JP4374185B2 - Method for dyeing cellulosic fiber structures - Google Patents

Method for dyeing cellulosic fiber structures Download PDF

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JP4374185B2
JP4374185B2 JP2002359043A JP2002359043A JP4374185B2 JP 4374185 B2 JP4374185 B2 JP 4374185B2 JP 2002359043 A JP2002359043 A JP 2002359043A JP 2002359043 A JP2002359043 A JP 2002359043A JP 4374185 B2 JP4374185 B2 JP 4374185B2
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Prior art keywords
dyeing
carbon dioxide
supercritical
dyed
disperse dye
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JP2004190169A (en
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小川  貴之
政則 中川
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Asahi Kasei Fibers Corp
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Asahi Kasei Fibers Corp
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Description

【0001】
【発明の属する技術分野】
本発明はセルロース系繊維構造物の染色方法に関し、さらに詳しくは超臨界または高圧二酸化炭素流体を用いたセルロース系繊維を含む繊維構造物の染色方法に関する。
【0002】
【従来の技術】
従来、直接染料または反応性染料を用いたセルロース系繊維の染色は、合成繊維の染色と比べ、染色によるシワの発生や染色ムラの発生が多いため、浴比を大きくして行われているが、この染色方法では染色後の廃液処理問題や大量の染色用水を必要とするという問題があった。環境問題が深刻化する昨今、セルロース系繊維の染色において、水などの資源の節約および硫酸ナトリウム使用量の低減など環境負荷の少ない染色法が望まれている。
近年、環境負荷の少ない染色法として、分散染料可染性の繊維を、超臨界状態の二酸化炭素流体に溶解可能な分散染料を用いて無水で染色する方法が提案されている(例えば、特許文献1および2参照)。
【0003】
また、セルロース系繊維のような分散染料では通常染色できない繊維構造物を染色する方法として、セルロース系繊維をアミノ基を有する化合物で変性した後、100〜150℃の温度および140〜250bar(14〜25MPa)の圧力で該繊維を反応性分散染料にて染色する方法が提案されている(例えば、特許文献3参照)。この方法ではセルロース系繊維を改質により分散染料可染化させた後に超臨界染色が行われるが、事前に溶剤でセルロース系繊維を改質しなければならないため、堅牢度が低く、風合いが粗硬になるなどの問題がある。
また、繊維を予めポリエチレングリコールで前処理した後、分散染料を用いて超臨界流体を溶媒として染色する方法が提案されている(例えば、特許文献4および非特許文献1参照)。しかし、この方法では、均一で十分な染着性が得られにくく、また堅牢な染色物が得られない。
また、超臨界またはほぼ臨界の流体中で1種類以上の繊維材料を反応性分散染料で染色する方法が提案されている(例えば、特許文献5参照)。この方法では、反応性分散染料を用い、流体内の相対湿度を50%〜100%にして超臨界染色が行われるが、284バール(28.4MPa)の超高圧下でセルロース系繊維に水分が付与されるため、高圧下での水の酸性化による被染物の風合いの変化や強度劣化などの問題が生じる。
【0004】
また、綿を超臨界染色するに際し、綿繊維を予め前処理した後、反応型分散染料を用いる超臨界染色方法が報告されている(例えば、特許文献6および非特許文献2参照)。この方法では、テトラエチレングリコールジメチルエーテル(以下、TEGDMEと称する)やN−メチルピロリドン(以下、NMPと称する)を前処理剤とし、アセトンを二酸化炭素の共溶媒として用い、さらに綿繊維をアルカリ水溶液で処理して染色が行われるが、綿繊維を水溶液で前処理する必要があるため、染色前の被染物の前処理や乾燥工程が必要となり、工程が長くなるなどの欠点があった。またアルカリ水溶液でセルロース系繊維を前処理すると、被染物の風合いが変化し易くなり、また上記TEGDMEは水との親和性が高いため、染色後の堅牢度を低下させる恐れがあった。
このように、セルロース系繊維を含む繊維構造物の染色において、環境負荷が少なく、均一かつ濃色に染色でき、さらに堅牢性に優れる染色方法はいまだ見出されていない。
【0005】
【特許文献1】
特開平4−245981号公報
【特許文献2】
特開2001−32134号公報
【特許文献3】
特開平8−74185号公報
【特許文献4】
米国特許第5298032号明細書
【特許文献5】
特開2001−316988号公報
【特許文献6】
特開2002−201575号公報
【非特許文献1】
M.L.Colomboらの報告(Proc.5th Meetingon Supercritical Fluids,351(1998))
【非特許文献2】
岡山県新技術振興財団らの報告(平成12年度地域コンソーシアム研究開発事業ベンチャー企業支援型地域コンソーシアム成果報告書)
【0006】
【発明が解決しようとする課題】
本発明の課題は、上記従来技術の問題点を解決し、超臨界または高圧二酸化炭素を媒体として、セルロース系繊維を改質することなく、少ない環境負荷で、均一かつ濃色に染色することができる、高堅牢性を有するセルロース系繊維構造物の染色方法を提供することにある。
【0007】
【課題を解決するための手段】
本発明者らは、上記課題について鋭意検討した結果、セルロース系繊維の染色において、分散染料可染性セルロース系繊維を含む構造物を用い、かつ助剤として低級アルコールおよび好ましくは環状アミン化合物を染色段階の超臨界または高圧二酸化炭素の染色槽に添加することにより、上記課題を解決できることを見出し、本発明に到達した。
すなわち、上記課題を達成するために本願で特許請求される発明は以下の通りである。
【0008】
(1)繰り返し単位の20〜95重量%が芳香環を有し、かつ該芳香環に隣接する炭素原子がエステル結合(−COO−)および/またはエーテル結合(−O−)を少なくとも1つ有する化合物より構成される重合体微粒子を1〜40重量%含有する分散染料可染性セルロース系繊維を含む構造物を超臨界または高圧二酸化炭素を媒体として分散染料により染色するに際し、前記媒体中に炭素数1〜4の低級アルコールを添加することを特徴とするセルロース系繊維構造物の染色方法。
)前記媒体中に、N−メチルピロリドンおよび4−メチルモルフォリン,N−オキシドから選ばれる無機性/有機性値が1.0〜4.5である環状アミン系化合物を添加することを特徴とする()に記載のセルロース系繊維構造物の染色方法。
【0009】
【発明の実施の形態】
本発明において、超臨界二酸化炭素とは、二酸化炭素に7.38MPa以上の圧力および31.1℃以上の温度をかけることにより製造される高密度流体をいい、高圧二酸化炭素とは、31.1℃で4.0MPa以上、7.38MPa未満のものをいう。また本発明の方法は、中空糸、多孔糸、綿、紐、不織布、織物、編物、糸条、およびこれらを使用した衣類、医療用製品、資材等の分散染料可染性セルロース系繊維を含む構造体に適用され、繊維の形状、織編物の組織、不織布等の構造、糸条形態等によらない。さらに本発明でいうセルロース系繊維は、綿などの天然セルロース系繊維以外のセルロース系繊維を意味し、短繊維または長繊維を含む。具体的には、銅アンモニアレーヨン繊維およびビスコースレーヨン繊維が挙げられ、繊維は樹脂加工されていても、セルロースと反応する2つ以上の官能基を有する化合物で架橋されていてもよい。
【0010】
本発明に用いられる分散染料可染性セルロース系繊維としては、繰り返し単位の20〜95重量%が芳香環を有し、かつ該芳香環に隣接する炭素原子がエステル結合(−COO−)および/またはエーテル結合(−O−)を少なくとも1つ有する化合物より構成されている重合体微粒子を1〜40重量%含有するセルロース系繊維、例えば、WO98/58104号公報記載の分散染料にて染色されうる重合体を含有するセルロース系繊維が挙げられる。
上記セルロース系繊維中に含有される重合体微粒子は、芳香環を有し、かつ芳香環または芳香環に隣接する炭素原子にエステル結合または/およびエーテル結合を少なくとも一つ以上有する化合物(以下、この繰り返しユニットを同色ユニットと称する)を20〜95重量%の範囲で重合されたものである。
【0011】
前記重合体を構成するポリマーは、単体で分散染料にて染色されうるものであるなら、その組成はいかなるものでもよいが、好ましくはビニル系ポリマーまたは重縮合系ポリマーを含有してなる組成物である。ビニル系ポリマーとしては、芳香族ビニルエステル系ポリマー、芳香族ビニルエーテル系ポリマー、芳香族ビニルケトン系ポリマー、芳香族メタアクリル酸エステル系ポリマー、スチレン誘導体系ポリマー、芳香族マレイン酸エステル系ポリマーなどが挙げられ、重縮合系ポリマーとしては、芳香族ポリエステル共重合などが挙げられる。同色ユニットについては芳香環が少なくとも一つあればよく、分散染料との親和性の点では平面性の高い多環式芳香環が優れるが、工業的にはベンゼン環系化合物が好ましい。
最も好ましいビニル系ポリマーとしては、芳香族メタアクリル酸ポリエステルポリマーおよび芳香族ビニルエステルポリマーが挙げられる。重縮合系としては、テレフタル酸/アジピン酸/エチレングリコール/ポリエチレングリコール系、テレフタル酸/アジピン酸/エチレングリコール/5−ナトリウムスルイソフタル酸系、等の分散染料易染性ポリエチレンテレフタレート等が挙げられる。
【0012】
本発明のセルロース系繊維中の含有粒子は、繊維内部で高分散しているほうが好ましい。また、染色工程、後加工工程、洗濯、ドライクリーニング等の処理の際に、重合体が溶出しない程度の重合度を有している必要がある。これら重合体の微粒子は、1種類またはそれ以上の種類の重合体を混合されたものでもよく、平均粒径、粒度分布、または分子量の異なる微粒子を含んでいてもよい。重合体の平均粒子径は特に限定するものではないが、好ましくはその平均粒子径が0.01〜5μmのものである。
【0013】
本発明に用いられる分散染料としては、超臨界または高圧二酸化炭素に溶解するものであればよい。染色槽への反応型分散染料の添加は、二酸化炭素の添加前または超臨界もしくは高圧二酸化炭素状態のいずれの段階で行ってもよいが、超臨界または高圧二酸化炭素状態で添加するのが好ましい。
超臨界または高圧二酸化炭素を媒体として染色を行う際には、セルロース系繊維を濃色に染色するために、染色槽に低級アルコールおよび無機性/有機性値が1.0〜4.5である環状アミン系化合物の少なくとも1種を助剤として添加することが好ましい。染色槽への上記助剤の添加は、二酸化炭素の添加前または超臨界もしくは高圧二酸化炭素状態のいずれの段階で行ってもよいが、超臨界または高圧二酸化炭素の状態で添加するのが好ましい。低級アルコールおよび環状アミン系化合物はそれぞれ単独で用いても両者を同時に用いてもよい。
【0014】
低級アルコールとしては、メタノール、エタノール、1−プロパノール、2−プロパノール、1−ブタノール等が挙げられるが、メタノールおよびエタノールが好ましく用いられる。低級アルコールの添加量は、染色槽の単位容積に対して0.1〜5vol.%の範囲が好ましく、より好ましくは0.5〜2vol.%である。
環状アミン系化合物としては、無機性/有機性値が1.0〜4.5のものが好ましく、より好ましくは1.4〜4.0であるものが用いられる。ここで環状アミン系化合物の無機性/有機性値は、有機化合物の一般性状を表す値であり、有機化合物は、その数値が小さいほど疎水性になり、大きいほど親水性になることを示す。この値が1.0未満では被染物の染料の未染着や脱落を起こし易く、4.5を超えると染料の色相が変化する場合がある。このような環状アミン系化合物としては、NMP、NMMO(4−メチルモルフォリン,N−オキシド)等が挙げられる。環状アミン系化合物の添加量は、染色槽の単位容積に対して0.1〜5vol.%の範囲が好ましく、より好ましくは0.3〜3vol.%である。
【0015】
次に、本発明の染色方法について説明する。超臨界の二酸化炭素を媒体とする場合、染色温度は二酸化炭素の臨界温度よりも5℃以上高いのが好ましく、より好ましくは70〜120℃である。染色温度を120℃以上にしても問題はないが、120℃以下で十分に染着可能であり、コスト高を招く。染色圧力は、二酸化炭素の臨界圧力である7.38MPa以上であればよく、好ましくは15〜25MPaである。超臨界状態の雰囲気を作るには、液化二酸化炭素またはドライアイスなどを用い、密閉系にて31.1℃以上で、かつ7.38MPa以上にすればよい。具体的には、例えば、オートクレーブ中に分散染料、被染物および低級アルコール、好ましくはさらに無機性/有機性値が1.0〜4.5の環状アミン系化合物などの助剤を入れ、その中にドライアイスまたは液化二酸化炭素などを入れて密閉し、加圧・加温して7.38MPa以上の圧力および31.1℃以上の温度を保持して染色を行う。
また高圧二酸化炭素を媒体とする場合は、染色濃度は60℃以上が好ましく、より好ましくは70〜120℃である。染色圧力は4.0MPa以上7.38MPa未満が好ましく、より好ましくは5.0〜7.0MPaである。
【0016】
【実施例】
以下に本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。染色後の被染物の評価は以下のようにして行った。
1)染色物の測色値
洗浄前およびボイル洗浄後の染色物について、マクベスCOLOR−EYE3000分光光度計を用い、色差式:CIELab法により、K/S(色濃度)値、L(明度)値およびC(彩度)値を測定した。なお、各測定値により、それぞれ下記のように評価される。
K/S値:表面染着濃度を表し、数値が大きいほど濃染である。
L値:明度を表し、数値が大きいほど明るく、淡染である。
C値:彩度を表し、数値が大きいほど鮮やかである。
2)洗濯堅牢度評価
洗浄前およびボイル洗浄後の被染物の洗濯堅牢度をJIS L−0884 A−2法に準じ、次のように評価した。すなわち、試験片の変褪色および添付白布片の汚染の程度をそれぞれ変褪色用グレースケールおよび汚染用グレースケールと比較して5級〜1級の5段階で評価した。なお、5級が変褪色または汚染がない場合を示し、数値が小さくなるほど変褪色、汚染が大きくなることを示す。
【0017】
3)昇華堅牢度評価
ボイル洗浄後の被染物の昇華堅牢度をJIS L−0854に準じ、次のように評価した。すなわち、試験片の変褪色および添付白布片の汚染の程度をそれぞれ変褪色用グレースケールおよび汚染用グレースケールと比較して5級〜1級の5段階で評価した。なお、5級が昇華堅牢度に優れることを示し、数値が小さくなるほど昇華堅牢度に劣ることを示す。
4)総合評価
上記1)〜3)の項目について下記のように総合判断した。
◎:非常に優れている。
○:優れている。
×:不適である
【0018】
実施例1
まず、下記に示す固形分濃度26.5%、平均粒径0.039μmの重合体エマルジョンと銅アンモニアセルロース溶液を混合し、紡糸させることで得られる135dtex/72fの繊維を、栄光産業社製試験筒編み機NCR−BW(編釜3.5インチ,針本数220本)にて筒編物とした。次に該編物を常法にて精練し、100℃で1分乾燥した。
上記重合体エマルジョンは、WO98/58104号公報実施例1の記載に従って重合して得た。すなわち、安息香酸ビニル、メチルメタアクリレート、スチレン、アクリルアミド、アントックスMS60(日本乳化剤社製アニオン系乳化剤)、水酸化ナトリウム10%水溶液、過硫酸カリウム水溶液、蒸留水を添加したプレ乳化物を、ニューコール707SF(日本乳化剤社製アニオン系界面活性剤)、アクアロンHS10(第一工業社製アニオン系乳化剤)、イタコン酸および過硫酸カリウムと混合後、攪拌しながらt−ブチルハイドロパーオキサイド水溶液と重亜硫酸ソーダ、エマルゲン950(花王社製ノニオン系界面活性剤)を加えて重合させてエマルジョンを得た。
【0019】
次に容積1000ccのオートクレーブ(材質SUS316)内に、上記筒編物2.8gおよび市販の分散染料(Ciba SC.社Terasil Black BFA)5%omf.およびメタノール10mlを入れた。次に該オートクレーブを20℃にて15分放置し、オートクレーブ内部が超臨界状態ではないことを確認した後、昇温速度2℃/分にてオートクレーブを昇温した。オートクレーブ内部の温度が120℃になったことを確認して、オートクレーブ内に液化二酸化炭素をオートクレーブの内圧が25MPaになるよう注入した後、120分間温度と圧力を保持し染色を行った。次に、オートクレーブの圧力を1.0MPa/分で減圧を行い5MPaまで減圧後はオートクレーブ内部圧力を大気圧まで開放した。
この結果、紺色に均一に染色され、かつ風合いの変化のない染色物を得た。得られた被染物を80℃で10分洗浄し乾燥後、測色した結果を表1に示したが、洗浄前とボイル洗浄後のK/S値の差が殆どなく、ボイル洗浄による染料脱落が極めて少なかった。
【0020】
実施例2
実施例1において、編物をオートクレーブに投入する際に、分散染料、メタノールと同時にNMPを3ml添加した以外は、実施例1と同条件にて染色を行った。
この結果、紺色に均一に染色され、かつ風合いの変化のない染色物を得た。得られた被染物を沸水洗浄、80℃で10分湯洗、乾燥後測色した結果を表1に示したが、洗浄前とボイル洗浄後のK/S値の差が殆どなく、ボイル洗浄により染料脱落が極めて少なかった。
【0021】
比較例1
実施例1において、編物をオートクレーブに投入する際に、メタノールを添加せずに、染色を行った以外は、実施例1と同条件にて染色を行った。この結果、被染物はかなり薄い紺色を呈しており染料本来の発色は見られなかった。80℃で10分湯洗、乾燥した結果、染料は布帛から脱落した。
【0022】
【表1】

Figure 0004374185
【0023】
表1から、実施例1、2では、いずれも洗浄前およびボイル洗浄後の染色物のK/S値、L値、C値共に殆ど差がなく、かつ、洗浄前とボイル洗浄後の洗濯堅牢度・昇華堅牢度が良好な結果が得られ、均一な染色物が得られることが確認された。これに対して、比較例1は染着が低く、かつ洗浄で簡単に染料が脱落し問題があった。
【0024】
【発明の効果】
本発明によれば、セルロース系繊維を含む繊維構造物を、少ない環境負荷で、セルロース系繊維の改質をすることなく、均一かつ濃色に染色でき、また堅牢性に優れた染色物を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for dyeing cellulosic fiber structures, and more particularly to a method for dyeing fiber structures containing cellulosic fibers using supercritical or high pressure carbon dioxide fluid.
[0002]
[Prior art]
Conventionally, dyeing of cellulosic fibers using direct dyes or reactive dyes has been carried out with a larger bath ratio because there are more wrinkles and uneven dyeing due to dyeing than dyeing synthetic fibers. This dyeing method has a problem of waste liquid treatment after dyeing and a large amount of dyeing water. In recent years when environmental problems have become more serious, dyeing methods with less environmental impact such as saving resources such as water and reducing the amount of sodium sulfate used are desired in dyeing cellulosic fibers.
In recent years, as a dyeing method with less environmental impact, a method has been proposed in which disperse dyeable fibers are dyed anhydrously using a disperse dye that can be dissolved in a carbon dioxide fluid in a supercritical state (for example, a patent document). 1 and 2).
[0003]
In addition, as a method of dyeing a fiber structure that cannot be usually dyed with a disperse dye such as a cellulose fiber, a cellulose fiber is modified with a compound having an amino group, and then a temperature of 100 to 150 ° C. and 140 to 250 bar (14 to 250 bar). A method of dyeing the fiber with a reactive disperse dye at a pressure of 25 MPa has been proposed (see, for example, Patent Document 3). In this method, supercritical dyeing is performed after the cellulosic fibers are dyed by disperse dye by modification. However, since the cellulosic fibers must be modified with a solvent in advance, the fastness is low and the texture is rough. There are problems such as becoming hard.
Further, a method has been proposed in which a fiber is pretreated with polyethylene glycol in advance and then dyed using a disperse dye as a supercritical fluid as a solvent (for example, see Patent Document 4 and Non-Patent Document 1). However, with this method, uniform and sufficient dyeing properties are difficult to obtain, and robust dyeings cannot be obtained.
Further, a method has been proposed in which one or more types of fiber materials are dyed with a reactive disperse dye in a supercritical or nearly critical fluid (see, for example, Patent Document 5). In this method, supercritical dyeing is performed using a reactive disperse dye and a relative humidity in the fluid of 50% to 100%. However, moisture is contained in the cellulosic fiber under an ultrahigh pressure of 284 bar (28.4 MPa). Therefore, problems such as a change in texture of the dyed material and deterioration of strength due to acidification of water under high pressure occur.
[0004]
In addition, there has been reported a supercritical dyeing method using a reactive disperse dye after pretreating cotton fibers in advance for supercritical dyeing of cotton (see, for example, Patent Document 6 and Non-Patent Document 2). In this method, tetraethylene glycol dimethyl ether (hereinafter referred to as TEGDME) or N-methylpyrrolidone (hereinafter referred to as NMP) is used as a pretreatment agent, acetone is used as a co-solvent for carbon dioxide, and cotton fibers are added with an alkaline aqueous solution. Dyeing is carried out by processing, but since cotton fibers need to be pretreated with an aqueous solution, pretreatment and drying steps of the dyed article before dyeing are necessary, and there are disadvantages such as a long process. In addition, when cellulose fibers are pretreated with an alkaline aqueous solution, the texture of the dyed product is likely to change, and the TEGDME has a high affinity with water, so that the fastness after dyeing may be reduced.
Thus, in dyeing of fiber structures containing cellulosic fibers, no dyeing method has yet been found that has a low environmental burden, can be dyed uniformly and in dark colors, and is excellent in fastness.
[0005]
[Patent Document 1]
JP-A-4-245981 [Patent Document 2]
JP 2001-32134 A [Patent Document 3]
JP-A-8-74185 [Patent Document 4]
US Pat. No. 5,298,032 [Patent Document 5]
JP 2001-316988 A [Patent Document 6]
JP 2002-201575 A [Non-Patent Document 1]
M.M. L. Report by Columbo et al. (Proc. 5th Meetingon Supercritical Fluids, 351 (1998))
[Non-Patent Document 2]
Report of Okayama Prefectural New Technology Promotion Foundation (2000 Regional Consortium R & D Project Venture Company Support Type Regional Consortium Results Report)
[0006]
[Problems to be solved by the invention]
The object of the present invention is to solve the above-mentioned problems of the prior art, and to dye uniformly and darkly with a small environmental load without modifying cellulosic fibers using supercritical or high-pressure carbon dioxide as a medium. Another object of the present invention is to provide a method for dyeing a cellulosic fiber structure having high fastness.
[0007]
[Means for Solving the Problems]
As a result of intensive studies on the above problems, the present inventors have used a structure containing a disperse dyeable cellulosic fiber and dyeing a lower alcohol and preferably a cyclic amine compound as an auxiliary agent in the dyeing of the cellulose fiber. The inventors have found that the above-mentioned problems can be solved by adding to a supercritical or high-pressure carbon dioxide dyeing tank at a stage, and have reached the present invention.
That is, the invention claimed in the present application in order to achieve the above-described problems is as follows.
[0008]
(1) 20 to 95% by weight of the repeating unit has an aromatic ring, and the carbon atom adjacent to the aromatic ring has at least one ester bond (—COO—) and / or ether bond (—O—). carbon structure including a disperse dye-dyeable cellulosic fibers upon staining with disperse dyes supercritical or high pressure carbon dioxide as a medium, in the medium containing 1 to 40% by weight than polymer composed particulate compound A method for dyeing a cellulosic fiber structure, which comprises adding a lower alcohol of formulas 1 to 4 .
( 2 ) adding a cyclic amine compound having an inorganic / organic value of 1.0 to 4.5 selected from N-methylpyrrolidone, 4-methylmorpholine, and N-oxide to the medium. The method for dyeing a cellulosic fiber structure according to ( 1 ), which is characterized.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, supercritical carbon dioxide refers to a high-density fluid produced by applying a pressure of 7.38 MPa or more and a temperature of 31.1 ° C. or more to carbon dioxide, and high-pressure carbon dioxide is 31.1 It means 4.0 MPa or more and less than 7.38 MPa at ° C. Further, the method of the present invention includes hollow fibers, porous yarns, cotton, strings, nonwoven fabrics, woven fabrics, knitted fabrics, yarns, and disperse dye-dyeing cellulosic fibers such as clothing, medical products, and materials using these. It is applied to the structure and does not depend on the shape of the fiber, the structure of the knitted or knitted fabric, the structure of the nonwoven fabric, the thread form, or the like. Furthermore, the cellulosic fiber referred to in the present invention means cellulosic fibers other than natural cellulosic fibers such as cotton, and includes short fibers or long fibers. Specific examples include copper ammonia rayon fiber and viscose rayon fiber. The fiber may be resin-processed or crosslinked with a compound having two or more functional groups that react with cellulose.
[0010]
The disperse dye-dyeable cellulosic fibers used in the present invention, 20 to 95 wt% that a repetitive unit having an aromatic ring, and the carbon atom adjacent to the aromatic ring is an ester bond (-COO-) And / or cellulose fiber containing 1 to 40% by weight of polymer fine particles composed of a compound having at least one ether bond (—O—), for example, dyed with a disperse dye described in WO98 / 58104 Cellulosic fibers containing polymers that can be made.
The polymer fine particles contained in the cellulosic fiber have an aromatic ring and a compound having an aromatic ring and at least one ester bond and / or ether bond at the carbon atom adjacent to the aromatic ring (hereinafter referred to as this compound). The repeating unit is referred to as the same color unit) in a range of 20 to 95% by weight.
[0011]
The polymer constituting the polymer may be any composition as long as it can be dyed alone with a disperse dye, but is preferably a composition containing a vinyl polymer or a polycondensation polymer. is there. Examples of vinyl polymers include aromatic vinyl ester polymers, aromatic vinyl ether polymers, aromatic vinyl ketone polymers, aromatic methacrylic acid ester polymers, styrene derivative polymers, and aromatic maleic acid ester polymers. Examples of the polycondensation polymer include aromatic polyester copolymerization. For the same color unit, at least one aromatic ring is sufficient, and a polycyclic aromatic ring having high planarity is excellent in terms of affinity with the disperse dye, but a benzene ring system compound is preferred industrially.
The most preferred vinyl polymers include aromatic methacrylic polyester polymers and aromatic vinyl ester polymers. Examples of the polycondensation system include terephthalic acid / adipic acid / ethylene glycol / polyethylene glycol system, terephthalic acid / adipic acid / ethylene glycol / 5-sodium sulphophthalic acid system, and the like, and dye-dispersible dyeable polyethylene terephthalate.
[0012]
The contained particles in the cellulose fiber of the present invention are preferably highly dispersed inside the fiber. Further, it is necessary to have a degree of polymerization such that the polymer does not elute during the dyeing process, post-processing process, washing, dry cleaning and the like. These polymer fine particles may be a mixture of one or more types of polymers, and may include fine particles having different average particle diameters, particle size distributions, or molecular weights. The average particle size of the polymer is not particularly limited, but preferably the average particle size is 0.01 to 5 μm.
[0013]
Any disperse dye may be used in the present invention as long as it is soluble in supercritical or high-pressure carbon dioxide. The reactive disperse dye may be added to the dyeing tank before addition of carbon dioxide or at any stage of the supercritical or high-pressure carbon dioxide state, but is preferably added in the supercritical or high-pressure carbon dioxide state.
When dyeing using supercritical or high-pressure carbon dioxide as a medium, the dyeing tank has a lower alcohol and an inorganic / organic value of 1.0 to 4.5 in order to dye cellulosic fibers darkly. It is preferable to add at least one cyclic amine compound as an auxiliary agent. The auxiliary agent may be added to the dyeing tank before addition of carbon dioxide or at any stage of supercritical or high-pressure carbon dioxide, but is preferably added in a supercritical or high-pressure carbon dioxide state. The lower alcohol and the cyclic amine compound may be used alone or in combination.
[0014]
Examples of the lower alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and the like, and methanol and ethanol are preferably used. The amount of the lower alcohol added is 0.1 to 5 vol. % Range is preferred, more preferably 0.5 to 2 vol. %.
As the cyclic amine compound, those having an inorganic / organic value of 1.0 to 4.5 are preferable, and those having a value of 1.4 to 4.0 are more preferable. Here, the inorganic / organic value of the cyclic amine compound is a value representing the general properties of the organic compound, and the organic compound becomes hydrophobic as the numerical value is small, and becomes hydrophilic as the value is large. If this value is less than 1.0, the dye of the article to be dyed is likely to be undyed or dropped, and if it exceeds 4.5, the hue of the dye may change. Examples of such cyclic amine compounds include NMP and NMMO (4-methylmorpholine, N-oxide). The addition amount of the cyclic amine compound is 0.1 to 5 vol. % Range is preferable, and more preferably 0.3 to 3 vol. %.
[0015]
Next, the staining method of the present invention will be described. When supercritical carbon dioxide is used as a medium, the dyeing temperature is preferably 5 ° C. or more higher than the critical temperature of carbon dioxide, and more preferably 70 to 120 ° C. Although there is no problem even if the dyeing temperature is 120 ° C. or higher, sufficient dyeing is possible at 120 ° C. or lower, resulting in an increase in cost. The dyeing pressure should just be 7.38 Mpa or more which is the critical pressure of a carbon dioxide, Preferably it is 15-25 Mpa. In order to create an atmosphere in a supercritical state, liquefied carbon dioxide, dry ice, or the like is used, and the temperature may be 31.1 ° C. or higher and 7.38 MPa or higher in a closed system. Specifically, for example, an auxiliary agent such as a disperse dye, a material to be dyed, and a lower alcohol, preferably a cyclic amine compound having an inorganic / organic value of 1.0 to 4.5 is placed in an autoclave. The sample is sealed with dry ice or liquefied carbon dioxide, etc., and dyeing is carried out by pressurizing and heating to maintain a pressure of 7.38 MPa or more and a temperature of 31.1 ° C. or more.
When high pressure carbon dioxide is used as a medium, the dyeing concentration is preferably 60 ° C. or higher, more preferably 70 to 120 ° C. The dyeing pressure is preferably 4.0 MPa or more and less than 7.38 MPa, more preferably 5.0 to 7.0 MPa.
[0016]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Evaluation of the dyed object after dyeing was performed as follows.
1) Colorimetric value of dyed product Before dyeing and after washing with boil, dyed product using a Macbeth COLOR-EYE 3000 spectrophotometer, color difference formula: CIELab method, K / S (color density) value, L (lightness) value And C (saturation) values were measured. Each measurement value is evaluated as follows.
K / S value: Represents the surface dyeing density. The larger the value, the deeper the dyeing.
L value: Represents lightness. The larger the value, the brighter and lighter the dye.
C value: represents saturation, and the larger the value, the brighter.
2) Evaluation of washing fastness The washing fastness of the dyed articles before washing and after boil washing was evaluated in the following manner according to JIS L-0884 A-2 method. That is, the discoloration color of the test piece and the degree of contamination of the attached white cloth piece were evaluated in five grades from Grade 5 to Grade 1 compared with the gray scale for color change and the gray scale for contamination, respectively. Grade 5 indicates no discoloration or contamination, and the smaller the value, the greater the discoloration or contamination.
[0017]
3) Sublimation fastness evaluation The sublimation fastness of the article to be dyed after boil washing was evaluated according to JIS L-0854 as follows. That is, the discoloration color of the test piece and the degree of contamination of the attached white cloth piece were evaluated in five grades from Grade 5 to Grade 1 compared with the gray scale for color change and the gray scale for contamination, respectively. In addition, grade 5 shows that it is excellent in sublimation fastness, and shows that it is inferior to sublimation fastness, so that a numerical value becomes small.
4) Comprehensive evaluation The above items 1) to 3) were comprehensively determined as follows.
A: Very good.
○: Excellent.
×: unsuitable [0018]
Example 1
First, a 135 dtex / 72f fiber obtained by mixing and spinning a polymer emulsion having a solid content concentration of 26.5% and an average particle size of 0.039 μm and spinning as shown below, manufactured by Glory Industries Co., Ltd. Cylinder knitting was made with a cylinder knitting machine NCR-BW (knitting hook 3.5 inches, number of needles 220). Next, the knitted fabric was scoured by a conventional method and dried at 100 ° C. for 1 minute.
The polymer emulsion was obtained by polymerization according to the description in Example 1 of WO98 / 58104. That is, a pre-emulsion obtained by adding vinyl benzoate, methyl methacrylate, styrene, acrylamide, Antox MS60 (anionic emulsifier manufactured by Nippon Emulsifier Co., Ltd.), sodium hydroxide 10% aqueous solution, potassium persulfate aqueous solution, distilled water, After mixing with Cole 707SF (anionic surfactant manufactured by Nippon Emulsifier Co., Ltd.), Aqualon HS10 (anionic emulsifier manufactured by Daiichi Kogyo Co., Ltd.), itaconic acid and potassium persulfate, t-butyl hydroperoxide aqueous solution and bisulfite with stirring Soda and Emulgen 950 (non-ionic surfactant manufactured by Kao Corporation) were added and polymerized to obtain an emulsion.
[0019]
Next, in a 1000 cc autoclave (material SUS316), 2.8 g of the above-mentioned tubular knitted fabric and a commercially available disperse dye (Ciba SC. Terasil Black BFA) 5% omf. And 10 ml of methanol. Next, the autoclave was allowed to stand at 20 ° C. for 15 minutes, and after confirming that the inside of the autoclave was not in a supercritical state, the autoclave was heated at a temperature rising rate of 2 ° C./min. After confirming that the temperature inside the autoclave reached 120 ° C., liquefied carbon dioxide was injected into the autoclave so that the internal pressure of the autoclave was 25 MPa, and then the temperature and pressure were maintained for 120 minutes for dyeing. Next, the pressure of the autoclave was reduced at 1.0 MPa / min, and after reducing the pressure to 5 MPa, the internal pressure of the autoclave was released to atmospheric pressure.
As a result, a dyed product that was uniformly dyed in amber color and did not change in texture was obtained. The obtained article was washed at 80 ° C. for 10 minutes, dried, and measured for color. The results of color measurement are shown in Table 1, but there is almost no difference in K / S value before washing and after washing with boil. There was very little.
[0020]
Example 2
In Example 1, dyeing was performed under the same conditions as in Example 1 except that 3 ml of NMP was added simultaneously with the disperse dye and methanol when the knitted fabric was put into the autoclave.
As a result, a dyed product that was uniformly dyed in amber color and did not change in texture was obtained. Table 1 shows the results of color washing after boiling water washing at 80 ° C. for 10 minutes and color measurement after drying. The difference in K / S values before washing and after boil washing is almost the same. As a result, dye dropout was extremely small.
[0021]
Comparative Example 1
In Example 1, dyeing was performed under the same conditions as in Example 1 except that when the knitted fabric was put into the autoclave, dyeing was performed without adding methanol. As a result, the object to be dyed had a fairly light amber color, and the original color of the dye was not observed. As a result of washing with hot water at 80 ° C. for 10 minutes and drying, the dye was removed from the fabric.
[0022]
[Table 1]
Figure 0004374185
[0023]
From Table 1, in Examples 1 and 2, there is almost no difference in K / S value, L value, and C value of the dyed product before washing and after boil washing, and washing fastness before washing and after boil washing. As a result, it was confirmed that a good dyeing fastness and sublimation fastness were obtained, and a uniform dyed product was obtained. On the other hand, in Comparative Example 1, there was a problem that the dyeing was low and the dye was easily removed by washing.
[0024]
【The invention's effect】
According to the present invention, a fiber structure containing cellulosic fibers can be dyed uniformly and deeply with little environmental load and without modification of cellulosic fibers, and a dyed product excellent in fastness is provided. can do.

Claims (2)

繰り返し単位の20〜95重量%が芳香環を有し、かつ該芳香環に隣接する炭素原子がエステル結合(−COO−)および/またはエーテル結合(−O−)を少なくとも1つ有する化合物より構成される重合体微粒子を1〜40重量%含有する分散染料可染性セルロース系繊維を含む構造物を超臨界または高圧二酸化炭素を媒体として分散染料により染色するに際し、前記媒体中に炭素数1〜4の低級アルコールを添加することを特徴とするセルロース系繊維構造物の染色方法。 20 to 95% by weight of the repeating unit is composed of a compound having an aromatic ring and a carbon atom adjacent to the aromatic ring having at least one ester bond (—COO—) and / or ether bond (—O—). upon staining with disperse dye structures containing a disperse dye-dyeable cellulosic fibers supercritical or high pressure carbon dioxide as a medium containing 1 to 40% by weight of polymer microparticles, to several carbons in said medium 4. A method for dyeing a cellulosic fiber structure, comprising adding 4 lower alcohol. 前記媒体中に、N−メチルピロリドンおよび4−メチルモルフォリン,N−オキシドから選ばれる無機性/有機性値が1.0〜4.5である環状アミン系化合物を添加することを特徴とする請求項に記載のセルロース系繊維構造物の染色方法。A cyclic amine compound having an inorganic / organic value of 1.0 to 4.5 selected from N-methylpyrrolidone, 4-methylmorpholine, and N-oxide is added to the medium. The method for dyeing a cellulose fiber structure according to claim 1 .
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