. Acylated polyether polyester block copolymer obtained by reacting a terminal hydroxyl group of the polyester block of the polyether polyester block copolymer with an acylating agent having 2 to 22 carbon atoms together with or in place of the polyether polyester block copolymer The processing agent of the polyolefin-type fiber for nonwoven fabric manufacture by the dry method of Claim 6 using coalescence. Furthermore, the polyoxyalkylene modified polyorganosiloxane which has 5 to 38 weight% of polyoxyalkylene groups is contained, The nonwoven fabric manufacture by the dry method of Claim 1, 2, 3, 4, 5, 6 or 7 Treatment agent for polyolefin fibers. The treatment agent for polyolefin fibers for producing a nonwoven fabric by a dry method according to claim 8, wherein the polyoxyalkylene-modified polyorganosiloxane is represented by the following formula 2.
[Formula 2]

{In Equation 2,
Y ¹ , Y ² , Y ³ : a methyl group or a polyoxyalkylene-modified group represented by R ⁴ —A ² —O—R ⁵ , at least one of which is the polyoxyalkylene-modified group (R ⁴ : carbon An alkylene group having 2 to 5 carbon atoms, R ⁵ : hydrogen or an alkyl group having 1 to 12 carbon atoms, A ² : a polyoxyalkylene group composed of repeating oxyalkylene units having 2 or 3 carbon atoms, (Polyoxyalkylene group having 10 to 100 alkylene units and having 50 mol% or more of oxyethylene units as the oxyalkylene units)
R ³ : an alkyl group having 2 to 5 carbon atoms or a phenyl group p, q: an integer in which p is 7 to 150, q is 0 to 20, and 7 ≦ p + q ≦ 150 is satisfied r: 0 to 10 Integer} In the polyoxyalkylene-modified polyorganosiloxane, Y ¹ and Y ² in Formula 2 are methyl groups, Y ³ is a polyoxyalkylene-modified group, and R ⁴ in the polyoxyalkylene-modified group is a trimethylene group. The treatment agent for polyolefin fibers for producing a nonwoven fabric by a dry method according to claim 9, wherein R ⁵ is hydrogen or a methyl group. The dry method according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, which is contained in a ratio of polyether compound / polyglycerin fatty acid ester = 20/80 to 90/10 (weight ratio). Treatment agent for polyolefin fibers for nonwoven fabric production. The total amount of polyether compound and polyglycerin fatty acid ester / polyether polyester block copolymer = 40/60 to 90/10 (weight ratio). The processing agent of the polyolefin-type fiber for nonwoven fabric manufacture by the dry process of 10 or 11. The total amount of the polyether compound, polyglycerin fatty acid ester and polyether polyester block copolymer / polyoxyalkylene-modified polyorganosiloxane = 40/60 to 95/5 (weight ratio). The processing agent of the polyolefin-type fiber for nonwoven fabric manufacture by the dry process of 10, 11, 12, or 13. The treatment agent according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13 is 0.05 to 5% by weight based on a polyolefin fiber for producing a nonwoven fabric by a dry method. A method for treating a polyolefin fiber for producing a nonwoven fabric by a dry method, characterized in that it is adhered.