JP3590456B2 - Warp glue - Google Patents

Description

【０００１】
【産業上の利用分野】
本発明は各種繊維を用いて製織する場合において，優れた製織性能を有する高速織機用として好適な経糸糊剤に関する。さらに詳細には，シャットル織機およびシャットルレス織機による製織に先立ち，フィラメント糸，加工糸，撚糸および紡績糸のような繊維糸条に糊付けすることにより抱合性および対摩耗性を付与するとともに，高温高湿時にも粘着性を生じることがなく，また低温低湿時にもその抱合性を失うことのない，工業的に有用な経糸糊剤に関する。
【０００２】
【従来の技術】
従来より織物の経糸を補強する目的で使用される糊剤として，ポリビニルアルコール系樹脂（以下ＰＶＡと略記する），でんぷん類，カルボキシメチルセルロース，水溶性アクリル糊剤等が使用されている。これらの糊剤はそれぞれ一長一短があるため，種々の繊維に対して単独では使用し難く，２種以上の糊剤を併用しているのが現状である。しかしその中でも特にＰＶＡは，水溶性糊剤として腐敗せずに長期保存が効くことや，得られる皮膜の強度が非常に強いため糊剤の主成分として使用されている。
【０００３】
【発明が解決しようとする課題】
製織方法は近年，織機のエアージェット化に伴って高速化が急速に進んでおり，高速製織に耐え得る物性を有する糊付糸を得る事ができない場合には，工業的価値は全くなくなる。しかし，高速製織に耐えうる糊付糸を製造するためＰＶＡの比率を増加させた経糸糊剤を使用すると，糊付糸ビームを保管している間に糊付糸が吸湿により粘着性を持ち，ビームからの糊付糸の解舒が困難になったり，糊付糸の摩擦係数増大に伴い製織性が悪化するという欠点があった。
【０００４】
【課題を解決するための手段】
本発明者等はかかる課題を解決すべく鋭意検討を重ねた結果，分子内に炭素数４以下のα−オレフィン単位を１〜２４モル％含有する変性ＰＶＡとでんぷん類を主剤とした経糸糊剤を使用することにより，高速製織に耐え得る物性を有する糊付糸が得られることを見いだし，本発明を完成するに至った。
【０００５】
以下に本発明についてさらに詳しく説明する。本発明の経糸糊剤に用いる変性ＰＶＡは，ビニルエステルと炭素数４以下のα−オレフィンとの共重合体をケン化することにより得られる。
ビニルエステルとしては，蟻酸ビニル，酢酸ビニル，プロピオン酸ビニル，ピバリン酸ビニル等が挙げられるが，酢酸ビニルが望ましい。
本発明に用いるα−オレフィンは，炭素数４以下のもので，例えばエチレン，プロピレン，ｎ−ブテン，イソブテン等が挙げられるが，原料入手の容易性および得られた糊付糸が製織時に織機上でガムアップしないという観点からエチレンが好ましい。
α−オレフィンの含有量としては，１〜２４モル％，好ましくは２〜９モル％であることが必要である。α−オレフィンの含有量が１モル％未満の場合には，上述した顕著な効果が得られず，２４モル％を越える場合には，水溶性もしくは水分散性が低下し製織した織物の糊抜き性が不良となるため不適当である。
【０００６】
本発明に用いる変性ＰＶＡは，炭素数４以下のα−オレフィンのみによる変性が最も好ましいが，該変性ＰＶＡの水溶性もしくは水分散性の点から，炭素数４以下のα−オレフィン以外のコモノマーにより該変性ＰＶＡをさらに変性することができる。このようなコモノマー単位としては，例えば，（無水）イタコン酸，（無水）マレイン酸，アクリルアミド−２−メチルプロパンスルホン酸およびそのナトリウム塩，ビニルスルホン酸ナトリウム，アリルスルホン酸ナトリウム等が挙げられるがこれらに限定されるものではない。該コモノマーの含有量は０．１〜１０モル％が好ましい。該コモノマーの含有量が０．１モル％未満の場合には水溶性または水分散性の向上が見られず，また１０モル％を越える場合には本発明の効果を阻害するようになり好ましくない。
【０００７】
また本発明に用いる変性ＰＶＡとしては，本発明の効果を損なわない範囲でエチレン性不飽和単量体を共重合したものでも良い。このようなエチレン性不飽和単量体としては，例えばアクリル酸，メタクリル酸，（無水）フタル酸，アクリロニトリル，メタクリロニトリル，アクリルアミド，メタクリルアミド，トリメチル−（３−アクリルアミド−３−ジメチルプロピル）−アンモニウムクロリド，エチルビニルエーテル，ブチルビニルエーテル，Ｎ−ビニルピロリドン，塩化ビニル，臭化ビニル，フッ化ビニル，塩化ビニリデン，フッ化ビニリデン，テトラフルオロエチレン等が挙げられる。
さらにチオール酢酸，メルカプトプロピオン酸等のチオール化合物の存在下で，酢酸ビニル等のビニルエステル系単量体を炭素数４以下のα−オレフィンと共重合し，それをケン化することによって得られる末端変性ＰＶＡも用いることができる。
これらのエチレン性不飽和単量体単位の含有量としては特に制限はないが，２モル％以下が好ましく，１モル％以下がより好ましく，０．５モル％以下がさらに好ましい。
【０００８】
本発明の経糸糊剤に用いる分子内に炭素数４以下のα−オレフィン単位を１〜２４モル％含有する変性ＰＶＡの平均重合度は，通常１００〜５０００，好ましくは２００〜３０００から選ばれ，またそのビニルエステル部分の平均ケン化度には特に限定はないが，通常６０〜１００モル％，好ましくは７０〜９９．９モル％である。平均重合度が１００未満では高速製織に耐えうる経糸糊剤としての性能，特に皮膜強度および繊維に対する接着力が低下し，５０００を越えると糊液の粘度が高くなりすぎるため，糊付け作業性の点で好ましくない。また平均ケン化度が６０モル％未満になると，水溶性もしくは水分散性が低下するため，製織した織物の糊抜き性が不良となり好ましくない。
【０００９】
さらに本発明の経糸糊剤に用いる分子内に炭素数４以下のα−オレフィン単位を１〜２４モル％含有する変性ＰＶＡに併用するでんぷん類としては，コーン，馬鈴薯，タピオカ，小麦等の生でんぷんおよびそれらの変性でんぷんが含まれる。変性でんぷんとしては，α化でんぷん，酸化でんぷん，エステル化でんぷん，エーテル化でんぷん，グラフトでんぷん，ジアルデヒドでんぷん，カチオン化でんぷん等が挙げられるが，これらに限定されるものではない。また，かかる変性ＰＶＡとでんぷん類の混合比率は，重量比において９０：１０〜５０：５０である。変性ＰＶＡの比率がでんぷん類に対して５０％未満になると，高速製織に耐えうる糊付糸を得るためには糊剤付着量を多くする必要が生じ経済的ではなく，また９０％を越えると，糊付け時の作業性，特にデバイド抵抗増加につながるため好ましくない。
【００１０】
一般に紡績糸の場合，経糸糊付け用糊剤の糊液粘度は毛羽伏せを良くするために比較的高粘度で用いられる。具体的に糊付け温度７０〜９５℃における粘度は５０〜２００センチポイズである。糊液の固形分濃度は３〜１５重量％が一般的である。対象とする糸は特に限定はなく，綿，ポリエステル，レーヨン，麻，ナイロン，羊毛，アクリル等の単独糸またはこれらの混紡糸に好適に用いられる。また，上述のように紡績糸の種類が非常に多くなっているため，糊液調製に当たっては対象とする経糸に見合った処方を組み立てる必要がある。
【００１１】
繊維に対する糊剤の付着量は織物の規格，使用する織機・糊付機等の設備等によって任意に選ばれる。一般に紡績糸の場合には，糊付糸の表面の毛羽伏せと内部浸透による補強を主目的としているため，要求される糊付糸性能を考えて糊剤付着量が決定されている。一般に糊剤付着量が多いほど糊付糸の対摩耗性，毛羽伏せ効果が向上し製織時の経糸切れが減少する。
【００１２】
以上のように，本発明は分子内に炭素数４以下のα−オレフィン単位を１〜２４モル％含有する変性ＰＶＡとでんぷん類を主剤とする経糸糊剤であるが，本発明の効果を損なわない範囲で一般のＰＶＡ系樹脂，カルボキシメチルセルロース，水溶性アクリル糊剤等の水溶性ポリマーやワックス，オイル等の平滑剤，その他の添加剤として消泡剤，帯電防止剤，防黴剤等を含むことができる。
さらに，本発明における糊付け方法については特に制限はなく，一斉スラッシャー糊付け，部分整経糊付け，テープ糊付け，チーズ糊付け等が例示できるがこれらに限定されるものではない。
【００１３】
以上は高速織機用経糸糊剤を例に挙げて説明してきたが，本発明の経糸糊剤は織物の樹脂加工，洗濯用糊剤，捺染用糊剤あるいはフェルトや不織布のバインダーとしても有効に利用できる。
【００１４】
【実施例】
以下，実施例により本発明をより具体的に説明するが，本発明はこれらの実施例により，なんら限定されるものではない。なお以下で，「部」および「％」は特に断らない限り，それぞれ「重量部」および「重量％」を意味する。
【００１５】
実施例１
エチレンと酢酸ビニルとの共重合体をアルカリケン化して，エチレンを７．１モル％含有し，酢酸ビニル単位のケン化度９５．４モル％，重合度１７００のエチレン変性ＰＶＡを得た。このエチレン変性ＰＶＡを用い下記の処方の糊液を調製し，糊付けを行い，製織に供した。
（１）糊処方
エチレン変性ＰＶＡ ７０部
加工でんぷん（マーメイドＭ−２００：シキシマスターチ製） ３０部
繊維糊剤用ワックス（ワプセット６００：竹本油脂（株）製） ５部
（２）糊化条件
エチレン変性ＰＶＡ７０Ｋｇおよび加工でんぷん３０Ｋｇを水中に投入し，撹拌下スチームを吹き込むことにより液温を１００℃まで上げ，１時間溶解した。最後に繊維糊剤用ワックスを５Ｋｇ添加し，さらに若干の温水で固形分濃度１２．７％になるように調製した。
（３）織物規格
経糸： 綿糸（東洋紡「金魚」Ｃ４０／１）
緯糸： 同上
経糸密度： １３６本／インチ
緯糸密度： ７２本／インチ
織り幅： ４７インチ
経糸総本数： ６４２０本
織組織： ブロード
織機： 津田駒社製エアージェット織機ＺＡ−２０９ｉ
織機回転数： ６００ｒｐｍ
（４）糊付条件
糊付機： 津田駒社製２ボックス２シート型
糊液温度： ９２℃
絞りロール幅：１８００ｍｍ
絞り荷重： ８００Ｋｇ／１８００ｍｍ幅
糸速度： ６０ヤード／分
乾燥温度： １００〜１３０℃
糊付糸長： ５６００ヤード
得られた糊付糸の糊剤付着量（以下着糊量と略記する）は１５．３％となり，製織性と対応した糸物性を測定した結果，１ｍｍ以上の毛羽数は８３個／ｍ，摩耗強度は１８７回と良好であり，また製織効率も９４．２％と満足できるものであった。
さらに，同時に糊付けした糊付糸ビームを夏期を想定した高湿度環境下（３０℃，８４％ＲＨ）に２０日間放置した後，製織に供し，ビーム設置後２日間の製織性を観察したが，吸湿によるトラブルはなく，その間の製織効率も９３．８％と良好であった。結果を表１に示す。
【００１６】
実施例２
エチレンを２．３モル％含有し，酢酸ビニル部分のケン化度８８．０モル％，重合度１２００のエチレン変性ＰＶＡを使用する以外は実施例１と同様の試験を行った。
得られた糊付糸の着糊量は１５．０％となり，糊付糸物性は１ｍｍ以上の毛羽数が８６個／ｍ，摩耗強度が１７１回と良好であり，また製織効率も９３．２％と満足できるものであった。
さらに，高湿度環境下に放置後の製織性を実施例１と同様の方法で行った結果，９２．９％と良好であった。結果を表１に示す。
【００１７】
実施例３
エチレンを７．１モル％含有し，酢酸ビニル部分のケン化度９５．４モル％，重合度１７００のエチレン変性ＰＶＡを使用し，糊処方を下記の如く変更する他は実施例１と同様の試験を行った。
（１）糊処方
エチレン変性ＰＶＡ ５０部
加工でんぷん（マーメイドＭ−２００：シキシマスターチ製） ５０部
繊維糊剤用ワックス（ワプセット６００：竹本油脂（株）製） ５部
得られた糊付糸の着糊量は１５．８％となり，糊付糸物性は１ｍｍ以上の毛羽数が７７個／ｍ，摩耗強度が１９３回と良好であり，また製織効率も９２．１％と満足できるものであった。
さらに，高湿度環境下に放置後の製織性を実施例１と同様の方法で行った結果，９４．０％と良好であった。結果を表１に示す。
【００１８】
比較例１
実施例１で使用したエチレン変性ＰＶＡの代わりに市販ＰＶＡ（クラレポバール２１７）を使用する以外は実施例１と同様に糊付けし，製織に供した。
得られた糊付糸の着糊量は１６．０％となり，製織性と対応した糸物性を測定した結果，１ｍｍ以上の毛羽数は７９個／ｍ，摩耗強度は１７８回となり，また製織効率も９０．６％と比較的良好であった。
さらに，高湿度環境下に放置後の製織性を実施例１と同様の方法で行った結果，吸湿により製織時における経糸の開口性がやや不良となるとともに，製織開始後約１時間で毛羽玉が発生し，経糸切れ，緯糸止まりが頻繁に起こり，２日間の平均製織効率も７８．３％と不良であった。結果を表１に示す。
【００１９】
実施例４
エチレンと酢酸ビニルとの共重合体をアルカリケン化して，エチレンを７．１モル％含有し，酢酸ビニル単位のケン化度８８．０モル％，重合度１７００のエチレン変性ＰＶＡを得た。
また，同様の手法でエチレンを７．１モル含有し，酢酸ビニル単位のケン化度８２．０モル％，重合度５００のエチレン変性ＰＶＡを得た。
これらのエチレン変性ＰＶＡを用い下記の処方の糊液を調製し，糊付けを行い，製織に供した。
（１）糊処方
エチレン変性ＰＶＡ
（変性度７．１モル％，ケン化度８８．０モル％，重合度１７００） ３５部
（変性度７．１モル％，ケン化度８２．０モル％，重合度５００） ３５部
加工でんぷん（マーメイドＭ−２００：シキシマスターチ製） ３０部
繊維糊剤用ワックス（ワプセット６００：竹本油脂（株）製） ５部
（２）糊化条件
エチレン変性ＰＶＡ７０Ｋｇ（３５Ｋｇ＋３５Ｋｇ）および加工でんぷん３０Ｋｇを水中に投入し，撹拌下スチームを吹き込むことにより液温を１００℃まで上げ，１時間溶解した。最後に繊維糊剤用ワックスを５Ｋｇ添加し，さらに若干の温水で固形分濃度１１．１％になるように調製した。
（３）織物規格
経糸： ポリエステル／綿混紡糸（クラレエステル１０１３Ｃ４５／１）
緯糸： 同上
経糸密度： １４０本／インチ
緯糸密度： ７５本／インチ
織り幅： ４８インチ
経糸総本数： ６７２０本
織組織： ブロード
織機： 津田駒社製エアージェット織機ＺＡ−２０９ｉ
織機回転数： ６００ｒｐｍ
（４）糊付条件
糊付機： 津田駒社製２ボックス２シート型
糊液温度： ９２℃
絞りロール幅：１８００ｍｍ
絞り荷重： ８００Ｋｇ／１８００ｍｍ幅
糸速度： ６０ヤード／分
乾燥温度： １００〜１３０℃
糊付糸長： ５６００ヤード
得られた糊付糸の着糊量は１３．４％となり，製織性と対応した糸物性を測定した結果，１ｍｍ以上の毛羽数は７４個／ｍ，摩耗強度は２２５回と良好であり，また製織効率も９３．８％と満足できるものであった。
さらに，高湿度環境下に放置後の製織性を実施例１と同様の方法で行った結果，９２．１％と良好であった。結果を表２に示す。
【００２０】
実施例５
エチレンおよびアリルスルホン酸ソーダ（以下ＳＡＳと略記する）と酢酸ビニルとの共重合体をアルカリケン化して，エチレンを７．０モル％，ＳＡＳを０．４モル％含有し，酢酸ビニル単位のケン化度７１．０モル％，重合度１１００のエチレン／ＳＡＳ変性ＰＶＡを得た。
このＰＶＡを用い下記の処方の糊液を調製し，糊付けを行い，製織に供した。
（１）糊処方
エチレン／ＳＡＳ変性ＰＶＡ ８０部
加工でんぷん（マーメイドＭ−２００：シキシマスターチ製） １０部
繊維糊剤用ワックス（ワプセット６００：竹本油脂（株）製） １０部
（２）糊化条件
エチレン／ＳＡＳ変性ＰＶＡ８０Ｋｇおよび加工でんぷん１０Ｋｇを水中に投入し，撹拌下スチームを吹き込むことにより液温を１００℃まで上げ，１時間溶解した。最後に繊維糊剤用ワックスを１０Ｋｇ添加し，さらに若干の温水で固形分濃度１１．３％になるように調製した。
（３）織物規格
経糸： ポリエステル１００％糸（クラレエステル１０１３Ｓ４０／１）
緯糸： 同上
経糸密度： １３６本／インチ
緯糸密度： ７２本／インチ
織り幅： ４７インチ
経糸総本数： ６４２０本
織組織： ブロード
織機： 津田駒社製エアージェット織機ＺＡ−２０９ｉ
織機回転数： ６００ｒｐｍ
（４）糊付条件
糊付機： 津田駒社製２ボックス２シート型
糊液温度： ８５℃
絞りロール幅：１８００ｍｍ
絞り荷重： ８００Ｋｇ／１８００ｍｍ幅
糸速度： ６０ヤード／分
乾燥温度： １００〜１３０℃
糊付糸長： ５６００ヤード
得られた糊付糸の着糊量は１２．８％となり，製織性と対応した糸物性を測定した結果，１ｍｍ以上の毛羽数は７６個／ｍ，摩耗強度は４１１回と良好であり，また製織効率も９４．３％と満足できるものであった。
さらに，高湿度下に放置後の製織性を実施例１と同様の方法で行った結果，９０．９％と良好であった。結果を表２に示す。
【００２１】
比較例２
実施例４で使用したエチレン変性ＰＶＡの代わりに市販ＰＶＡ（クラレポバール２１７＋クラレポバール２０５：３５部＋３５部）を使用する以外は実施例４と同様に糊付けし，製織に供した。
得られた糊付糸の着糊量は１３．７％となり，製織性と対応した糸物性を測定した結果，１ｍｍ以上の毛羽数は７５個／ｍ，摩耗強度は２０６回となり，また製織効率も９０．２％と比較的良好であった。
さらに，高湿度環境下に放置後の製織性を実施例１と同様の方法で行った結果，吸湿により製織時における経糸の開口性が不良となるとともに，製織開始後約０．５時間で毛羽玉が発生し，経糸切れ，緯糸止まりが頻繁に起こり，２日間の平均製織効率も７２．１％と不良であった。結果を表２に示す。
【００２２】
比較例３
実施例５で使用したエチレン変性ＰＶＡの代わりに市販ＰＶＡ（クラレポバール２１７＋クラレポバール２０５：４０部＋４０部）を使用する以外は実施例５と同様に糊付けし，製織に供した。
得られた糊付糸の着糊量は１３．１％となり，製織性と対応した糸物性を測定した結果，１ｍｍ以上の毛羽数は８６個／ｍ，摩耗強度は３９６回となり，また製織効率も８９．９％と比較的良好であった。
さらに，高湿度環境下に放置後の製織性を実施例１と同様の方法で行った結果，吸湿により製織時における経糸の開口性が不良となるとともに，製織開始後約０．５時間で毛羽玉が発生し，経糸切れ，緯糸止まりが頻繁に起こり，２日間の平均製織効率も６９．８％と不良であった。結果を表２に示す。
【００２３】
上記の実施例および比較例において，着糊量として表現してある値は，『たて糸糊付』（深田 要，一見 輝彦共著，日本繊維機械学会発行）２９９〜３０２頁に記述してある，糊抜き洗浄時の毛羽の脱落部分を補正する方法により測定した値である。また，毛羽数は毛羽カウンター（ダイワボウ製ＤＫ−１０３）を用い，１ｍｍ以上について測定した値である。また，摩耗強度は，ＴＭ式抱合力試験機（（株）大栄科学精器製作所製）で荷重１００ｇ／本で切断するまでの回数を測定した値である。
【００２４】
【表１】

【００２５】
【表２】

【００２６】
【発明の効果】
本発明の経糸糊剤は，高速製織に耐え得る物性を有する糊付糸が得られ，また高温高湿度下で糊付糸ビームを保管しても糊付糸の解舒性，開口性に優れ，製織効率を大幅に向上させることができる点で工業的価値が極めて高いものである。[0001]
[Industrial applications]
The present invention relates to a warp size agent suitable for high-speed looms having excellent weaving performance when weaving using various fibers. More specifically, prior to weaving by shuttle looms and shuttle-less looms, the yarns such as filament yarns, processed yarns, twisted yarns and spun yarns are glued to impart conjugation properties and abrasion resistance. The present invention relates to an industrially useful warp sizing agent which does not produce tackiness even when wet and does not lose its conjugation property even at low temperature and low humidity.
[0002]
[Prior art]
Hitherto, as a sizing agent used to reinforce the warp of a woven fabric, a polyvinyl alcohol-based resin (hereinafter abbreviated as PVA), starch, carboxymethyl cellulose, a water-soluble acryl sizing agent and the like have been used. Since each of these sizing agents has advantages and disadvantages, it is difficult to use it alone for various fibers. At present, two or more sizing agents are used in combination. However, among them, PVA is particularly used as a main component of the glue because it is effective as a water-soluble glue for long-term storage without decay and the strength of the obtained film is very strong.
[0003]
[Problems to be solved by the invention]
In recent years, the weaving method has been rapidly increasing in speed with the use of air jets in looms. If a glued yarn having physical properties that can withstand high-speed weaving cannot be obtained, there is no industrial value. However, if a warp sizing agent with an increased ratio of PVA is used to produce a sized yarn that can withstand high-speed weaving, the sized yarn will become sticky due to moisture absorption while the sized yarn beam is stored. There are drawbacks in that it is difficult to unwind the glued yarn from the beam, and that the weavability deteriorates with an increase in the friction coefficient of the glued yarn.
[0004]
[Means for Solving the Problems]
The inventors of the present invention have conducted intensive studies in order to solve such problems, and as a result, a warp sizing agent containing starch as a main component and modified PVA containing 1 to 24 mol% of α-olefin units having 4 or less carbon atoms in the molecule. It has been found that a glued yarn having physical properties that can withstand high-speed weaving can be obtained by using, and the present invention has been completed.
[0005]
Hereinafter, the present invention will be described in more detail. The modified PVA used in the warp paste of the present invention is obtained by saponifying a copolymer of a vinyl ester and an α-olefin having 4 or less carbon atoms.
Examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate and the like, with vinyl acetate being preferred.
The α-olefin used in the present invention has 4 or less carbon atoms and includes, for example, ethylene, propylene, n-butene, isobutene, and the like. Ethylene is preferred from the viewpoint that it does not gum up.
It is necessary that the content of the α-olefin is 1 to 24 mol%, preferably 2 to 9 mol%. When the content of α-olefin is less than 1 mol%, the above-mentioned remarkable effects cannot be obtained. When the content exceeds 24 mol%, the water solubility or water dispersibility is reduced, and the woven fabric is desizing. This is unsuitable because of poor properties.
[0006]
The modified PVA used in the present invention is most preferably modified only with an α-olefin having 4 or less carbon atoms. However, from the viewpoint of water solubility or water dispersibility of the modified PVA, it is preferable to use a comonomer other than the α-olefin having 4 or less carbon atoms. The modified PVA can be further modified. Examples of such a comonomer unit include (anhydride) itaconic acid, (anhydride) maleic acid, acrylamido-2-methylpropanesulfonic acid and its sodium salt, sodium vinyl sulfonate and sodium allyl sulfonate. However, the present invention is not limited to this. The content of the comonomer is preferably 0.1 to 10 mol%. When the content of the comonomer is less than 0.1 mol%, no improvement in water solubility or water dispersibility is observed, and when it exceeds 10 mol%, the effect of the present invention is impaired, which is not preferable. .
[0007]
The modified PVA used in the present invention may be a copolymer of an ethylenically unsaturated monomer as long as the effects of the present invention are not impaired. Such ethylenically unsaturated monomers include, for example, acrylic acid, methacrylic acid, (phthalic anhydride), acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, trimethyl- (3-acrylamido-3-dimethylpropyl)- Examples thereof include ammonium chloride, ethyl vinyl ether, butyl vinyl ether, N-vinylpyrrolidone, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene.
Furthermore, in the presence of a thiol compound such as thiolacetic acid or mercaptopropionic acid, a vinyl ester-based monomer such as vinyl acetate is copolymerized with an α-olefin having 4 or less carbon atoms, and a terminal obtained by saponifying it. Modified PVA can also be used.
The content of these ethylenically unsaturated monomer units is not particularly limited, but is preferably 2 mol% or less, more preferably 1 mol% or less, and even more preferably 0.5 mol% or less.
[0008]
The average degree of polymerization of the modified PVA containing 1 to 24 mol% of α-olefin units having 4 or less carbon atoms in the molecule used for the warp size agent of the present invention is generally selected from 100 to 5000, preferably 200 to 3000, The average degree of saponification of the vinyl ester portion is not particularly limited, but is usually from 60 to 100 mol%, preferably from 70 to 99.9 mol%. If the average degree of polymerization is less than 100, the performance as a warp sizing agent that can withstand high-speed weaving, particularly the film strength and the adhesive strength to the fiber, decrease. If the average polymerization degree exceeds 5,000, the viscosity of the sizing solution becomes too high. Is not preferred. On the other hand, if the average saponification degree is less than 60 mol%, the water solubility or water dispersibility decreases, and the desizing of the woven fabric becomes poor, which is not preferable.
[0009]
Further, starches used in combination with modified PVA containing 1 to 24 mol% of α-olefin units having 4 or less carbon atoms in the molecule used in the warp paste of the present invention include raw starches such as corn, potato, tapioca, wheat and the like. And their modified starches. Modified starches include, but are not limited to, pregelatinized starch, oxidized starch, esterified starch, etherified starch, grafted starch, dialdehyde starch, cationized starch, and the like. The mixing ratio of the modified PVA and starch is 90:10 to 50:50 by weight. If the ratio of the modified PVA is less than 50% with respect to starch, it is not economical to use a large amount of sizing agent to obtain a sized yarn that can withstand high-speed weaving. This is not preferable because it leads to an increase in workability at the time of gluing, particularly, an increase in divide resistance.
[0010]
Generally, in the case of spun yarn, the size liquid viscosity of the sizing agent for warp sizing is used with a relatively high viscosity in order to improve fluffiness. Specifically, the viscosity at a gluing temperature of 70 to 95 ° C. is 50 to 200 centipoise. The solid content concentration of the size liquid is generally 3 to 15% by weight. The target yarn is not particularly limited, and is preferably used as a single yarn such as cotton, polyester, rayon, hemp, nylon, wool, and acrylic, or a blended yarn thereof. Also, as described above, since the types of spun yarns are extremely large, it is necessary to assemble a prescription suitable for the target warp in preparing the size liquid.
[0011]
The amount of the glue adhering to the fibers is arbitrarily selected depending on the specifications of the woven fabric and the equipment used such as a loom and a sizing machine. In general, in the case of spun yarn, the main purpose is to reinforce the surface of the glued yarn by fluffing and internal permeation. Therefore, the amount of the glue applied is determined in consideration of required glued yarn performance. In general, the larger the amount of glue adhered, the better the abrasion resistance and fluffing effect of the sized yarn and the less warp breakage during weaving.
[0012]
As described above, the present invention is a warp paste mainly composed of modified PVA and starch containing 1 to 24 mol% of α-olefin units having 4 or less carbon atoms in the molecule, but the effect of the present invention is impaired. Water-soluble polymers such as general PVA-based resin, carboxymethylcellulose, water-soluble acrylic glue, and leveling agents such as wax and oil, and other additives include antifoaming agents, antistatic agents, antifungal agents, etc. be able to.
Further, the gluing method in the present invention is not particularly limited, and examples include, but not limited to, simultaneous slasher gluing, partial warping gluing, tape gluing, cheese gluing, and the like.
[0013]
Although the warp sizing agent for high-speed looms has been described above as an example, the warp sizing agent of the present invention can be effectively used as a resin for woven fabric, a sizing agent for washing, a sizing agent for printing, or a binder for felt or nonwoven fabric. it can.
[0014]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following, “parts” and “%” mean “parts by weight” and “% by weight”, respectively, unless otherwise specified.
[0015]
Example 1
The copolymer of ethylene and vinyl acetate was alkali-saponified to obtain ethylene-modified PVA containing 7.1 mol% of ethylene, a saponification degree of vinyl acetate units of 95.4 mol%, and a polymerization degree of 1700. Using this ethylene-modified PVA, a size liquid having the following formulation was prepared, glued, and provided for weaving.
(1) Glue formulation Ethylene-modified PVA 70 parts Processed starch (Mermaid M-200: manufactured by Sixi Mastachi) 30 parts Wax for fiber sizing agent (Wapset 600: manufactured by Takemoto Yushi Co., Ltd.) 5 parts (2) Gelatinization conditions ethylene-modified 70 kg of PVA and 30 kg of processed starch were put into water, and the temperature of the solution was raised to 100 ° C. by blowing steam with stirring, and dissolved for 1 hour. Finally, 5 kg of a wax for fiber sizing agent was added, and the solid content was adjusted to 12.7% with a little warm water.
(3) Fabric standard warp: Cotton yarn (Toyobo “Goldfish” C40 / 1)
Weft: Same as above Warp density: 136 yarns / inch Weft density: 72 yarns / inch Weaving width: 47 inches Total number of warp yarns: 6420 yarns Organization: Broad loom: Air jet loom ZA-209i manufactured by Tsuda Komasha
Loom rotation speed: 600 rpm
(4) Gluing conditions Gluing machine: 2-box 2-sheet type size liquid manufactured by Tsuda Komasha Inc. Temperature: 92 ° C
Squeeze roll width: 1800mm
Squeezing load: 800 Kg / 1800 mm Width Yarn Speed: 6 0 yards / min Drying temperature: 100 to 130 ° C.
Glued yarn length: The glued amount (hereinafter abbreviated as “glue amount”) of the glued yarn obtained for 5600 yards was 15.3%. As a result of measuring the yarn physical properties corresponding to the weaving property, the fluff of 1 mm or more was obtained. The number was 83 pieces / m, the abrasion strength was good at 187 times, and the weaving efficiency was 94.2%, which was satisfactory.
Furthermore, the glued yarn beam simultaneously glued was left for 20 days in a high humidity environment (30 ° C., 84% RH) assuming the summer, and then subjected to weaving, and weaving was observed for 2 days after the beam was installed. There was no trouble due to moisture absorption, and the weaving efficiency during that time was as good as 93.8%. Table 1 shows the results.
[0016]
Example 2
The same test as in Example 1 was conducted except that ethylene-modified PVA containing 2.3 mol% of ethylene, a saponification degree of a vinyl acetate portion of 88.0 mol%, and a polymerization degree of 1200 was used.
The glued amount of the obtained glued yarn was 15.0%, the physical properties of the glued yarn were 86 fuzzes / m with 1 mm or more, the abrasion strength was good at 171 times, and the weaving efficiency was 93.2. % Was satisfactory.
Further, the weaving properties after being left in a high humidity environment were measured in the same manner as in Example 1. It was as good as 9 %. Table 1 shows the results.
[0017]
Example 3
The same as Example 1 except that ethylene-modified PVA containing 7.1 mol% of ethylene, a saponification degree of vinyl acetate portion of 95.4 mol% and a polymerization degree of 1700 was used, and the paste formulation was changed as follows. The test was performed.
(1) Glue formulation Ethylene-modified PVA 50 parts Processed starch (Mermaid M-200: manufactured by Sixi Mastachi) 50 parts Wax for fiber sizing agent (Wapset 600: manufactured by Takemoto Yushi Co., Ltd.) 5 parts Adhesive yarn obtained The size of the glue was 15.8%, the physical properties of the glued yarn were as good as 77 / m for the number of fluffs with 1 mm or more, the abrasion strength was good at 193 times, and the weaving efficiency was 92.1%, which was satisfactory. .
Furthermore, the weaving property after being left in a high humidity environment was determined by the same method as in Example 1, and as a result, it was as good as 94.0%. Table 1 shows the results.
[0018]
Comparative Example 1
Gluing was carried out in the same manner as in Example 1 except that commercial PVA (Kuraray Povar 217) was used in place of the ethylene-modified PVA used in Example 1, and the resultant was subjected to weaving.
The gluing amount of the obtained glued yarn was 16.0%, and the yarn physical properties corresponding to the weaving property were measured. As a result, the number of fluffs of 1 mm or more was 79 / m, the abrasion strength was 178 times, and the weaving efficiency was high. Was also relatively good at 90.6%.
Further, the weaving properties after being left in a high humidity environment were measured in the same manner as in Example 1. As a result, the opening properties of the warp during weaving were slightly deteriorated due to moisture absorption, and fluff balls were formed about one hour after the start of weaving. And warp breakage and weft stoppage occurred frequently, and the average weaving efficiency for 2 days was poor at 78.3%. Table 1 shows the results.
[0019]
Example 4
The copolymer of ethylene and vinyl acetate was alkali-saponified to obtain ethylene-modified PVA containing 7.1 mol% of ethylene, a saponification degree of vinyl acetate units of 88.0 mol%, and a polymerization degree of 1700.
In the same manner, ethylene-modified PVA containing 7.1 mol of ethylene, a saponification degree of vinyl acetate units of 82.0 mol% and a polymerization degree of 500 was obtained.
A paste solution having the following formulation was prepared using these ethylene-modified PVAs, glued, and provided for weaving.
(1) Glue formulation ethylene-modified PVA
35 parts (modification degree 7.1 mol%, saponification degree 88.0 mol%, polymerization degree 1700) 35 parts (modification degree 7.1 mol%, saponification degree 82.0 mol%, polymerization degree 500) 35 parts modified starch (Mermaid M-200: manufactured by Sixi Mastachi) 30 parts wax for fiber sizing agent (Wapset 600: manufactured by Takemoto Yushi Co., Ltd.) 5 parts (2) Gelatinization conditions 70 kg (35 kg + 35 kg) of ethylene-modified PVA and 30 kg of modified starch are put into water. Then, the liquid temperature was raised to 100 ° C. by blowing steam under stirring to dissolve for 1 hour. Finally, 5 kg of a wax for fiber sizing agent was added, and the solid content was adjusted to 11.1% with a little warm water.
(3) Fabric standard warp: polyester / cotton blended yarn (Kuraray ester 1013C45 / 1)
Weft: Same as above Warp density: 140 yarns / inch Weft density: 75 yarns / inch Weaving width: 48 inches Total number of warps: 6720 yarns Organization: Broad loom: Air jet loom ZA-209i manufactured by Tsuda Komasha
Loom rotation speed: 600 rpm
(4) Gluing conditions Gluing machine: 2-box 2-sheet type size liquid manufactured by Tsuda Komasha Inc. Temperature: 92 ° C
Squeeze roll width: 1800mm
Squeezing load: 800 Kg / 1800 mm Width Yarn Speed: 6 0 yards / min Drying temperature: 100 to 130 ° C.
Glued yarn length: The size of the glued yarn obtained for 5600 yards is 13. Becomes 4%, the results of measurement of the yarn physical properties corresponding to the weaving property, hairiness number of more than 1mm 74 pieces / m, was good and the wear strength 225 times, also weaving efficiency satisfactory as 93.8% there were.
Furthermore, the weaving property after being left in a high-humidity environment was measured by the same method as in Example 1, and as a result, it was as good as 92.1%. Table 2 shows the results.
[0020]
Example 5
Alkaline saponification of a copolymer of ethylene and sodium allyl sulfonate (hereinafter abbreviated as SAS) and vinyl acetate contains 7.0 mol% of ethylene and 0.4 mol% of SAS, An ethylene / SAS modified PVA having a degree of polymerization of 71.0 mol% and a degree of polymerization of 1100 was obtained.
Using this PVA, a size liquid having the following formulation was prepared, glued, and provided for weaving.
(1) Glue formulation Ethylene / SAS-modified PVA 80 parts Modified starch (Mermaid M-200: manufactured by Sixi Mastachi) 10 parts Wax for fiber sizing agent (Wapset 600: manufactured by Takemoto Yushi Co., Ltd.) 10 parts (2) Gelatinization conditions 80 kg of ethylene / SAS-modified PVA and 10 kg of modified starch were put into water, and the temperature of the solution was raised to 100 ° C. by blowing steam with stirring to dissolve for 1 hour. Finally, 10 kg of a wax for fiber sizing agent was added, and the mixture was further adjusted to a solid concentration of 11.3% with a little warm water.
(3) Fabric standard warp: 100% polyester yarn (Kuraray ester 1013S40 / 1)
Weft: Same as above Warp density: 136 yarns / inch Weft density: 72 yarns / inch Weaving width: 47 inches Total number of warp yarns: 6420 yarns Organization: Broad loom: Air jet loom ZA-209i manufactured by Tsuda Komasha
Loom rotation speed: 600 rpm
(4) Gluing conditions Gluing machine: 2-box 2-sheet type size liquid manufactured by Tsuda Komasha Inc. Temperature: 85 ° C
Squeeze roll width: 1800mm
Squeezing load: 800 Kg / 1800 mm Width Yarn Speed: 6 0 yards / min Drying temperature: 100 to 130 ° C.
Glued yarn length: The glued amount of the glued yarn obtained for 5600 yards was 12.8%, and as a result of measuring the yarn physical properties corresponding to the weaving property, the number of fluffs of 1 mm or more was 76 pieces / m, and the abrasion strength was The result was good at 411 times, and the weaving efficiency was 94.3%, which was satisfactory.
Further, the weaving property after being left under high humidity was measured by the same method as in Example 1, and as a result, it was as good as 90.9%. Table 2 shows the results.
[0021]
Comparative Example 2
Gluing was carried out in the same manner as in Example 4 except that commercial PVA (Kurarepovar 217 + Kuraray Povar 205: 35 parts + 35 parts) was used instead of the ethylene-modified PVA used in Example 4, and the knitted fabric was subjected to weaving.
The size of the obtained glued yarn was 13.7%, and the yarn properties corresponding to the weaving property were measured. As a result, the number of fluffs of 1 mm or more was 75 pieces / m, the abrasion strength was 206 times, and the weaving efficiency was high. Was also relatively good at 90.2%.
Further, as a result of performing the weaving property after being left in a high humidity environment in the same manner as in Example 1, the opening property of the warp at the time of weaving becomes poor due to moisture absorption, and the fluffing about 0.5 hour after the start of weaving. Balls were generated, warp breakage and weft stoppage occurred frequently, and the average weaving efficiency for 2 days was 72.1%, which was poor. Table 2 shows the results.
[0022]
Comparative Example 3
Gluing was carried out in the same manner as in Example 5, except that commercial PVA (Kurarepovar 217 + Kuraray Povar 205: 40 parts + 40 parts) was used in place of the ethylene-modified PVA used in Example 5, and the resultant was subjected to weaving.
The size of the obtained glued yarn was 13.1%, and the yarn properties corresponding to the weaving property were measured. As a result, the number of fluffs of 1 mm or more was 86 pieces / m, the abrasion strength was 396 times, and the weaving efficiency was high. Was also relatively good at 89.9%.
Further, as a result of performing the weaving property after being left in a high humidity environment in the same manner as in Example 1, the opening property of the warp at the time of weaving becomes poor due to moisture absorption, and the fluffing about 0.5 hour after the start of weaving. Balls were generated, warp breakage and weft stoppage frequently occurred, and the average weaving efficiency for 2 days was poor at 69.8%. Table 2 shows the results.
[0023]
In the above Examples and Comparative Examples, the value expressed as the amount of glue is described in “Glue of warp yarn” (Kaname Fukada, Teruhiko Kazumi, published by The Japan Textile Machinery Society) pages 299-302. This is a value measured by a method of correcting a part of the fluff that has fallen off during the cleaning. The number of fluff is a value measured using a fluff counter (DK-103 made by Daiwabo) for 1 mm or more. The abrasion strength is a value obtained by measuring the number of times until cutting is performed with a load of 100 g / piece using a TM-type embracing force tester (manufactured by Daiei Kagaku Seiki Seisaku-sho, Ltd.).
[0024]
[Table 1]

[0025]
[Table 2]

[0026]
【The invention's effect】
The warp sizing agent of the present invention can provide a sized yarn having physical properties that can withstand high-speed weaving, and is excellent in the unwinding property and opening property of the sized yarn even when the sized yarn beam is stored under high temperature and high humidity. It has a very high industrial value in that weaving efficiency can be greatly improved.

Claims (1)

分子内にエチレン単位を１〜２４モル％含有する変性ポリビニルアルコールとでんぷん類を主剤とした経糸糊剤。A warp sizing agent mainly comprising modified polyvinyl alcohol containing 1 to 24 mol% of ethylene units in the molecule and starch.