JP3862063B2 - Method for dyeing polyester fabric having flame retardancy and antibacterial properties - Google Patents

Description

（式中、Ｒ1は１価のエステル形成性官能基であり、Ｒ2、Ｒ3は同じか或いは異なる基であり、それぞれハロゲン原子、炭素数１〜１０個の炭化水素基、Ｒ1より選ばれ、Ａは２価又は３価の有機残基を表す。また、ｎ1は１又は２であり、n2、n3はそれぞれ０〜４の整数を表す。）
【００１０】
本発明において、布帛は抗菌性を付与する為に染色工程に於ける染浴中の水素イオン濃度ｐＨを８〜１０のアルカリサイドとすることが必要である。通常、分散染料による高圧染色では粗製酢酸や酢酸ソーダを処方し酸性サイドで染色処理を実施するが、この場合は抗菌性を布帛に与えることが出来ない。染浴をアルカリサイドにするにはエチレンジアミン四酢酸（ＥＤＴＡ）のようなポリアミノカルボン酸類及びその関連化合物、第二リン酸ナトリウム、ピロリン酸ナトリウム、トリポリリン酸ナトリウム、等が硬水軟化も兼ねて使用出来る。
【００１１】
その内、エチレンジアミン四酢酸（ＥＤＴＡ）或いはその誘導体は硬水中の金属イオンを安定的な水溶性キレート錯体とし硬水軟化させる効果があり、染色性を向上させるにも効果的である。またエチレンジアミン等と比較し弱アルカリである為に染浴中のｐＨコントロールがし易く、リン系化合物が排水富栄養に起因する公害の対象物質となっており使用を制限されている観点から、特に好ましく使用される。染浴中のｐＨについては８〜１０の範囲であることが必要である。フォスファフェナンスレン環を有する共重合ポリエステルにアルカリ処理することによって抗菌性が得られるメカニズムは現在のところ解明には至っていないが、驚くべきことに発明者らが鋭意検討を繰り返した結果、適度な抗菌特性を有することが確認された。
【００１２】
ｐＨが１０を超過する範囲では分散染料の分解が生じ始める為に色調のリピート性が得難い上、染色堅牢度が低下してしまい好ましくない。またｐＨが８未満であると上記フォスファフェナンスレン環を有する共重合ポリエステルに与える抗菌特性が満足なものにはならない。染色及び抗菌性能両者の観点からより好適と考えられる水素イオン濃度ｐＨの範囲は８．５〜１０．０である。
【００１３】
布帛については織物、編物、不織布など形態を規定するものではなく、２次元乃至３次元構造物として形をなしているものであれば何れをも含む。染色に於いてはポリエステル短繊維、ポリエステル長繊維からなる従来の布帛に用いる、市販の機種を使用することが可能であるが、十分な難燃性能を与えるには紡糸油剤及び糊剤等を布帛構造物から排除することが必要である。また、用途に応じて後加工剤の併用も可能であるが、難燃性能や抗菌性能に悪影響を及ぼす薬剤の選定は望ましくなく、十分考慮する必要がある。
【００１４】
布帛に十分な難燃性を与える為には染色前に紡糸油剤、糊剤、オリゴマー成分その他夾雑物を精練リラックス工程で除去することが必要である。精練リラックス工程における機種としては高圧ロータリーワッシャー、液流リラクサー等、特に限定されるものではなく、市販の機種を使用することが出来る。精練温度としては浴温として１００〜１３０℃程度の高圧条件が好適である。精練リラックスは苛性ソーダ、ハイドロサルファイトナトリウム、ノニオン系界面活性剤等を適当量処方して実施するが、シリコン系消泡剤の使用は難燃性を阻害するため、使用に適さない。
【００１５】
本発明において、布帛は分散染料による１００℃以上の高圧染色で染色することが出来る。染色温度としてより好ましくは１２０℃以上、更に好ましくは１３０℃以上である。１００℃未満の染色温度では完全吸尽に至る迄の時間が掛り過ぎる他、染色堅牢度や染品位の観点からも好適であるとは言えない。染色における浴比については使用する染色機の機種や染法によって異なる為、特に規定されるものではないが、従来の液流染色機の使用を想定すると浴比としては被染物：染浴容量＝１：７〜１：１５程度が好ましく用いられる。
【００１６】
染色加工後に未吸尽の染料、染色助剤を除去する為、苛性ソーダ、ハイドロサルファイトナトリウム、ノニオン系界面活性剤等を適当量処方した水溶液中に被染物（布帛）を投入し浴温８０℃〜９０℃で３０〜６０分程度の還元洗浄した後に排液し、湯洗いを繰り返した後、脱水、スカッチャによる拡布を実施し乾燥した後、ヒートセッターにより仕上げセットを施す。仕上げセット温度も特に限定を加えないが乾熱１５０〜１７０℃でセットを実施することが染色堅牢度を考慮すると好ましい。
【００１７】
使用する染色機については特に限定を加えるものではなく、市販の液流染色機（ジェット染色機）、ジッカー染色機、ウインス染色機、低浴比の気流染色機などを使用することが出来るが、高圧染色に耐え得る仕様のものを用いることが望ましい。本発明にて使用するフォスファフェナンスレン環を有する共重合ポリエステル繊維は分子構造的に嵩高く、分子回転が阻害されている他、分子間空隙がポリエチレンテレフタレートホモポリマーからなる繊維対比で大きいものとなっている為に、１００℃未満の常圧領域でも染色可能であるが、鮮明色が得られないばかりか染色堅牢度も良好なものとならず好ましいものにはならない。
【００１８】
防汚加工剤などの仕上剤や精練剤については原糸の難燃性を阻害しない化合物を選定することが望ましく、特に限定を加えるものではないが例示すると柔軟剤としては高松油脂社製ＥＸ−２００、防汚加工剤として高松油脂社製ＳＲ−１０００などが好適に用いられる。また、用途展開として車両内装材やカーシート材などへは耐光堅牢性を向上させる為に日華化学社製サンライフＬＰ−２００に代表される紫外線吸収剤を染色同浴吸尽処方にて付与することが好ましい。
【００１９】
本発明の布帛は用途や意匠性等、必要に応じてエアー交絡処理、高圧流体撹乱処理、仮撚加工、交撚・合撚その他撚糸を共重合ポリエステル繊維糸条に施した後、布帛構造物を構成してもよい。また、共重合ポリエステル繊維は長繊維の形態のみならず短繊維の形態であってもよく、オープンエンド紡績糸、リング紡績糸、結束紡績等各種紡績糸の形態、ドラフト及び複合方法を調整した紡績スラブ糸その他、形態は特に規定されるものではなく何れの形態も含まれる。
【００２０】
更に布帛の風合いに応じて水酸化ナトリウム、水酸化カリウム等の水溶液によるアルカリ減量加工によって、ポリエステルを加水分解させ風合いをソフトにさせることも可能である。処理方法についてはパッドスチームキュア法等の連続加工法、吊り減量や液流減量等のバッチ加工法の何れであってもよい。減量完了後は加水分解されたポリエステルダイマー、トリマー等の不純物を湯洗い、水洗いを繰り返して十分に除去することが望ましい。
【００２１】
抗菌性能評価については抗菌防臭加工製品の評価試験マニュアル・菌数測定法（繊維製品衛生加工協議会；現・繊維製品新機能評価協議会，昭和６３年）に準拠した方法で評価するものであり、黄色ブドウ球菌の菌数増減値差を求めるものである。菌数増減値差が１．６を超過すれば合格であり、１．６未満であれば性能的に不満足なものとなり、抗菌製品として認定されるものにはならない。菌数増減値差については特に上限を定めるものではないが、測定範囲上限値が４〜５近辺であり、好適と考えられる数値としては２〜４である。測定範囲上限値程度の高度抗菌性を欲する場合には染色同浴吸尽法、パディング法、サーモゾール法等による後加工抗菌剤付与を併用しても構わない。
【００２２】
［実施例］以下、実施例に従い本発明を更に詳細に説明する。いうまでもないが本発明は以下の実施例に何等限定されるものではない。
【００２３】
尚、本文中及び実施例中の特性値、物性値は以下の測定方法に基づいて測定される。
［染浴中の水素イオン濃度］平間理化研究所社製染色液コントローラＰＰＣ−８Ａ型を染色オンラインで評価する為に熱交換器の配管手前で検出出来るように設置し染液１００℃±５℃条件における水素イオン濃度を直読した。
【００２４】
［製品布帛の水素イオン濃度］布帛試料を０．３ｇ採取し２０ｍｌ蒸留水中に浸漬し、２０℃環境下にて２時間経過後の水溶液に対する水素イオン濃度について堀場製作所社製ｐＨメーターＦ−２１型を使用し水溶液温度２０℃の条件で数値を直読した。
【００２５】
［難燃性能］１９９９年度版ＪＩＳ Ｌ−１０９１ Ａ−１法（４５°ミクロバーナー法）に従い、１分加熱及び着炎後３秒加熱の燃焼面積（ｃｍ²）、残炎時間（秒）、残塵時間（秒）を評価する。更に財団法人 日本防炎協会 防炎製品認定委員会発行の防炎製品の性能試験基準（平成１１年１月１日改正）第１ 寝具類−２防炎性能試験．１．（１）．▲(4)▼に記載のコイル法に従い評価した。尚、布帛試料の洗濯方法（水洗い洗濯、ドライクリーニング）はそれぞれＪＩＳ Ｌ−１０１８の８．５８．４ｂ）６．２のＦ−２法、ＪＩＳ Ｌ−１０１８の８．５８．４ｂ）５．２）のＥ−２法に準じて実施し、洗濯初期及び水洗い洗濯５回、ドライクリーニング５回後の難燃性能（残炎時間、残塵時間、燃焼面積）を評価する。
【００２６】
［抗菌性能］抗菌防臭加工製品の評価試験マニュアル・菌数測定法（繊維製品衛生加工協議会；現・繊維製品新機能評価協議会，昭和６３年）により、滅菌した液体ブイヨンに黄色ブドウ球菌（Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ ＦＤＡ２０９Ｐ）を懸濁させ、この液を０．２ｇの試験片上に０．２ｍｌ接種（菌数は約１０万個）し、３７℃×１８時間培養後に取り出す。培養前後の試験片上の生菌数を測定し、次の計算式によって菌数増減値差を求めた。該菌数増減値差が１．６を超過すれば合格となる。
菌数増減値＝ｌｏｇ１０（１８時間培養後の試験片上の生菌数）―ｌｏｇ１０（培養直前の生菌数）
菌数増減値差＝標準試料の菌数増減値―抗菌試料の菌数増減値
【００２７】
［実施例１］
フォスファフェナンスレン環を有し、リン原子含有量が原子換算で５５００ppmである共重合ポリエステルを溶融紡糸し、１２０デシテックス４８フィラメントの丸断面セミダル部分配向糸Ａ（ＰＯＹ）及び２４０デシテックス４８フィラメントの丸断面セミダル部分配向糸Ｂ（ＰＯＹ）を得た。これら部分配向糸Ａ、Ｂに延伸仮撚加工を施し、それぞれ８４デシテックス４８フィラメント、１６７デシテックス４８フィラメントの仮撚加工糸とした。
【００２８】
部分配向糸Ａ（ＰＯＹ）を使用して得られた８４デシテックス４８フィラメントの共重合ポリエステルマルチフィラメント仮撚加工糸にＳ方向４００回／ｍの実撚を挿入した後、経糸ビームに巻き取った。また緯糸として部分配向糸Ｂ（ＰＯＹ）を使用して得られた１６７デシテックス４８フィラメントの共重合ポリエステルマルチフィラメント仮撚加工糸を無撚の形態で打ち込み、エアージェットルームを使用し七枚朱子（右上り２飛び６／１サテン）に製織し、織物生機を得た。
【００２９】
得られた生機をニッセン社製ソフサーを用いて前浴６０℃、処理温度９０℃で湿熱前処理を施した後、ソーダ灰、ノニオン系界面活性剤を適当量溶解し、日阪製作所社製サーキュラー液流リラクサーによる精練リラックス処理を最高到達点温度１１０℃で実施、排液後に湯洗を十分に実施し、夾雑物その他を除去した後に表面温度１３０℃のシリンダードライヤーで乾燥処理した。次いで日阪製作所社製サーキュラー液流染色機を使用し分散染料による１３０℃高圧染色を実施した。浴比は１：１０であり、染浴中にエチレンジアミン四酢酸（ＥＤＴＡ）を添加して水素イオン濃度ｐＨ＝９．２のアルカリサイドで行った。詳細条件及び物性値測定結果を表１、表２に示した。難燃性及びマイルドな抗菌性を有する布帛が得られ、カーテンその他用途に適したものに仕上がった。
【００３０】
［実施例２］フォスファフェナンスレン環を有し、リン原子含有量が原子換算で５５００ppmである共重合ポリエステルを溶融紡糸し、１２０デシテックス４８フィラメントの丸断面セミダル部分配向糸Ａ（ＰＯＹ）を得た。引き続き延伸撚糸機を使用し、延伸処理を実施しして８４デシテックス４８フィラメントの延伸糸（ＦＯＹ）とした。該延伸糸について経糸用にはＳ撚及びＺ撚方向に１０００Ｔ／ｍの実撚を挿入、緯糸用には該延伸糸にＳ撚及びＺ撚方向に２５００Ｔ／ｍの実撚を挿入し、８０℃×４０分の条件で撚り止めセットを施した後、レピアルームにて五枚経朱子（右上り２飛び４／１サテン）に製織、経糸及び緯糸がＳ撚、Ｚ撚２本交互の配列で織物生機を得た。
【００３１】
染浴中にエチレンジアミン四酢酸（ＥＤＴＡ）を添加して水素イオン濃度ｐＨ＝９．０のアルカリサイドにして染色した他は実施例１同様の方法で染色加工布を得た。詳細条件及び物性値測定結果を表１、表２に示す。実施例１同様、難燃性及びマイルドな抗菌性を有する布帛が得られ、カーテンやクッション材その他用途に適したものに仕上がった。
【００３２】
［実施例３］フォスファフェナンスレン環を有し、リン原子含有量が原子換算で５５００ppmである共重合ポリエステルを溶融紡糸し、１２０デシテックス２４フィラメントの丸断面セミダル部分配向糸Ａ（ＰＯＹ）を得た。引き続き延伸撚糸機を使用し、延伸処理を実施しして８４デシテックス２４フィラメントの延伸糸（ＦＯＹ）とした。該延伸糸についてＳ撚及びＺ撚方向に２０００Ｔ／ｍの実撚を挿入、８０℃×４０分の条件で撚り止めセットを施し、レピアルームにて梨地組織（一完全；経１２０本×緯１２０本）に製織、経糸及び緯糸がＳ撚、Ｚ撚２本交互の配列で織物生機を得た。
【００３３】
得られた生機をニッセン社製ソフサーを用いて前浴６０℃、処理温度９０℃で湿熱前処理を施した後、ソーダ灰、ノニオン系界面活性剤を適当量溶解し、日阪製作所社製サーキュラー液流リラクサーによる精練リラックス処理を最高到達点温度１２０℃で実施、排液後に湯洗を十分に実施し、夾雑物その他を除去した後に表面温度１３０℃のシリンダードライヤーで乾燥処理し、次いでヒートセッターで乾熱１８０℃×２分間の生地セットを実施した。
【００３４】
引き続き、生地を連続減量機にてパッドスチーム法による減量を減量率８％条件で実施し、十分湯洗し乾燥させた後に日阪製作所社製サーキュラー液流染色機を使用し分散染料による１３０℃高圧染色を実施した。浴比は１：１０であり、染浴中にエチレンジアミン四酢酸（ＥＤＴＡ）を添加して水素イオン濃度ｐＨ＝８．７のアルカリサイドで行った。詳細条件及び物性値測定結果を表１、表２に示した。難燃性及びマイルドな抗菌性を有する布帛が得られ、ベッドカバー、テーブルクロスその他用途に適したものに仕上がった。
【００３５】
［比較例１］染浴中の水素イオン濃度ｐＨ＝５．９とした他は実施例１同様の方法にて染色加工布を得た。詳細条件及び物性測定結果を表１、表２に示した。難燃性は認められるが、抗菌性は不合格となった。
【００３６】
［比較例２］染浴中の水素イオン濃度ｐＨ＝５．７とした他は実施例３同様の方法にて染色加工布を得た。詳細条件及び物性測定結果を表１、表２に示した。難燃性は認められるが、抗菌性は不合格となった。
【００３７】
［比較例３］ポリエチレンテレフタレートセミダルレジン（固有粘度[η]＝０．６３）を溶融紡糸し、１２２デシテックス４８フィラメントの丸断面部分配向糸Ａ（ＰＯＹ）を得た。引き続き延伸撚糸機を使用し、延伸処理を実施しして８４デシテックス４８フィラメントの延伸糸（ＦＯＹ）とした。該延伸糸についてＳ撚方向に４００Ｔ／ｍの実撚を挿入し経糸ビームに巻き取った。緯糸にはポリエチレンテレフタレートセミダル５００デニール９６フィラメントの丸断面部分配向糸を延伸仮撚し、３３５デシテックス９６フィラメントのポリエステル仮撚加工糸としたものを用い、七枚朱子組織（右上り２飛び６／１サテン）の織物生機を得た。使用した織機はレピアルームである。
【００３８】
得られた生機をニッセン社製ソフサーを用いて前浴６０℃、処理温度９０℃で湿熱前処理を施した後、ソーダ灰、ノニオン系界面活性剤を適当量溶解し、日阪製作所社製サーキュラー液流リラクサーによる精練リラックス処理を最高到達点温度１１０℃で実施、排液後に湯洗を十分に実施し、夾雑物その他を除去した後に表面温度１３０℃のシリンダードライヤーで乾燥処理した。次いで日阪製作所社製サーキュラー液流染色機を使用し分散染料による１３０℃高圧染色を実施した。染浴中には染色同時吸尽法にて難燃加工剤、及び抗菌加工剤を適用し、後加工難燃・抗菌処理を施した。詳細条件及び物性測定結果を表１、表２に示した。適度な難燃性、抗菌性を有するものに仕上ったが、水洗濯、ドライクリーニングにおける耐久性に問題があり、繰り返し使用に耐えるものにはならなかった。また高価な難燃剤、抗菌剤を処方する為に加工工賃増加や鮮明な色調が得難いなどの問題を含むものであった。
【００３９】
【表１】

【００４０】
【表２】

【００４１】
【発明の効果】
上述の如く、本発明によると難燃性及び抗菌性を併せ持ったポリエステル布帛を得ることが可能となり、特にカーテン、テーブルクロス、ベッドカバー、壁紙材、クッション等の生活資材用途に好適な素材となる。また、従来の難燃後加工素材、抗菌後加工素材では洗濯耐久性に乏しく、劇場やホテル等の公共用途には好適とは言えなかったが、本発明によると難燃性能及び抗菌性能は洗濯を繰り返し実施しても保持するものであり、後加工によって難燃剤、抗菌剤処理を実施しないために環境に及ぼす負荷も小さく、経済的且つ効率よく性能を付与することが出来る。また燃焼に至る場合も従来の後加工難燃布帛のようなハロゲンガス、ハロゲン化水素ガス、シアンガス等の有害ガス発生の問題がないなどの効果を奏するものである。The present invention relates to a method for producing a polyester cloth 帛 having flame retardancy and antibacterial properties, curtains and more particularly, upholstery, bedspreads, flame retardancy suitable Forest applications such as wallpaper, an antimicrobial a process for producing a polyester fabric 帛 having, machining flame retardant after the dyeing process, due to post-processing antimicrobial treatment rather than the performance imparted, since a fiber obtained by copolymerizing a polymer phase is a material excellent in durability And the like.
[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for dyeing a polyester fabric having flame retardancy and antibacterial properties, and more particularly to a polyester fabric suitable for use in daily life materials such as curtains, bed covers, cushions, chair upholstery, and wallpaper materials. .
[0002]
[Prior art]
Conventionally, there has been a strong demand for flame retardancy in interior applications such as curtains, chair upholstery, bed covers and the like, and many flame retardant products have been put on the market and deployed especially as equipment for public organizations. In recent years, in addition to flame retardancy, antibacterial properties are imparted, and it is also considered to be used in a wider range. Most of these performances are given by post-processing such as simultaneous dye exhaustion and padding. The imparting of various performances by post-processing is often difficult because the performance is often primary, and the washing durability is poor, and furthermore, the environmental impact of dyeing processing wastewater is large.
[0003]
Also, as post-processing flame retardants, those containing halogenated cycloalkane compounds such as hexabromocyclododecane as flame retardant components are common, but from the viewpoint of protecting the global environment and living environment, flame retardant materials made of non-halogen compounds are used. There is a very strong demand, and in particular, there is an extremely high demand for flame retardant materials that do not generate toxic gases such as halogens or residue even during incineration due to environmental conservation problems. Furthermore, as for antibacterial agents, zeolite-silver system is mainly used for kneading and chitin chitosan derivatives and quaternary ammonium salts are mainly used for post-processing. However, both the former and the latter have high drug costs. Like the treatment, unreacted / unexhausted chemicals are discharged out of the system, which is not preferable from the viewpoint of protecting the living environment.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for dyeing a polyester fabric that can be realized without treatment with a post-processing agent in a dyeing process in order to impart flame retardancy and antibacterial properties. Permanent flame retardancy and antibacterial properties of woven and knitted fabrics using at least a part of copolymer polyester with phenanthrene ring without increasing the number of steps in the conventional dyeing process and with less environmental impact It is an object of the present invention to provide a dyeing method for imparting to a fabric.
[0005]
[Means for Solving the Problems]
The present invention has the following configuration. It was 500~50000ppm containing a phosphorus atom in terms of atom, viewed contains at least a portion of the copolymerized polyester fiber having a phosphazene phenanthrene ring, a dyeing method of woven or knitted fabrics having the following antimicrobial performance, pH = It consists of a dyeing method for a polyester fabric having flame retardancy and antibacterial properties, in which dyeing is carried out at a hydrogen ion concentration of 8 to 10 at a treatment temperature of 100 ° C. or higher . Here, the antibacterial property refers to the difference in the number of bacteria increased or decreased according to the evaluation test manual for the antibacterial and deodorant processed product / bacteria count method (Textile Products Sanitary Processing Council; current Textile Product New Function Evaluation Council, 1988). It means 1.6 or more.
[0006]
Further, preferably, a method for dyeing and processing a polyester fabric having flame retardancy and antibacterial properties, characterized in that ethylenediaminetetraacetic acid (EDTA) or a derivative thereof is formulated in a dye bath. Provided is a method for dyeing a polyester fabric having flame retardancy and antibacterial properties, wherein an alkali weight loss treatment is performed on the fabric structure.
DETAILED DESCRIPTION OF THE INVENTION
[0007]
The copolymerized polyester fiber used for the polyester fabric in the present invention needs to contain 500 to 50,000 ppm of phosphorus atoms in terms of atoms. If the phosphorus atom content is less than 500 ppm, moderate flame retardancy cannot be imparted, and if it exceeds 50000 ppm, the flame retardancy is improved, but the spinning operability such as spun yarn breakage is reduced. However, it is not a preferable range because it does not finish to satisfy general consumption performance in terms of yarn strength.
[0008]
In addition, the copolyester used for the polyester fabric in the present invention must have a phosphaphenanthrene ring, and is preferably copolymerized with a compound represented by the general formula of [Formula 2]. .
[0009]
[Chemical 2]

(Wherein R1 is a monovalent ester-forming functional group, R2 and R3 are the same or different groups, each selected from a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and R1; Represents a divalent or trivalent organic residue, n1 is 1 or 2, and n2 and n3 each represent an integer of 0 to 4.)
[0010]
In the present invention , in order to impart antibacterial properties , the fabric needs to have an alkali side having a hydrogen ion concentration pH of 8 to 10 in the dyeing bath in the dyeing step. Usually, in high-pressure dyeing with disperse dyes, crude acetic acid or sodium acetate is prescribed and dyeing is carried out on the acidic side, but in this case, antibacterial properties cannot be imparted to the fabric. In order to make the dye bath alkaline, polyaminocarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and related compounds, dibasic sodium phosphate, sodium pyrophosphate, sodium tripolyphosphate, etc. can also be used for softening water.
[0011]
Among them, ethylenediaminetetraacetic acid (EDTA) or a derivative thereof has an effect of softening hard water with a metal ion in hard water as a stable water-soluble chelate complex, and is also effective in improving dyeability. In addition, since it is weakly alkaline compared to ethylenediamine, etc., it is easy to control the pH in the dyeing bath, and from the viewpoint that the phosphorus compound is a target substance of pollution caused by wastewater eutrophication and its use is restricted. Preferably used. The pH in the dye bath needs to be in the range of 8-10. Although the mechanism by which antibacterial properties can be obtained by alkali treatment of a copolyester having a phosphaphenanthrene ring has not yet been elucidated, surprisingly, as a result of repeated repeated studies by the inventors, It was confirmed that it has excellent antibacterial properties.
[0012]
In the range where the pH exceeds 10, disperse dyes start to be decomposed, so that it is difficult to obtain color repeatability and the dyeing fastness is lowered, which is not preferable. On the other hand, if the pH is less than 8, the antibacterial properties given to the copolymer polyester having the phosphaphenanthrene ring are not satisfactory. The range of hydrogen ion concentration pH that is considered more suitable from the viewpoint of both dyeing and antibacterial performance is 8.5 to 10.0.
[0013]
The fabric does not define the form such as a woven fabric, a knitted fabric, and a non-woven fabric, and includes any fabric that has a shape as a two-dimensional or three-dimensional structure. In dyeing, it is possible to use a commercially available model used for a conventional fabric composed of polyester short fibers and polyester long fibers. However, in order to give sufficient flame retardancy, a spinning oil and a paste are used as the fabric. It is necessary to exclude it from the structure. In addition, a post-processing agent can be used in combination depending on the application, but selection of a drug that adversely affects flame retardancy and antibacterial performance is not desirable and should be fully considered.
[0014]
In order to impart sufficient flame retardancy to the fabric, it is necessary to remove spinning oils, glues, oligomer components and other contaminants in a scouring relaxation step before dyeing. The model in the scouring relaxation process is not particularly limited, such as a high-pressure rotary washer or a liquid flow relaxer, and a commercially available model can be used. The scouring temperature is preferably a high pressure condition of about 100 to 130 ° C. as the bath temperature. Scouring relaxation is carried out by prescribing an appropriate amount of caustic soda, sodium hydrosulfite, nonionic surfactant, etc., but the use of a silicon-based antifoaming agent is not suitable for use because it inhibits flame retardancy.
[0015]
In the present invention , the fabric can be dyed by high-pressure dyeing at 100 ° C. or higher with a disperse dye. The dyeing temperature is more preferably 120 ° C. or higher, further preferably 130 ° C. or higher. When the dyeing temperature is less than 100 ° C., it takes too much time until complete exhaustion, and it is not preferable from the viewpoint of dyeing fastness and dyeing quality. Since the bath ratio in dyeing varies depending on the type of dyeing machine used and the dyeing method, it is not specified, but assuming the use of a conventional liquid dyeing machine, the bath ratio is as follows: A ratio of about 1: 7 to 1:15 is preferably used.
[0016]
In order to remove unexhausted dyes and dyeing assistants after dyeing processing, a dyed article (fabric) is put into an aqueous solution formulated with appropriate amounts of caustic soda, sodium hydrosulfite, nonionic surfactant, etc., and bath temperature is 80 ° C. After reducing and washing at ˜90 ° C. for about 30 to 60 minutes, draining, repeating hot water washing, dehydrating and spreading by scatcher, drying, and then finishing setting with a heat setter. The finishing set temperature is not particularly limited, but it is preferable to perform the setting at a dry heat of 150 to 170 ° C. in consideration of dyeing fastness.
[0017]
The dyeing machine to be used is not particularly limited, and a commercially available liquid dyeing machine (jet dyeing machine), a zicker dyeing machine, a wins dyeing machine, an airflow dyeing machine with a low bath ratio, etc. can be used. It is desirable to use a specification that can withstand high-pressure dyeing. The copolyester fiber having a phosphaphenanthrene ring used in the present invention is bulky in terms of molecular structure and has a large intermolecular void compared to a fiber composed of a polyethylene terephthalate homopolymer in addition to hindering molecular rotation. Therefore, although it is possible to dye even in a normal pressure region of less than 100 ° C., not only a clear color is not obtained, but also the dyeing fastness is not good and is not preferable.
[0018]
For finishing agents such as antifouling agents and scouring agents, it is desirable to select a compound that does not inhibit the flame retardancy of the raw yarn, but there is no particular limitation, but as a softener, EX- manufactured by Takamatsu Yushi Co., Ltd. 200, SR-1000 manufactured by Takamatsu Yushi Co., Ltd. is preferably used as an antifouling agent. In addition, in order to improve the light fastness to vehicle interior materials and car seat materials as application development, UV absorbers represented by Sun Life LP-200 made by Nikka Chemical Co., Ltd. are applied in the dyeing and bath exhaustion prescription. It is preferable to do.
[0019]
The fabric of the present invention is applied to the copolyester fiber yarn by applying air entanglement treatment, high-pressure fluid disturbance treatment, false twisting treatment, false twisting / twisting or other twisted yarn to the copolymerized polyester fiber yarn as necessary, such as use and design properties, and then the fabric structure May be configured. In addition, the copolyester fiber may be in the form of not only long fibers but also short fibers, and various spinning yarns such as open-end spun yarn, ring spun yarn, bundled spun yarn, drafts, and composite spinning methods are adjusted. The slab yarn and other forms are not particularly defined, and any form is included.
[0020]
Furthermore, it is possible to hydrolyze the polyester and soften the texture by alkali weight reduction with an aqueous solution of sodium hydroxide, potassium hydroxide or the like according to the texture of the fabric. The processing method may be any of a continuous processing method such as a pad steam cure method, and a batch processing method such as hanging loss and liquid flow reduction. After completion of the weight reduction, it is desirable to thoroughly remove impurities such as hydrolyzed polyester dimer and trimer with hot water and repeated washing with water.
[0021]
About antibacterial performance evaluation, the evaluation test manual of antibacterial and deodorant processed products, bacteria count method (Textile Products Sanitary Processing Council; current Textile Products New Function Evaluation Council, 1988) The difference in the number of increase / decrease values of Staphylococcus aureus is obtained. If the difference in the number of bacteria increase / decrease exceeds 1.6, it is acceptable, and if it is less than 1.6, the performance is unsatisfactory and the product is not certified as an antibacterial product. Although there is no particular upper limit for the difference in the number of bacteria increase / decrease, the upper limit of the measurement range is around 4 to 5, and 2 to 4 are considered suitable. When high antibacterial properties of the upper limit of the measurement range are desired, post-processing antibacterial agent application by the dyeing and bathing method, padding method, thermosol method or the like may be used in combination.
[0022]
[Examples] The present invention will now be described in more detail with reference to examples. Needless to say, the present invention is not limited to the following examples.
[0023]
The characteristic values and physical property values in the text and in the examples are measured based on the following measuring methods.
[Hydrogen ion concentration in the dyeing bath] Dyeing solution 100 ° C ± 5 ° C installed so that it can be detected in front of the heat exchanger piping in order to evaluate dyeing solution controller PPC-8A manufactured by Hirama Rika Laboratory Co., Ltd. The hydrogen ion concentration under the conditions was read directly.
[0024]
[Hydrogen ion concentration of product fabric] 0.3 g of a fabric sample was taken and immersed in 20 ml distilled water, and the hydrogen ion concentration with respect to the aqueous solution after 2 hours in a 20 ° C. environment was measured by Horiba Ltd. pH meter F-21 type The value was directly read under the conditions of an aqueous solution temperature of 20 ° C.
[0025]
[Flame Retardant Performance] According to 1999 version JIS L-1091 A-1 method (45 ° micro burner method), combustion area (cm ² ) for 1 minute heating and 3 seconds heating after ignition, afterflame time (seconds), Evaluate the residual dust time (seconds). In addition, the flame test product performance test standard (revised on January 1, 1999) issued by the Japan Flame Protection Association Flame Test Product Certification Committee. 1. (1). Evaluation was made according to the coil method described in (4). In addition, the washing method (washing washing, dry cleaning) of the fabric sample is JIS L-1018 8.58.4b) 6.2 F-2 method, JIS L-1018 8.58.4b) 5.2. ) In accordance with the E-2 method, and the flame retardancy (residual flame time, residual dust time, combustion area) at the initial stage of washing and after washing with water 5 times and after dry cleaning 5 times is evaluated.
[0026]
[Antibacterial performance] Evaluation test manual for antibacterial and deodorant processed products / Bacteria count method (Textile Products Hygiene Processing Council; current Textile Products New Function Evaluation Council, 1988). Staphylococcus aureus FDA209P) is suspended, 0.2 ml of this solution is inoculated on a 0.2 g test piece (the number of bacteria is about 100,000), and taken out after incubation at 37 ° C. for 18 hours. The number of viable bacteria on the test piece before and after the culture was measured, and the difference in the number of bacteria increased or decreased was determined by the following formula. If the difference in the number of bacteria increase / decrease exceeds 1.6, the test is passed.
Increase / decrease value of the number of bacteria = log 10 (the number of viable bacteria on the test piece after 18 hours of culture) −log 10 (the number of viable bacteria just before the cultivation)
Increase / decrease difference in the number of bacteria = Increase / decrease in the number of bacteria in the standard sample-Increase / decrease in the number of bacteria in the antibacterial sample
[Example 1]
A copolyester having a phosphaphenanthrene ring and a phosphorus atom content of 5500 ppm in terms of atoms is melt-spun, and a 120-dtex 48 filament round cross-section semidal partially oriented yarn A (POY) and a 240 dtex 48-filament A round section semi-dal partially oriented yarn B (POY) was obtained. These partially oriented yarns A and B were subjected to drawing false twisting to obtain false twisting yarns of 84 dtex 48 filament and 167 dtex 48 filament, respectively.
[0028]
A real twist of 400 times / m in the S direction was inserted into a copolyester multifilament false twisted yarn of 84 dtex 48 filaments obtained using the partially oriented yarn A (POY), and then wound around a warp beam. In addition, 167 decitex 48 filament copolyester multifilament false twisted yarn obtained using partially oriented yarn B (POY) as weft was driven in a non-twisted form, and seven pieces of red satin (right Weaving to 2/1 (6/1 satin uphill) gave a woven fabric machine.
[0029]
The obtained raw machine was subjected to wet heat pretreatment at a pre-bath 60 ° C. and a treatment temperature 90 ° C. using a Nissen softener, and then dissolved in appropriate amounts of soda ash and nonionic surfactant to obtain a circular made by Nisaka Manufacturing Co., Ltd. A scouring relaxation process with a liquid flow relaxer was performed at a maximum temperature of 110 ° C., and after draining, hot water was sufficiently washed, and after removing impurities and other substances, the surface was dried with a cylinder dryer having a surface temperature of 130 ° C. Subsequently, using a circular liquid flow dyeing machine manufactured by Nisaka Seisakusho, 130 ° C. high-pressure dyeing with disperse dyes was carried out. The bath ratio was 1:10, and ethylenediaminetetraacetic acid (EDTA) was added to the dyeing bath, and the reaction was carried out with an alkali side having a hydrogen ion concentration of pH = 9.2. Detailed conditions and physical property measurement results are shown in Tables 1 and 2. A fabric having flame retardancy and mild antibacterial properties was obtained, and finished to be suitable for curtains and other applications.
[0030]
[Example 2] A copolyester having a phosphaphenanthrene ring and a phosphorus atom content of 5500 ppm in terms of atoms is melt-spun, and a 120 dtex 48 filament round section semi-dal partially oriented yarn A (POY) is obtained. Obtained. Subsequently, using a drawing twisting machine, a drawing process was carried out to obtain a drawn yarn (FOY) of 84 dtex 48 filaments. For the drawn yarn, a 1000 T / m real twist is inserted in the S twist and Z twist directions for warp yarn, and a 2500 T / m real twist is inserted in the drawn yarn in the S twist and Z twist directions for the weft yarn. After applying a twist set under the condition of ℃ x 40 minutes, weaving in a rapier room on 5 warp reds (upper right 2 jump 4/1 satin), warp and weft are S twist and Z twist 2 A woven fabric was obtained.
[0031]
A dyed fabric was obtained in the same manner as in Example 1, except that ethylenediaminetetraacetic acid (EDTA) was added to the dye bath to dye the alkali side with a hydrogen ion concentration of pH = 9.0. Detailed conditions and physical property measurement results are shown in Tables 1 and 2. As in Example 1, a fabric having flame retardancy and mild antibacterial properties was obtained, and finished into a curtain, a cushion material and other suitable materials.
[0032]
[Example 3] A copolyester having a phosphaphenanthrene ring and having a phosphorus atom content of 5500 ppm in terms of atoms is melt-spun, and a 120 dtex 24 filament round section semi-dal partially oriented yarn A (POY) is obtained. Obtained. Subsequently, a drawing process was performed using a drawing twisting machine to obtain a drawn yarn (FOY) of 84 dtex 24 filaments. Insert a 2000 T / m real twist in the S and Z twist directions of the drawn yarn, apply a twist set under conditions of 80 ° C x 40 minutes, and create a satin texture (one complete; warp 120 x weft 120) ), Weaving, warp and weft were obtained by arranging two S twists and two Z twists alternately.
[0033]
The obtained raw machine was subjected to wet heat pretreatment at a pre-bath 60 ° C. and a treatment temperature 90 ° C. using a Nissen softener, and then dissolved in appropriate amounts of soda ash and nonionic surfactant to obtain a circular made by Nisaka Manufacturing Co., Ltd. A scouring relaxation treatment with a liquid flow relaxer is performed at a maximum temperature of 120 ° C. After draining, hot water is thoroughly washed, and impurities and other substances are removed, followed by drying with a cylinder dryer with a surface temperature of 130 ° C. The dough was set at 180 ° C. for 2 minutes with dry heat.
[0034]
Subsequently, the fabric was weight-reduced by the pad steam method with a continuous weight loss machine under the condition of a weight loss rate of 8%, sufficiently washed with hot water and dried, and then a circular liquid flow dyeing machine manufactured by Hisaka Seisakusho was used. High pressure staining was performed. The bath ratio was 1:10, and ethylenediaminetetraacetic acid (EDTA) was added to the dye bath, and the test was carried out with an alkali side having a hydrogen ion concentration of pH = 8.7. Detailed conditions and physical property measurement results are shown in Tables 1 and 2. A fabric having flame retardancy and mild antibacterial properties was obtained, and finished into a bed cover, table cloth and other suitable items.
[0035]
[Comparative Example 1] A dyed fabric was obtained in the same manner as in Example 1 except that the hydrogen ion concentration in the dyeing bath was pH = 5.9. Detailed conditions and physical property measurement results are shown in Tables 1 and 2. Although flame retardancy was observed, the antibacterial property was rejected.
[0036]
[Comparative Example 2] A dyed fabric was obtained in the same manner as in Example 3 except that the hydrogen ion concentration in the dyeing bath was pH = 5.7. Detailed conditions and physical property measurement results are shown in Tables 1 and 2. Although flame retardancy was observed, the antibacterial property was rejected.
[0037]
[Comparative Example 3] Polyethylene terephthalate semidal resin (intrinsic viscosity [η] = 0.63) was melt-spun to obtain a 122 dtex 48 filament round section partially oriented yarn A (POY). Subsequently, using a drawing twisting machine, a drawing process was carried out to obtain a drawn yarn (FOY) of 84 dtex 48 filaments. A 400 T / m real twist was inserted in the S twist direction of the drawn yarn and wound around a warp beam. For the weft, a polyethylene terephthalate semi-dal 500 denier 96 filament round section partially oriented yarn was drawn and twisted into a 335 dtex 96 filament polyester false twisted yarn. 1 satin) was obtained. The loom used was a rapier room.
[0038]
The obtained raw machine was subjected to wet heat pretreatment at a pre-bath 60 ° C. and a treatment temperature 90 ° C. using a Nissen softener, and then dissolved in appropriate amounts of soda ash and nonionic surfactant to obtain a circular made by Nisaka Manufacturing Co., Ltd. A scouring relaxation process with a liquid flow relaxer was performed at a maximum temperature of 110 ° C., and after draining, hot water was sufficiently washed, and after removing impurities and other substances, the surface was dried with a cylinder dryer having a surface temperature of 130 ° C. Subsequently, using a circular liquid flow dyeing machine manufactured by Nisaka Seisakusho, 130 ° C. high-pressure dyeing with disperse dyes was carried out. In the dyeing bath, flame retardant processing agent and antibacterial processing agent were applied by the simultaneous dyeing exhaustion method, and post-processing flame retardant / antibacterial treatment was applied. Detailed conditions and physical property measurement results are shown in Tables 1 and 2. Although it finished to the thing which has moderate flame retardance and antibacterial property, there was a problem in the durability in water washing and dry cleaning, and it did not endure repeated use. In addition, since expensive expensive flame retardants and antibacterial agents are prescribed, there are problems such as increased processing costs and difficulty in obtaining a clear color tone.
[0039]
[Table 1]

[0040]
[Table 2]

[0 04 1]
【The invention's effect】
As described above, according to the present invention, it is possible to obtain a polyester fabric having both flame retardancy and antibacterial properties, and in particular, it is a material suitable for use in daily life materials such as curtains, tablecloths, bed covers, wallpaper materials, cushions and the like. . Further, conventional post-flame retardant processed materials and antibacterial post-processed materials have poor washing durability and are not suitable for public uses such as theaters and hotels. However, according to the present invention, flame retardant performance and antibacterial performance are Since the post-processing is not performed with the flame retardant and antibacterial agent treatment, the load on the environment is small, and performance can be imparted economically and efficiently. Further, in the case of combustion, there is an effect that there is no problem of generation of harmful gases such as halogen gas, hydrogen halide gas, and cyan gas as in the conventional post-processed flame retardant fabric.

Claims (4)

It was 500~50000ppm containing a phosphorus atom in terms of atom, viewed contains at least a portion of the copolymerized polyester fiber having a phosphazene phenanthrene ring, a dyeing method of woven or knitted fabrics having the following antimicrobial performance, pH = A method for dyeing and processing a polyester fabric having flame retardancy and antibacterial properties, wherein the dyeing is performed under a high pressure condition of a treatment temperature of 100 ° C. or higher at a hydrogen ion concentration of 8 to 10. Evaluation test manual for antibacterial and deodorant processed products, bacteria count measurement method (Textile Products Sanitary Processing Council; current Textile Products New Function Evaluation Council, 1988) Difference in bacterial count increase or decrease is 1.6 or more. The flame retardant and antibacterial properties according to claim 1, wherein the copolymer polyester fiber is a fiber formed by using a copolymer polyester obtained by adding a phosphorus compound represented by [Chemical Formula 1]. A method for dyeing polyester fabric.

(Wherein R1 is a monovalent ester-forming functional group, R2 and R3 are the same or different groups, each selected from a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and R1; Represents a divalent or trivalent organic residue, n1 is 1 or 2, and n2 and n3 each represent an integer of 0 to 4.) Ethylenediaminetetraacetic acid (EDTA) or dyeing a polyester fabric having flame retardancy and antibacterial properties according to claim 1 or 2, characterized in that formulated in the dye bath and derivatives thereof. 4. The method for dyeing and processing a flame retardant and antibacterial polyester fabric according to claim 1, wherein the fabric structure is subjected to an alkali weight loss treatment in the knitting and knitting processing step.