JP3991476B2 - Cellulosic fiber-containing fabric - Google Patents

Description

ここで、Ｒ₁ 、Ｒ₂ は、−Ｈ、炭素数１〜４のアルキル基または−ＣＨ₂ ＯＲ₇ のいずれかである、同種または異種の基であり、Ｒ₃ 、Ｒ₄ 、Ｒ₅ 、Ｒ₆ は、−Ｈまたは−ＯＲ8 のいずれかである、同種または異種の基であり、Ｒ₇ 、Ｒ₈ は、−Ｈまたは炭素数１〜４のアルキル基のいずれかである、同種または異種の基であることを示す。
【００１２】
かかる架橋剤のセルロース系繊維への付与方法としては、一般の各種の手段を採用することができ、具体的には、架橋剤をガス状にして付与する方法、パディング法、浸漬法、スプレー法、プリント法、コーティング法、グラビア加工法、泡加工法等が使用されるが、なかでも、架橋剤がホルムアルデヒドの場合には、ガス状にして付与する方法が、また、架橋剤が繊維素反応型樹脂、ポリカルボン酸類、イソシアネート類等である場合には、パディング法が、それぞれ好ましく使用される。
【００１３】
かかる架橋剤によるセルロース系繊維の架橋改質の方法としては、一般の架橋改質方法が採用することができ、具体的には、縫製品の状態にしたセルロース系繊維含有布帛に対しホルムアルデヒドで気相処理する方法、布帛の状態のままのセルロース系繊維含有布帛に対し上述の架橋剤を付与し、縫製した後、加熱処理を施すポストキュア法、布帛の状態のままのセルロース系繊維含有布帛に対し上述の架橋剤を付与して熱処理まで行うプレキュア法等が使用されるが、これらに限定されるものではない。なお、熱処理温度としては、好ましくは８０〜２２０℃の範囲の条件が使用される。
【００１４】
セルロース系繊維の架橋改質を行うにあたり、架橋剤の反応を促進する目的で、触媒を併用することも好ましく行われ、具体的には、有機酸、有機アミン塩、塩化マグネシウム、硝酸亜鉛、ホウフッ化亜鉛、硝酸マグネシウム、塩化亜鉛等の金属塩などを用いることができる。
【００１５】
本発明のセルロース系繊維含有布帛は、かかる方法により架橋改質されたセルロース系繊維を含むものであるが、その改質の程度は、下記式で定義される架橋指数が１〜４の範囲内、好ましくは２〜３．５の範囲内にあるものが採用される。
【００１６】
架橋指数＝（Ａ−Ｂ）
ここで、Ａ：温度３０℃、相対湿度９０％ＲＨ雰囲気下での架橋改質後のセルロース系繊維の吸湿率（％）。
【００１７】
Ｂ：温度２０℃、相対湿度６５％ＲＨ雰囲気下での架橋改質後のセルロース系繊維の吸湿率（％）。
【００１８】
かかる架橋指数は、架橋改質後のセルロース系繊維の温度３０℃、相対湿度９０％ＲＨ雰囲気下で吸湿率の値から温度２０℃、相対湿度６５％ＲＨ雰囲気下で吸湿率の値を差し引いて算出されるものであり、セルロース系繊維がどの程度架橋改質されているかを知る上での指標となる。すなわち、これは、架橋改質によりセルロース分子中の水酸基が封鎖され、結果として吸湿率の値が低下することを利用したものである。この指数が小さいものほど架橋改質の度合いが大きく、大きいものほど架橋改質の度合いが小さい。一般に未加工の木綿、麻で４〜５程度である。
【００１９】
かかる架橋指数が、１より小さい場合、架橋が過度に形成され、布帛の強力や柔軟性が低下し、形態安定性は良好であるものの、実用に耐えないものとなってしまう。布帛の強力や柔軟性が低下する場合、それらを改善する目的で、一般にはアミノ変性シリコーン系柔軟剤等による処理が行われるが、アミノ変性シリコーン等の柔軟剤を併用した場合、それらが疎水性であるため、それによって処理された布帛の吸水性が低下し、実際に衣料として着用した場合、吸汗性の悪い、着心地感の悪いものとなってしまう。一方、架橋指数が４より大きい場合は、セルロース繊維の架橋改質が十分でなく、必要とされるレベルの防しわ性、防縮性等の形態安定性能が付与できない。布帛の強力、柔軟性と形態安定性のバランスを考えた場合には、該架橋指数が、２〜３．５の範囲内にあるものがより好ましく使用される。
【００２０】
また、本発明のセルロース系繊維含有布帛は、ＪＩＳ Ｌ−１０９６バイレック法で測定した吸水性が５０ｍｍ以上であるものである。吸水性が５０ｍｍに満たない場合、かかる布帛を縫製して得られた衣料は、吸汗性の悪い、着心地感の悪いものとなってしまう。
【００２１】
次に、本発明でいう抗菌性樹脂とは、１価および／または２価のリン酸エステル基ならびに水酸基を有しリン酸エステル基が４級アンモニウム塩化されたビニル共重合体からなるものであり、下記化学式２または３で示される構造を有するものである。
【００２２】
【化３】

【化４】

上記の化学式中、〜Ｐは高分子主鎖を示し、Ｒ' 、Ｒ''、Ｒ''' は、有機基を示し、Ｒ₁ は、炭素数８〜１８のアルキル基または置換アリール基を示し、Ｒ₂ は、炭素数１〜１８のアルキル基、フェニル基または置換アリール基を示す。
【００２３】
かかる抗菌性樹脂は、例えば、１価および／または２価のリン酸エステル基を有するビニルモノマに第３級アミンを反応させ、該リン酸エステル基をアミン塩としてから水酸基を有するビニルモノマおよび第３成分のビニルモノマとを共重合させたのち、１価のグリシジル化合物を反応せしめ、第４級アンモニウム塩化することで得られる。
【００２４】
かかる抗菌性樹脂は、そのポリマ側鎖に水酸基を有しているため、架橋剤を用いて分子間および／またはセルロース系繊維との間を架橋させることで、より洗濯耐久性に優れた抗菌防臭性能を有する布帛を提供することができる。かかる架橋剤としては、セルロース系繊維の架橋改質に用いるものと同様のものを使用することができが、具体的には、ホルムアルデヒドや、ジメチロールエチレン尿素、ジメチロールトリアゾン、ジメチロールウロン、ジメチロールグリオキザールモノウレイン、ジメチロールプロピレン尿素、これらのメチロール基の一部または全部をメトキシ化、エトキシ化したもの等の繊維素反応型樹脂、ポリカルボン酸類、イソシアネート類等を使用することができる。
【００２５】
かかる抗菌性樹脂および架橋剤の布帛への付与方法としては、一般の各種の手段が採用することができ、具体的には、パディング法、浸漬法、スプレー法、プリント法、コーティング法、グラビア加工法、泡加工法等の手段を使用することができるが、作業効率の面からは、セルロース繊維の架橋改質用架橋剤と同時付与、同時処理が好ましく採用される。
【００２６】
かかる抗菌性樹脂の含有量は、繊維重量に対して０．２〜１０ｗｔ％であることが好ましい。含有量が０．２ｗｔ％に満たないと十分な抗菌防臭性が得られないし、また、１０ｗｔ％を越えると布帛の風合いが粗硬なものとなってしまうばかりでなく、コストも高くなる。
【００２７】
本発明においては、布帛の柔軟性を向上させる目的で、シリコーン系柔軟剤を付与するとことも好ましく行われる。ただし、通常一般に用いられてるシリコーン系柔軟剤、とりわけアミノアルキル基含有ポリシロキサンを主成分とするアミノ変性シリコーン系柔軟剤を用いて布帛を処理した場合、処理された布帛の柔軟性やその効果の耐久性は優れるものの、処理布帛が撥水性を示すようになり、本発明の防しわ性、防縮性等の形態安定性能と吸水性を兼ね備えたセルロース系繊維含有布帛に適用するには不向きである。
【００２８】
従って、本発明におけるシリコーン系柔軟剤は、該布帛の吸水性を阻害することなく、柔軟な風合いを与えるものが好ましく、具体的には、１分子中にアミノ基とポリオキシアルキル基の両方を含有するオルガノポリシロキサンと、分子中にアミンまたは水酸基と反応可能な基を少なくとも１個含有するポリエチレンポリアミン高級脂肪酸型アミド化合物とを主成分とするものが好ましく使用される。
【００２９】
かかるオルガノポリシロキサンは、１分子中にアミノ基とポリオキシアルキル基の両方を含有するもの、すなわちアミノポリエーテル変性シリコーンであれば特に限定されるものではないが、好ましくは２５℃における粘度が１００〜１０００００ｃｓｔ、さらにアミノ等量が３００〜３０００の範囲にあるものが好ましく使用される。
【００３０】
また、アミノポリエーテル変性シリコーンのアミノ基は、黄変防止のため該アミノ基と反応性を有する化合物、有機酸または有機酸の無水物もしくは塩化物等により該アミノ基の一部もしくは全部が封鎖されていてもよい。
【００３１】
また、ポリエチレンポリアミン高級脂肪酸型アミド化合物としては、ポリエチレンポリアミン高級脂肪酸アミド、ポリエチレンポリアミン高級脂肪酸アミドの尿素縮合物、ポリエチレンポリアミン高級脂肪酸型アミド部分のイミダゾリニウム塩などとジカルボン酸、環状酸無水物、ジグリシジルエーテル、ジイソシアネート等との反応物などが使用される。
【００３２】
これらの構成成分であるポリエチレンポリアミンとしては、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンベンタミン、アミノエチルエタノールアミンなどが使用される。高級脂肪酸としては、パーム油、牛脂、ナタネ油、米糠油、魚油などの天然油脂由来のものが一般的であるが、化学的に合成した高級脂肪酸も使用することができる。これらのうち好ましいものは、ヨウ素価が５０以下で炭素数が１２〜２４の高級脂肪酸である。ジカルボン酸、環状酸無水物としては、マレイン酸、無水マレイン酸、フマル酸、リンゴ酸、コハク酸、無水コハク酸、酒石酸、フタル酸、無水フタル酸などが使用される。ジグリシジルエーテルとしては、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリオキシアルキレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテルなどを使用することができる。ジイソシアネートとしては、トリレンジイソシアネート、キシレンジイソシアネート、ジフェニルメタンジイソシアネート等の芳香族ジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、リジンジイソシアネート等の脂肪族ジイソシアネートなどを使用することができる。
【００３３】
ポリエチレンポリアミン高級脂肪酸型アミド化合物を構成するポリエチレンポリアミンと高級脂肪酸のモル比は、好ましくは１：１．０〜２．５、さらに好ましくは１：１．２〜１．８である。
【００３４】
かかるシリコーン系柔軟剤の主成分であるアミノポリエーテル変性シリコーンとポリエチレンポリアミン高級脂肪酸アミドの重量比は、好ましくは１：０．２〜１．５、さらに好ましくは１：０．３〜１．０である。ポリエチレンポリアミン高級脂肪酸アミドが０．２未満の場合には、十分な柔軟性が得られず、また、１．５を越える場合は、処理された布帛の吸水性が低下するので好ましくない。かかるシリコーン系柔軟剤の繊維重量に対する付着量は、０．０６〜１．０ｗｔ％の範囲であることが好ましい。付着量が０．０６ｗｔ％未満の場合、布帛に十分な柔軟性、平滑性を付与することが困難であり、また１．０ｗｔ％より大きい場合には、柔軟性、平滑性は向上するものの、目ズレなどの欠点を引き起こす原因となる。
【００３５】
本発明においては、布帛の吸水性を向上させる目的で親水性樹脂、好ましくは親水性ポリエステル樹脂を付与する。中でもポリアルキレングリコール−ポリエステルブロック共重合体を主成分とするものが、より好ましく使用される。ここでいうポリアルキレングリコールとは、分子中に−Ｃ_n Ｈ_2nＯ−（ｎ＝２〜４）なる主鎖を有するものを意味するものであり、具体的にはポリエチレングリコール、ポリプロピレングリコール、または、これらのブロックポリマー等を使用することができる。かかるポリアルキレングリコールの分子量は、好ましくは３００〜４００００、より好ましくは１０００〜１００００の範囲にあるものが使用される。分子量が３００に満たない場合、繊維への付着耐久性が不十分になる傾向にあり、分子量が４００００を越えると、分散性が低下する傾向にある。
【００３６】
また、かかるポリアルキレングリコールをブロック共重合するポリエステルとは、芳香族ジカルボン酸とアルキレングリコールからなるものが好ましく使用される。かかる芳香族ジカルボン酸としては、例えばテレフタル酸、テレフタル酸の低級アルキルエステル、イソフタル酸、イソフタル酸の低級アルキルエステル等が使用される。また、アルキレングリコールとしては、例えばエチレングリコール、プロピレングリコール、ブチレングリコール等が使用される。
【００３７】
かかる親水性ポリエステル樹脂の繊維重量に対する付着量は、０．０３〜１．０ｗｔ％の範囲であることが好ましい。付着量が０．０３ｗｔ％未満の場合、親水性ポリエステル樹脂を付与したことによる効果は少なく、また１．０ｗｔ％より大きい場合には、布帛の吸水性は向上するものの、布帛にヌメリ感が起こり、また染色堅牢度低下の原因ともなる。
【００３８】
本発明のセルロース系繊維含有布帛を用いてなる繊維製品は、防しわ性、防縮性等の形態安定性、吸水性、抗菌防臭性に優れており、ドレスシャツ、学童用スクールシャツ、ユニフォーム、婦人衣料、スポーツ衣料、下着類、靴下類等の用途に好適である。
【００３９】
【実施例】
以下、実施例により、さらに詳細に説明する。
【００４０】
評価には、常法により精錬、漂白、マーセライズを行った、タテ・ ヨコ ４５番手のポリエステル４５％、綿５５％からなる目付１１２ｇ／ｍ² のブロード織物を用いた。かかる織物を架橋剤、触媒、抗菌性樹脂、シリコーン系柔軟剤、親水性ポリエステル樹脂等を含む加工液に浸漬し、絞り率８０％でパディングした後、１００℃×２分予備乾燥し、ついで１７０℃×１分熱処理して、試料を得た。
【００４１】
なお、実施例中の架橋剤、触媒、抗菌性樹脂、シリコーン系柔軟剤、親水性ポリエステル樹脂としては、以下のものを用いた。
【００４２】
架橋剤：ジメチロールジヒドロキシエチレン尿素樹脂水溶液（固形分２０％）
触媒：塩化マグネシウム
抗菌性樹脂：リン酸エステル基を有するビニルモノマとして下記化学式４で示される化合物を３６部と、第３級アミンとしてＮ, Ｎ−ジメチルラウリルアミン３９部とを反応させ、リン酸エステル基をアミン塩としてから、水酸基を有するビニルモノマとして、２−ヒドロキシエチルアクリレート２４部、および、第３成分のビニルモノマとして、メトキシポリエチレングリコールメタクリレー（エチレングリコール繰り返し単位２３）６０部と共重合させた後、１価のグリシジル化合物として、ｎ−ブチルグリシジルエーテルを用いて、４級アンモニウム塩化した化合物を用いた。
【００４３】
【化５】

シリコーン系柔軟剤：アミノポリエーテル変性シリコーン（粘度３００ｃｓｔ、アミノ当量４０００）１０部、ジエチレントリアミンとステアリン酸と無水マレイン酸とのアミド化合物３部、水８７部 からなるエマルジョン（固形分２０％）、比較として市販のアミノ変性シリコーン系柔軟剤も使用した。
【００４４】
親水性ポリエステル樹脂：ジメチルテレフタレート５００部、エチレングリコール４００部、ポリエチレングリコール（分子量３０００）の共重合エマルジョン（固形分１０％）を用いた。
【００４５】
実施例および比較例中の評価は、下記の方法で行った。
【００４６】
［架橋指数］
架橋指数＝（Ａ−Ｂ）
ここで、Ａ：温度３０℃、相対湿度９０％ＲＨ雰囲気下での架橋改質後のセルロース系繊維の吸湿率（％）。
【００４７】
Ｂ：温度２０℃、相対湿度６５％ＲＨ雰囲気下での架橋改質後のセルロース系繊維の吸湿率（％）。
【００４８】
［吸水性（バイレック法）］
ＪＩＳ Ｌ−１０９６ バイレック法 で吸水高さを測定した。数値が大きいほど、吸水性が良好なことを示す。
【００４９】
［吸水性（滴下法）］
ＪＩＳ Ｌ−１０１８ Ａ法 滴下法 で吸水時間を測定した。数値が小さいほど、吸水性が良好なことを示す。
【００５０】
［防しわ性］
ＡＡＴＣＣ−１２４−１９８４ ５段階レプリ法に基づいて判定を行った。
【００５１】
５級（良好）〜１級（不良）
［洗濯収縮］
ＪＩＳ Ｌ−１０４２ Ｇ法 家庭洗濯法で布帛のタテ方向、ヨコ方向の収縮率を測定した。なお、洗濯後は脱水機で絞らずに、乾燥ろ紙の間にはさみ、軽く押さえて脱水し、水平に置いた金網の上で乾燥した。
【００５２】
［引裂強力］
ＪＩＳ Ｌ−１０９６ Ｄ法 ペンジュラム法で布帛のタテ糸切断方向、ヨコ糸切断方向の引裂強力を測定した。
【００５３】
［風合い］
ハンドリングにより以下の基準で評価した。
【００５４】
○ ：柔軟性に富んだ風合いである。
【００５５】
△ ：やや粗硬感で、芯の残る風合いである。
【００５６】
× ：粗硬で、柔軟性の全くない風合いである。
【００５７】
［抗菌性］
菌数測定法により評価した。試験菌として黄色ブドウ球菌（stapylococcus aureus 209p ）を用い、滅菌試料布上に上記試験菌のブイヨン懸濁液を注加し、密閉容器注で３７℃、１８時間培養後の生菌数を測定した。合格レベルは、測定結果から次の基準に従って判定した。
【００５８】
ｌｏｇ（Ｂ／Ａ）＞２の条件下、ｌｏｇ（Ｂ／Ｃ）を菌数増減値差とし、１．６以上を合格レベルとした。ただしＡは未加工品の接種直後分散回収した菌数、Ｂは未加工品の１８時間培養後分散回収した菌数、Ｃは加工品の１８時間培養後分散回収した菌数をあらわす。
【００５９】
実施例１〜３
表１に示された組成の加工液を用い、試料を作製した。評価結果を併せて表１に示す。
【００６０】
比較例１〜４
表１に示された組成の加工液を用い、試料を作製した。評価結果を併せて表１に示す。
【００６１】
表１から、比較例１および３の布帛は、架橋指数が４より大きく、十分な形態安定性能が得られないことがわかる。比較例２の布帛は、抗菌性樹脂を含まない加工液で処理した布帛についての結果であるが、上記判定基準より抗菌性能が合格レベルに達していないことがわかる。比較例４の布帛は、従来一般のアミノ変性シリコーン樹脂で処理して得られた布帛であるが、十分な吸水性が得られていないことがわかる。
【００６２】
【表１】

【００６３】
【発明の効果】
本発明によれば、防しわ性、防縮性等の形態安定性能と吸水性を兼ね備えたセルロース系繊維含有布帛を安定して提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a fabric containing a cellulosic fiber that has been modified by crosslinking and an antibacterial resin.
[0002]
[Prior art]
BACKGROUND ART Conventionally, fabrics containing cellulosic fibers have been widely used in various fields such as clothing because they have various advantages such as high water absorption and good touch. On the other hand, however, there are drawbacks such as wrinkles and shrinkage due to washing as compared with synthetic fiber fabrics, and various processes have been studied for the purpose of improving these. Among them, a method for imparting shape stability performance such as wrinkle resistance and shrinkage resistance is widely performed by using a crosslinking agent such as formaldehyde or a fibrin-reactive resin to crosslink and modify cellulose fibers. If this modification is excessively performed, the flexibility of the fabric is reduced due to the formation of crosslinks, and therefore treatment with an amino-modified silicone softener is generally required. However, when softening agents such as amino-modified silicones are used in combination, they are hydrophobic, so the water absorption of the treated fabric is lowered, and when actually worn as clothing, the sweat absorption is poor and the feeling of comfort. There was a problem that it would be bad. On the other hand, if the cross-linking modification is not sufficiently performed, the present state is that the required level of form-stabilizing performance such as wrinkle resistance and shrinkage resistance cannot be imparted.
[0003]
In addition, fabrics that have undergone such form-stabilized processing generally tend to be stuffy due to a decrease in hygroscopicity, and when worn as clothes in summer and other times, they tend to become sweaty due to the propagation of various bacteria. There were also drawbacks.
[0004]
[Problems to be solved by the invention]
In view of such a background, the present invention is to provide a cellulosic fiber-containing fabric having both shape stability performance such as wrinkle resistance and shrinkage resistance and water absorption, and also excellent antibacterial and deodorant properties.
[0005]
[Means for Solving the Problems]
The present invention employs the following means in order to solve such problems. That is, the cellulosic fiber-containing fabric of the present invention is a fabric containing cellulosic fibers subjected to cross-linking modification, and the cross-linking index defined by the following formula of the fabric is 1 to 4, and the fabric The water absorption of the fabric is 50 mm or more when measured according to JIS L-1096 Bayrec method, and the fabric has a monovalent and / or divalent phosphate group and a hydroxyl group, and the phosphorus It is characterized by containing an antibacterial resin made of a vinyl copolymer in which the acid ester group is quaternary ammonium salified.
[0006]
Cross-linking index = (A−B)
Here, A: moisture absorption rate (%) of the cellulosic fiber after cross-linking modification in an atmosphere of a temperature of 30 ° C. and a relative humidity of 90% RH.
[0007]
B: Moisture absorption rate (%) of the cellulosic fiber after cross-linking modification under an atmosphere of a temperature of 20 ° C. and a relative humidity of 65% RH.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The present invention has been studied on the above-mentioned problem, that is, a cellulosic fiber-containing fabric having both shape stability performance such as wrinkle resistance and shrinkage resistance and water absorption, and excellent antibacterial and deodorant properties. It has been clarified that such a problem can be solved at once by a combination with a fiber-containing fabric, a water absorption level and a specific antibacterial resin.
[0009]
The cellulosic fiber-containing fabric referred to in the present invention is a fabric containing natural cellulose fibers such as cotton, hemp, and pulp, and regenerated cellulose fibers such as viscose rayon, and polyester such as polyethylene terephthalate and polybutylene terephthalate. Blended fibers, blended fibers such as polyamide fibers such as nylon 6 and nylon 66, polyolefin fibers such as polyethylene and polypropylene, protein fibers such as wool and silk, polyvinyl chloride fibers, vinylon fibers, acetate fibers, etc. Also included are those used in combination with weaving and knitting. In addition, from the aspect of the effect to be obtained, when mixed with other fibers, it is preferable that the cellulosic fibers contain 10 wt% or more by fiber weight.
[0010]
As a crosslinking agent used for crosslinking modification, it reacts with hydroxyl groups in cellulose molecules constituting cellulosic fibers, particularly wrinkles during washing, and hydroxyl groups in an amorphous region that cause shrinkage, and between cellulose molecules and molecules. It is a compound that can form a cross-link in the inside, specifically formaldehyde, dimethylol ethylene urea, dimethylol triazone, dimethylol uron, dimethylol glyoxal monourene, dimethylol propylene urea, these Fibrin-reactive resins such as those obtained by methoxylation or ethoxylation of some or all of the methylol groups, polycarboxylic acids, isocyanates and the like are used. Among these crosslinking agents, formaldehyde or a compound represented by the following chemical formula 1 is preferably used in order to more efficiently and effectively perform crosslinking modification of cellulosic fibers.
[0011]
[Chemical 2]

Here, R ₁ and R ₂ are the same or different groups that are either —H, an alkyl group having 1 to 4 carbon atoms, or —CH ₂ OR ₇ , and R ₃ , R ₄ , R ₅ , R ₆ is the same or different group that is either —H or —OR ₈ , and R ₇ and R ₈ are either the same or different group that is either —H or an alkyl group having 1 to 4 carbon atoms. It is a group of
[0012]
As a method for applying such a crosslinking agent to the cellulose fiber, various general means can be employed. Specifically, a method in which the crosslinking agent is applied in a gaseous state, a padding method, a dipping method, a spray method. , Printing method, coating method, gravure processing method, foam processing method, etc. are used. Especially, when the cross-linking agent is formaldehyde, the method of applying it in the form of gas is used. In the case of mold resins, polycarboxylic acids, isocyanates, etc., the padding method is preferably used.
[0013]
As a method for cross-linking modification of cellulosic fibers with such a cross-linking agent, a general cross-linking modification method can be employed. Specifically, the cellulosic fiber-containing fabric in the form of a sewn product is exposed with formaldehyde. Phase treatment method, post-cure method in which the above-mentioned crosslinking agent is applied to the fabric containing cellulosic fibers in the state of the fabric, sewing, and then heat treatment is applied to the cellulosic fiber-containing fabric in the state of the fabric On the other hand, a precure method or the like in which the above-described cross-linking agent is applied and the heat treatment is performed is used, but is not limited thereto. In addition, as heat processing temperature, the conditions of the range of 80-220 degreeC are used preferably.
[0014]
In carrying out cross-linking modification of cellulosic fibers, it is also preferable to use a catalyst in combination for the purpose of accelerating the reaction of the cross-linking agent. Specifically, organic acids, organic amine salts, magnesium chloride, zinc nitrate, borofluoride are used. Metal salts such as zinc halide, magnesium nitrate, and zinc chloride can be used.
[0015]
The cellulosic fiber-containing fabric of the present invention contains cellulosic fibers crosslinked and modified by such a method, and the degree of modification is preferably within the range of a crosslinking index defined by the following formula of 1 to 4. Is within the range of 2 to 3.5.
[0016]
Cross-linking index = (A−B)
Here, A: moisture absorption rate (%) of the cellulosic fiber after cross-linking modification in an atmosphere of a temperature of 30 ° C. and a relative humidity of 90% RH.
[0017]
B: Moisture absorption rate (%) of the cellulosic fiber after cross-linking modification under an atmosphere of a temperature of 20 ° C. and a relative humidity of 65% RH.
[0018]
The crosslinking index is obtained by subtracting the value of the moisture absorption rate at a temperature of 20 ° C. and a relative humidity of 65% RH from the value of the moisture absorption rate at a temperature of 30 ° C. and a relative humidity of 90% RH. It is calculated and serves as an index for knowing how much the cellulosic fiber is crosslinked and modified. That is, this utilizes the fact that the hydroxyl group in the cellulose molecule is blocked by the cross-linking modification, and as a result, the value of the moisture absorption rate decreases. The smaller the index, the greater the degree of crosslinking modification, and the greater the index, the smaller the degree of crosslinking modification. Generally, it is about 4 to 5 for raw cotton and hemp.
[0019]
When the cross-linking index is less than 1, the cross-linking is excessively formed, the strength and flexibility of the fabric is lowered, and the shape stability is good, but it is not practical. When the strength and flexibility of the fabric are reduced, treatment with an amino-modified silicone softener is generally performed for the purpose of improving them. However, when a softener such as amino-modified silicone is used in combination, they are hydrophobic. Therefore, the water absorption of the treated fabric is lowered, and when it is actually worn as a garment, the sweat absorbency is poor and the feeling of comfort is poor. On the other hand, when the cross-linking index is greater than 4, the cellulose fiber is not sufficiently cross-linked and the required level of form-stabilizing performance such as wrinkle resistance and shrinkage resistance cannot be imparted. In consideration of the balance of strength, flexibility and shape stability of the fabric, those having a crosslinking index in the range of 2 to 3.5 are more preferably used.
[0020]
The cellulose fiber-containing fabric of the present invention has a water absorption of 50 mm or more as measured by the JIS L-1096 birec method. If the water absorption is less than 50 mm, the clothing obtained by sewing such a fabric has poor sweat absorption and poor comfort.
[0021]
Next, the antibacterial resin referred to in the present invention comprises a vinyl copolymer having a monovalent and / or divalent phosphate group and a hydroxyl group, and the phosphate group is quaternary ammonium salified. And having a structure represented by the following chemical formula 2 or 3.
[0022]
[Chemical 3]

[Formula 4]

In the above chemical formula, ˜P represents a polymer main chain, R ′, R ″, R ′ ″ represents an organic group, and R ₁ represents an alkyl group having 8 to 18 carbon atoms or a substituted aryl group. R ₂ represents an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a substituted aryl group.
[0023]
Such an antibacterial resin is obtained by, for example, reacting a tertiary amine with a vinyl monomer having a monovalent and / or divalent phosphate ester group, converting the phosphate ester group into an amine salt, and then a vinyl monomer having a hydroxyl group and a third component. It is obtained by copolymerizing with a vinyl monomer and then reacting with a monovalent glycidyl compound, followed by quaternary ammonium chloride.
[0024]
Since such an antibacterial resin has a hydroxyl group in its polymer side chain, the antibacterial and deodorant with better washing durability can be obtained by crosslinking between molecules and / or cellulosic fibers using a crosslinking agent. A fabric having performance can be provided. As such a cross-linking agent, the same ones used for cross-linking modification of cellulosic fibers can be used. Specifically, formaldehyde, dimethylol ethylene urea, dimethylol triazone, dimethylol uron, Fibrin-reactive resins such as dimethylol glyoxal monourein, dimethylol propylene urea, methoxylated or ethoxylated part or all of these methylol groups, polycarboxylic acids, isocyanates, etc. can be used. .
[0025]
As a method for applying the antibacterial resin and the crosslinking agent to the fabric, various general means can be employed. Specifically, padding, dipping, spraying, printing, coating, gravure processing However, from the viewpoint of work efficiency, simultaneous application and simultaneous treatment with a crosslinking agent for crosslinking modification of cellulose fibers are preferably employed.
[0026]
The content of the antibacterial resin is preferably 0.2 to 10 wt% with respect to the fiber weight. If the content is less than 0.2 wt%, sufficient antibacterial and deodorizing properties cannot be obtained. If the content exceeds 10 wt%, not only the texture of the fabric becomes rough but also the cost increases.
[0027]
In the present invention, for the purpose of improving the flexibility of the fabric, it is also preferable to apply a silicone softener. However, when a fabric is treated with a commonly used silicone softener, particularly an amino-modified silicone softener based on an aminoalkyl group-containing polysiloxane, the flexibility of the treated fabric and its effects Although the durability is excellent, the treated fabric comes to exhibit water repellency, and is unsuitable for application to a cellulosic fiber-containing fabric having both shape stability performance such as wrinkle resistance and shrinkage resistance and water absorption of the present invention. .
[0028]
Accordingly, the silicone softener in the present invention is preferably one that gives a soft texture without impairing the water absorption of the fabric. Specifically, both an amino group and a polyoxyalkyl group are contained in one molecule. Those containing as a main component an organopolysiloxane containing and a polyethylene polyamine higher fatty acid amide compound containing at least one group capable of reacting with an amine or a hydroxyl group in the molecule are preferably used.
[0029]
Such an organopolysiloxane is not particularly limited as long as it contains both an amino group and a polyoxyalkyl group in one molecule, that is, an amino polyether-modified silicone, but preferably has a viscosity at 25 ° C. of 100. Those having ˜100,000 cst and further amino equivalents in the range of 300 to 3,000 are preferably used.
[0030]
The amino group of the amino polyether-modified silicone is partially or completely blocked by a compound having reactivity with the amino group, an organic acid, an organic acid anhydride or chloride to prevent yellowing. May be.
[0031]
Further, as the polyethylene polyamine higher fatty acid type amide compound, polyethylene polyamine higher fatty acid amide, urea condensate of polyethylene polyamine higher fatty acid amide, imidazolinium salt of polyethylene polyamine higher fatty acid type amide part and dicarboxylic acid, cyclic acid anhydride, A reaction product with diglycidyl ether, diisocyanate or the like is used.
[0032]
Diethylenetriamine, triethylenetetramine, tetraethylenebentamine, aminoethylethanolamine, etc. are used as the polyethylene polyamine which is these constituent components. Higher fatty acids are generally derived from natural fats and oils such as palm oil, beef tallow, rapeseed oil, rice bran oil, and fish oil, but chemically synthesized higher fatty acids can also be used. Among these, higher fatty acids having an iodine value of 50 or less and 12 to 24 carbon atoms are preferable. As the dicarboxylic acid and cyclic acid anhydride, maleic acid, maleic anhydride, fumaric acid, malic acid, succinic acid, succinic anhydride, tartaric acid, phthalic acid, phthalic anhydride and the like are used. As the diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyoxyalkylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and the like can be used. Examples of the diisocyanate include aromatic diisocyanates such as tolylene diisocyanate, xylene diisocyanate, and diphenylmethane diisocyanate, and aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.
[0033]
The molar ratio of the polyethylene polyamine and the higher fatty acid constituting the polyethylene polyamine higher fatty acid type amide compound is preferably 1: 1.0 to 2.5, more preferably 1: 1.2 to 1.8.
[0034]
The weight ratio of aminopolyether-modified silicone, which is the main component of such a silicone softener, and polyethylenepolyamine higher fatty acid amide is preferably 1: 0.2 to 1.5, more preferably 1: 0.3 to 1.0. It is. When the polyethylene polyamine higher fatty acid amide is less than 0.2, sufficient flexibility cannot be obtained, and when it exceeds 1.5, the water absorption of the treated fabric is lowered, which is not preferable. It is preferable that the adhesion amount with respect to the fiber weight of such a silicone type softening agent is in the range of 0.06 to 1.0 wt%. When the adhesion amount is less than 0.06 wt%, it is difficult to impart sufficient flexibility and smoothness to the fabric, and when it is greater than 1.0 wt%, the flexibility and smoothness are improved. This causes defects such as eye misalignment.
[0035]
In the present invention, a hydrophilic resin, preferably a hydrophilic polyester resin is added for the purpose of improving the water absorption of the fabric. Among them, those having a polyalkylene glycol-polyester block copolymer as a main component are more preferably used. The polyalkylene glycol here means one having a main chain of —C _n H _2n O— (n = 2 to 4) in the molecule, specifically, polyethylene glycol, polypropylene glycol, or These block polymers can be used. The molecular weight of such polyalkylene glycol is preferably 300 to 40000, more preferably 1000 to 10,000. When the molecular weight is less than 300, the adhesion durability to the fiber tends to be insufficient, and when the molecular weight exceeds 40000, the dispersibility tends to decrease.
[0036]
Moreover, what consists of aromatic dicarboxylic acid and alkylene glycol is preferably used as polyester which carries out block copolymerization of this polyalkylene glycol. Examples of the aromatic dicarboxylic acid include terephthalic acid, lower alkyl esters of terephthalic acid, isophthalic acid, and lower alkyl esters of isophthalic acid. Moreover, as alkylene glycol, ethylene glycol, propylene glycol, butylene glycol etc. are used, for example.
[0037]
The adhesion amount of the hydrophilic polyester resin with respect to the fiber weight is preferably in the range of 0.03 to 1.0 wt%. When the adhesion amount is less than 0.03 wt%, the effect of applying the hydrophilic polyester resin is small. When the adhesion amount is greater than 1.0 wt%, the water absorption of the fabric is improved, but the cloth has a slimy feeling. Moreover, it also causes a decrease in dyeing fastness.
[0038]
The fiber product using the cellulosic fiber-containing fabric of the present invention is excellent in form stability such as wrinkle resistance and shrinkage resistance, water absorption, antibacterial and deodorant properties, dress shirts, school shirts for school children, uniforms, women It is suitable for uses such as clothing, sports clothing, underwear and socks.
[0039]
【Example】
Hereinafter, an example explains in detail.
[0040]
For the evaluation, a broad woven fabric having a basis weight of 112 g / m ² made of 45% polyester and 55% cotton, which had been refined, bleached and mercerized by a conventional method, was used. The woven fabric is immersed in a processing solution containing a crosslinking agent, a catalyst, an antibacterial resin, a silicone softener, a hydrophilic polyester resin, etc., padded at a drawing rate of 80%, preliminarily dried at 100 ° C. for 2 minutes, and then 170. A sample was obtained by heat treatment at 1 ° C. for 1 minute.
[0041]
In addition, the following were used as the crosslinking agent, catalyst, antibacterial resin, silicone softener, and hydrophilic polyester resin in the examples.
[0042]
Cross-linking agent: dimethylol dihydroxyethylene urea resin aqueous solution (solid content 20%)
Catalyst: Magnesium chloride antibacterial resin: 36 parts of a compound represented by the following chemical formula 4 as a vinyl monomer having a phosphate ester group and 39 parts of N, N-dimethyllaurylamine as a tertiary amine are reacted to form a phosphate ester After copolymerization with an amine salt, as a vinyl monomer having a hydroxyl group, 24 parts of 2-hydroxyethyl acrylate, and as a third component vinyl monomer, 60 parts of methoxypolyethylene glycol methacrylate (ethylene glycol repeating unit 23) As the monovalent glycidyl compound, a compound obtained by quaternary ammonium chloride using n-butyl glycidyl ether was used.
[0043]
[Chemical formula 5]

Silicone softener: Emulsion (solid content 20%) consisting of 10 parts aminopolyether-modified silicone (viscosity 300 cst, amino equivalent 4000), 3 parts amide compound of diethylenetriamine, stearic acid and maleic anhydride, 87 parts water A commercially available amino-modified silicone softener was also used.
[0044]
Hydrophilic polyester resin: A copolymer emulsion (solid content 10%) of dimethyl terephthalate 500 parts, ethylene glycol 400 parts, and polyethylene glycol (molecular weight 3000) was used.
[0045]
The evaluation in Examples and Comparative Examples was performed by the following method.
[0046]
[Crosslinking index]
Cross-linking index = (A−B)
Here, A: moisture absorption rate (%) of the cellulosic fiber after cross-linking modification in an atmosphere of a temperature of 30 ° C. and a relative humidity of 90% RH.
[0047]
B: Moisture absorption rate (%) of the cellulosic fiber after cross-linking modification under an atmosphere of a temperature of 20 ° C. and a relative humidity of 65% RH.
[0048]
[Water absorption (Bilec method)]
The water absorption height was measured by JIS L-1096 Bayrec method. It shows that water absorption is so favorable that a numerical value is large.
[0049]
[Water absorption (Drip method)]
The water absorption time was measured by JIS L-1018 A method dropping method. It shows that water absorption is so favorable that a numerical value is small.
[0050]
[Wrinkle resistance]
The determination was made based on the AATCC-124-1984 5-step replication method.
[0051]
Grade 5 (good) to Grade 1 (bad)
[Laundry shrinkage]
JIS L-1042 G method The shrinkage | contraction rate of the vertical direction of a fabric and the horizontal direction was measured by the home washing method. In addition, after washing, without squeezing with a dehydrator, it was sandwiched between dry filter papers, dehydrated by lightly pressing, and dried on a horizontal wire net.
[0052]
[Tearing strength]
JIS L-1096 D method The tear strength of the warp yarn cutting direction and weft yarn cutting direction of the fabric was measured by the pendulum method.
[0053]
[Texture]
The following criteria were evaluated by handling.
[0054]
○: The texture is rich in flexibility.
[0055]
Δ: A texture with a slightly coarse and hard core.
[0056]
X: A texture that is coarse and hard and has no flexibility.
[0057]
[Antimicrobial]
Evaluation was carried out by the method for measuring the number of bacteria. Staphylococcus aureus 209p was used as a test bacterium, a bouillon suspension of the test bacterium was poured onto a sterilized sample cloth, and the number of viable cells after culturing at 37 ° C. for 18 hours was measured in a sealed container. . The acceptance level was determined from the measurement results according to the following criteria.
[0058]
Under the condition of log (B / A)> 2, log (B / C) was defined as the difference in the number of bacteria, and 1.6 or more was determined as the pass level. However, A represents the number of bacteria dispersed and recovered immediately after inoculation of the raw product, B represents the number of bacteria dispersed and recovered after 18 hours of incubation of the raw product, and C represents the number of bacteria dispersed and recovered after 18 hours of incubation of the processed product.
[0059]
Examples 1-3
A sample was prepared using a working fluid having the composition shown in Table 1. The evaluation results are also shown in Table 1.
[0060]
Comparative Examples 1-4
A sample was prepared using a working fluid having the composition shown in Table 1. The evaluation results are also shown in Table 1.
[0061]
From Table 1, it can be seen that the fabrics of Comparative Examples 1 and 3 have a cross-linking index greater than 4, and a sufficient form-stable performance cannot be obtained. The fabric of Comparative Example 2 is the result of the fabric treated with the processing liquid not containing the antibacterial resin, but it can be seen that the antibacterial performance has not reached the acceptable level from the above criteria. The fabric of Comparative Example 4 is a fabric obtained by treating with a conventional amino-modified silicone resin, but it is understood that sufficient water absorption is not obtained.
[0062]
[Table 1]

[0063]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the cellulosic fiber containing fabric which has form stability performance, such as wrinkle resistance and shrinkage resistance, and water absorption can be provided stably.

Claims (11)

A cloth containing cellulosic fibers modified by crosslinking, wherein the cloth has a cross-linking index defined by the following formula of 1 to 4, and the water absorption of the cloth is based on the JISL-1096 birec method. The vinyl copolymer is 50 mm or more when measured, and the fabric has a monovalent and / or divalent phosphate group and a hydroxyl group, and the phosphate group is quaternary ammonium salified. A cellulosic fiber-containing fabric comprising an antibacterial resin made of a polymer, wherein the antibacterial resin is crosslinked with itself and / or the cellulosic fiber with a crosslinking agent .
Cross-linking index = (A−B)
Here, A: moisture absorption rate (%) of the cellulosic fiber after cross-linking modification in an atmosphere of a temperature of 30 ° C. and a relative humidity of 90% RH.
B: Moisture absorption rate (%) of the cellulosic fiber after cross-linking modification under an atmosphere of a temperature of 20 ° C. and a relative humidity of 65% RH. The cellulosic fiber-containing fabric according to claim 1, wherein the fabric contains 0.2 to 10 wt% of the antibacterial resin with respect to the fiber weight. The cellulosic fiber-containing fabric according to claim 1 or 2 , wherein the crosslinking index is 2 to 3.5. The cellulosic fiber-containing fabric according to any one of claims 1 to 3 , wherein the fabric contains 10 wt% or more of cellulosic fibers crosslinked and modified with a crosslinking agent. The cellulosic fiber-containing fabric according to any one of claims 1 to 4 , wherein the crosslinking agent is formaldehyde. The cellulosic fiber-containing fabric according to any one of 1 to 4 , wherein the crosslinking agent is a compound represented by the following chemical formula 1.

Wherein, R _1, R ₂ are, -H, or an alkyl group or -CH ₂ OR ₇ from 1 to 4 carbon atoms, a group of the same or _{different, R 3, R 4, R} 5, R ₆ is the same or different group that is either —H or —OR ₈ , and R ₇ and R ₈ are either the same or different group that is either —H or an alkyl group having 1 to 4 carbon atoms. It is a group of An organic polysiloxane containing both an amino group and a polyoxyalkyl group in one molecule; and a polyethylene polyamine higher fatty acid amide compound containing at least one group capable of reacting with an amine or a hydroxyl group in the molecule; cellulosic fiber-containing fabric according to any one of claims 1 to 6 and a silicone-based softening agent mainly composed of are those that have been granted. The polyethylene polyamine higher fatty acid type amide compound is obtained by reacting at least one selected from polyethylene polyamine and higher fatty acid, and lower dicarboxylic acid, cyclic acid anhydride, lower diglycidyl ether, and diisocyanate. The cellulosic fiber-containing fabric according to claim 7 . The fabric, cellulosic fiber-containing fabric according to claim 7 or 8, wherein the silicone softening agent is made by applying 0.06～1.0Wt% relative to the fiber weight. The fabric, polyalkylene glycol - cellulosic fiber-containing fabric according to any one of claims 1 to 9 in which the hydrophilic polyester resin mainly composed of polyester block copolymer is granted. Said fabric, said polyalkylene glycol - cellulosic fiber-containing fabric of claim 1 0, wherein the polyester block copolymer is made by applying 0.03～1.0Wt% relative to the fiber weight.