JP3753407B2 - Method for improving light resistance of wholly aromatic polyamide - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は耐光性に優れた全芳香族ポリアミド繊維、紡績糸、編織物、フェルト、不織布、紙などの布帛を製造するするための全芳香族ポリアミドの耐光性改善方法に関する。
【０００２】
【従来の技術】
パラ系全芳香族ポリアミド繊維は、高強度、高弾性率、高耐熱性、非導電性、錆びない等の高い機能性と、有機繊維のしなやかさと軽量性を合わせ持った合成繊維である。これらの特長から、自動車タイヤ、自動車用伝動ベルト、コンベヤ、光ファイバーの補強等の産業用資材として用いられている。
【０００３】
一方、衣料用途や繊維製品としては、刃物に対する切れにくさを応用した作業用手袋や作業服、スポーツ衣料などに使用されている。また、限界酸素指数が２９で、本質的に燃えにくいことや、５００℃という高温において融けたり収縮したりせずに炭化することから、消防服や燃えにくさの要求される椅子貼り地やカーテンなどのインテリヤ用品としての開発が進められている。
【０００４】
パラ系全芳香族ポリアミド繊維は、淡黄色を呈しているが、紫外線に曝されると褐色に変色する。紫外線は、直射日光中に多量に含まれ、パラ系全芳香族ポリアミド繊維を屋外に暴露して置くと、数時間で淡い褐色に変色する。紫外線は、昼間の日陰の光にも含まれているし、白熱電灯や、蛍光灯の光の中にも微量に含まれているので、パラ系全芳香族ポリアミド繊維からなる繊維製品の紫外線による変色は、流通や使用段階において大きな問題である。
【０００５】
特に、タイヤやベルト、ロープなど産業用資材とは異なり、審美性が要求される衣料用やインテリヤ製品にパラ系全芳香族ポリアミド繊維を応用する場合、紫外線による変色の問題は大きい。
【０００６】
これに対し、パラ系全芳香族ポリアミド繊維を他の繊維で被覆する事によりパラ系全芳香族ポリアミド繊維を隠ぺいし、光による変色の影響を改善する方法がある。例えば、特開平３ー８３０号公報には、芯成分の主体が芳香族ポリアミドであり、鞘成分の主体がポリエステル繊維の短繊維あるいは長繊維である芯鞘型複合糸であり、芯成分が１０〜５０重量％、鞘成分が９０〜５０重量％の割合で構成された芯鞘型複合糸が提案されている。衣料を始めとする繊維製品においては、２０ｓ／１以下の細い糸が要求されるが、この太さにおいては鞘成分によって完全に芯成分を被覆する事は困難で、パラ系全芳香族ポリアミド繊維の一部が露出したり、鞘成分を通して紫外線が入ったりして変色がおこるので問題の解決にはなっていない。
【０００７】
また、特開平０１−１７４６８０号公報には、パラ系全芳香族ポリアミド繊維にポリエチレンイミン系化合物を付着させた後、１３０〜２５０℃で熱処理する事が提案されている。しかし、該繊維表面にポリエチレンイミン系化合物の樹脂皮膜が形成されるので該繊維の柔軟性が損なわれ、実質的に衣料やインテリヤ用途への応用は不可能である。
【０００８】
パラ系全芳香族ポリアミド繊維を亜塩素酸ナトリウムや次亜塩素酸ナトリウム水溶液で処理すると、褐色に変色しその後は変色しにくいので、光による変色の影響は少なくなる。しかし、亜塩素酸ナトリウムや次亜塩素酸ナトリウム水溶液による処理は、パラ系全芳香族ポリアミド繊維を著しく劣化させ強力を低下させるので実用的でない。
【０００９】
特開昭６２ー９７９６７号公報には、全芳香族ポリアミド成型物の表面を次亜塩素酸金属塩水溶液中で処理する事を特長とする、有機高分子マトリックスとの接着性の改善された全芳香族ポリアミド成型物の製造方法が記載されているが、この処理による強力低下の問題や、その改善方法については述べられていない。
【００１０】
【発明が解決しようとする課題】
本発明の目的は、耐光性に優れた全芳香族ポリアミド繊維、紡績糸、編織物、フェルト、不織布、紙などの布帛を製造するするための全芳香族ポリアミドの耐光性改善方法を提供することにある。
【００１１】
【課題を解決するための手段】
上記目的を達成するため、本発明に係る全芳香族ポリアミドの耐光性改善方法は、（１）パラ系全芳香族ポリアミド繊維を、強力保持率が６５％以上となるように、（２）かつ、ＪＩＳ Ｌ ０８４２ カーボンアーク灯光に対する染色堅牢度試験方法に準じて、パラ系全芳香族ポリアミド繊維試験片をブルースケール３級が標準退色するまで露光させた前後の色差ΔＥ*ａｂが１２以下となるように、（３）酸化剤と硫酸ナトリウムの水溶液からなる処理液で処理することを特徴とする方法からなる。
【００１２】
この耐光性改善方法においては、酸化剤が塩素系酸化剤であることが好ましい。また、酸化剤に亜塩素酸ナトリウム（ＮａＣｌＯ2）を用いることが好ましい。また、酸化剤に塩素酸ナトリウム（ＮａＣｌＯ3）または次亜塩素酸ナトリウム（ＮａＣｌＯ）を用いることが好ましい。さらに、処理液に、スルホン化化合物からなる界面活性剤を添加することが好ましい。
【００１３】
【発明の実施の形態】
本発明において用いるパラ系全芳香族ポリアミド繊維とは、ポリパラフェニレンテレフタルアミドなどのパラ系全芳香族ポリアミド繊維があげられる。
【００１４】
紫外線を含む光に対するパラ系全芳香族ポリアミド繊維の耐光性を改善する方法は、パラ系全芳香族ポリアミド繊維を、亜塩素酸ナトリウム（ＮａＣｌＯ2）などの酸化剤と硫酸ナトリウムの水溶液からなる処理液で処理する事により、パラ系全芳香族ポリアミド繊維の強度を低下させる事無く淡黄色から淡い褐色に変色させる事によって達成される。さらに、処理液にラウリル硫酸塩などのスルホン化界面活性剤を添加すると該繊維の強度低下防止により効果的である。
【００１５】
亜塩素酸ナトリウムなどの酸化剤のみでもパラ系全芳香族ポリアミド繊維を淡黄色から褐色に変色させる事はできるが、強度低下が著しく、実用的でない。
【００１６】
本発明の酸化処理において酸化剤として塩素酸ナトリウム（ＮａＣｌＯ3）または次亜塩素酸ナトリウム（ＮａＣｌＯ）を用いても良いが、強度保持率と、酸化処理による変色の程度を考慮すると、亜塩素酸ナトリウムの使用が好ましい。
【００１７】
硫酸ナトリウムのかわりに、塩化ナトリウムを添加した場合は、強度低下防止の効果が認められなかった。このことから、硫酸ナトリウムの作用は、中性塩の効果ではなく硫酸塩としての効果によるものと考えられる。
【００１８】
スルホン化界面活性剤は、例えば、ラウリル硫酸ソーダ塩、直鎖アルキルベンゼンスルホン酸ナトリウム、アルケンモノスルホン酸ナトリウム、ヒマシ油スルホン酸ナトリウム、アルカンモノジスルホン酸ナトリウム、スルホコハク酸モノ・ジアルキルエステルのナトリウム塩、ポリオキシエチレンヤシ脂肪酸アミドエーテルサルフェートナトリウム塩、ヤシ脂肪酸メチルタウリンナトリウム、ポリオキシエチレンラウリルエーテルサルフェートナトリウム塩などがある。
【００１９】
処理の方法は、上記塩素系酸化剤と硫酸ナトリウムを適量水に溶かし、パラ系全芳香族ポリアミド繊維をこれに浸して加熱処理し、水洗乾燥する。このとき、スルホン化界面活性剤を添加併用すると、該繊維の強度低下防止に著しく効果的である。処理温度は５０〜１００℃がよいが、望ましくは、６０〜９５℃が効率的である。
【００２０】
処理時間は、１〜４０分でよいが、処理の均一性と効率を考慮すると２０〜３５分が望ましい。
【００２１】
ステープルを紡績の前に酸化処理する場合は、紡績糸の酸化処理よりも処理条件を強く、すなわち酸化剤の量をやや多く、処理温度をやや高くする必要がある。紡績工程において繊維１本１本まで櫛削られ、繊維表面に微細な傷ができた紡績糸にくらべ、ステープルは繊維表面の傷が少ないので酸化剤の影響を受けにくいためである。
【００２２】
処理後のパラ系全芳香族ポリアミド繊維の引っ張り強さに対する処理前の引っ張り強さの比を強力保持率で表す。強力保持率は６５％以上が望ましい。６５％以下では、パラ系全芳香族ポリアミド繊維本来の高強力特性を生かす事ができない。
【００２３】
処理の程度は、ＪＩＳ Ｌ ０８４２ カーボンアーク灯光に対する染色堅牢度試験方法に準じて、パラ系全芳香族ポリアミド繊維試験片をブルースケール３級が標準退色するまで露光させた前後の色差ΔＥ*ａｂが１２以下となるように処理するのが望ましい。色差ΔＥ*ａｂが１２以上では、パラ系全芳香族ポリアミド繊維を使用した製品の光すなわち紫外線による変色が著しく、色調の安定を欠くことになる。
【００２４】
本発明の適用されるパラ系全芳香族ポリアミド繊維の形態は、フィラメント、ステープル、チョップドファイバー、紡績糸、織物、編み物、フェルト、不織布、紙などがあげられる。これらは本発明の処理をされたあと、それぞれに適した後加工工程を通して加工してもよい。例えば、フィラメントにあっては、本発明の処理後、撚糸、製織などができ、またステープル加工などの後加工工程をへて紡績糸、紡績糸織物、編組等に加工できる。ステープルにあっては、本発明の処理後パラ系全芳香族ポリアミド繊維１００％の紡績糸あるいは、ナイロン、ポリエステル、木綿などの他素材との混紡糸に加工できる。紡績糸にあっては、本発明の処理の後、単独叉は他素材との交編、交織ができる。これらはまた、本発明の処理後、染色加工や、撥水、柔軟加工などができる。
【００２５】
また、パラ系全芳香族ポリアミド繊維とポリエステル、ナイロン、木綿等の他素材とのミックス品、混紡、交織品であっても本発明の処理をする事ができる。
【００２６】
【実施例】
以下、実施例を挙げて本発明を詳細に説明する。なお、本実施例において用いた評価項目は次の試験法によるものである。
【００２７】
強力保持率
パラ系全芳香族ポリアミド繊維の強力保持率（％）は、次のように計算される。
強力保持率（％）＝（処理後の引っ張り強さ×１００）／（処理前の引っ張り強さ）
引っ張り強さの測定は、繊維の形態がフィラメントの場合はＪＩＳ Ｌ １０１３化学繊維フィラメント試験方法、 ステープルの場合はＪＩＳ Ｌ １０１５化学繊維ステープル試験方法、紡績糸の場合はＪＩＳ Ｌ １０９５ 一般紡績糸試験方法、織物の場合はＪＩＳ Ｌ１０９６ 一般織物試験方法に準じて測定した。
【００２８】
色差
パラ系全芳香族ポリアミド繊維の色差は、ＪＩＳ Ｚ ８７３０ 色の表示方法−物体色の色差・により，Ｌ*ａ*ｂ表色系による色差ΔＥ*ａｂであらわした。測定は、（株）住化分析センター製分光光度計 Ｍａｃｂｅｔｈ ＣｏｌｏｒＥｙｅ ３０００により、Ｄ６５−１０光源を用いて、Ｌ*，ａ*，ｂ*を求め，比較するふたつの値の差をΔＬ*、Δａ*、Δｂ*とし、次式により算出した。
（ΔＥａｂ）2＝（ΔＬ*）2＋（Δａ*）2＋（Δｂ*）2
【００２９】
耐光染色堅牢度
ＪＩＳ Ｌ ０８４２カーボンアーク灯光に対する染色堅牢度試験方法によった。
【００３０】
実施例１〜６、比較例１〜１３
パラ系全芳香族ポリアミド繊維（商品名；ケブラー、東レ・デュポン（株）製）の紡績糸（綿番手２０／２）と、酸化剤Ａ（亜塩素酸ナトリウム ＮａＣｌＯ2）、硫酸ナトリウム（Ｎａ2ＳＯ4）、界面活性剤Ｂ（ラウリル硫酸塩 Ｃ12Ｈ25ＯＳＯ3Ｎａ）の純分がそれぞれ第１表に示すように配合した処理液とを、浴比１：２０で８０℃で３０分間処理した。十分にすすぎ、遮光した状態で乾燥した。処理後の紡績糸の強力を測定して、処理前の紡績糸の強力と比較し強力保持率を計算した。該紡績糸をカーボンアーク灯形染色堅牢度試験器によりブルースケール３級が標準退色するまで露光させ、前記試験器により露光前後の色差ΔＥ*ａｂを測定した。
【００３１】
これらの結果を表１に示す。実施例１〜６は、処理による強力保持率が６５％以上で高強力繊維としての特長を維持し、かつΔＥ*ａｂは１２以下で比較例１３の未処理のΔＥ*ａｂ１８．３にくらべ大幅に改善されている。
【００３２】
酸化剤（Ａ）のみで処理された比較例７〜１２は、強力保持率６５％以上でかつΔＥ*ａｂ以下の条件を満たすことができなかった。
【００３３】
実施例７〜８
酸化剤Ｃ（塩素酸ナトリウム ＮａＣｌＯ3）、酸化剤Ｄ（次亜塩素酸ナトリウム ＮａＣｌＯ）を用いたほかは、実施例３と同じ方法で処理を行い、強力保持率と色差ΔＥ*ａｂを測定した。
【００３４】
実施例９〜１１
界面活性剤Ｄ（直鎖アルキルベンゼンスルホン酸ナトリウム）、Ｅ（アルケンモノスルホン酸ナトリウム）、Ｆ（ヒマシ油スルホン酸ナトリウム）、を用いた他は実施例４と同じ方法で処理を行い、強力保持率と色差ΔＥ*ａｂを測定した。
これらの結果を表２に示す。
【００３５】
実施例１２
パラ系全芳香族ポリアミド繊維（商品名；ケブラー）のステープル（１．５ｄ、繊維長５１ｍｍ）と、酸化剤Ａ（亜塩素酸ナトリウム ＮａＣｌＯ2）、硫酸ナトリウム（Ｎａ2ＳＯ4）、界面活性剤Ｂ（ラウリル硫酸塩 Ｃ12Ｈ25ＯＳＯ3Ｎａ）の純分がそれぞれ２（％ｏｗｆ）、８８（ｇ／ｌ）、２（％ｏｗｆ）となるように配合した処理液を、浴比１：２０で８０℃ｘ６０分間処理した。十分にすすぎ、遮光した状態で乾燥した。処理後のパラ系全芳香族ポリアミド繊維ステープルの強力は、処理前が３４．５（ｇ）に対し処理後は２９．３（ｇ）で強力保持率は８５．０％であった。該紡績糸をカーボンアーク灯式染色堅牢度試験器によりブルースケール３級が標準退色するまで露光させた。前記試験器により測定した露光前後の色差ΔＥ*ａｂは７．０であった。
【００３６】
実施例１３
実施例１２で得た、酸化剤で処理されたパラ系全芳香族ポリアミド繊維のステープル（商品名；ケブラー）と、繊度１．５ｄ，繊維長５１ｍｍのポリエステル繊維を混紡して、ケブラー１０％、ポリエステル９０％の綿番手２０／１の混紡糸をリング精紡機でつくった。これを双糸加工して綿番手２０／２とした。
【００３７】
この混紡糸を、分散染料Ｃｌ Ｄｉｓｐｅｒｓｅ Ｂｌｕｅ ５６，Ｋａｙａｌｏｎ Ｐｏｌｙｅｓｔｅｒ Ｂｌｕｅ ＥＢＬ−Ｅ（日本火薬製）１．２％ｏｗｆと、酢酸で染浴をＰＨ５．５に調整した染浴に浴比１：２０で入れ、１３０℃ｘ６０分間染色した。十分にすすいで乾燥し、主としてポリエステル繊維が染色されたブルーの先染め糸を得た。この先染め糸の染色耐光堅牢度を、ＪＩＳ Ｌ ０８４２カーボンアーク灯に対する染色堅牢度試験方法で評価したところ、染色耐光堅牢度は４級でインテリヤ用品に用いる織り編み物用の糸としては問題の無いレベルであった。
【００３８】
比較例１４
酸化剤で処理されないパラ系全芳香族ポリアミド繊維のステープルを用いた他は、実施例１３と同様に混紡糸をつくり、実施例１３と同じ方法により染色した先染め糸を得た。
この先染め糸の耐光染色堅牢度は２−３級で、インテリヤ用基布に用いる先染め糸としては耐光堅牢度が不十分である。
【００３９】
実施例１４
パラ系全芳香族ポリアミド繊維（商品名；ケブラー、東レ・デュポン（株）製）の紡績糸織物（綿番手２０／２、密度５８×４７本／ｉｎ、組織２／２綾織り）を用いたほかは、実施例３と同じ方法で処理を行った。十分にすすぎ、遮光した状態で乾燥した。処理後のパラ系全芳香族ポリアミド繊維織物の引っ張り強力は、処理前のタテｘヨコが１７５×１６０（ｋｇ／ｉｎ）に対し処理後はそれぞれ１４３×１２８（ｋｇ／ｉｎ）で強力保持率は８１．７×８０（％）であった。該処理後の織物をカーボンアーク灯形染色堅牢度試験器によりブルースケール３級が標準退色するまで露光させた。露光前後の色差ΔＥ*ａｂは７．０であった。
【００４０】
【表１】
【表２】
【発明の効果】
本発明の方法によれば、耐光性の改善されたパラ系全芳香族ポリアミド繊維および紡績糸、または編織物、あるいはフェルト、不織布、紙などを製造することができる。特に、審美性が要求される衣料用や、インテリヤ製品にパラ系全芳香族ポリアミド繊維を応用することが容易になる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for improving light resistance of wholly aromatic polyamides for producing fabrics such as wholly aromatic polyamide fibers, spun yarns, knitted fabrics, felts, nonwoven fabrics, and papers that are excellent in light resistance.
[0002]
[Prior art]
Para-based wholly aromatic polyamide fibers are synthetic fibers that combine high functionality such as high strength, high elastic modulus, high heat resistance, non-conductivity, and no rust, and the flexibility and lightness of organic fibers. Because of these features, they are used as industrial materials such as automobile tires, automobile transmission belts, conveyors, and optical fiber reinforcement.
[0003]
On the other hand, as clothing and textile products, it is used for work gloves, work clothes, sports clothes, etc. that apply the difficulty of cutting to a knife. In addition, because it has a critical oxygen index of 29, it is essentially nonflammable and carbonizes without melting or shrinking at a high temperature of 500 ° C. Development of interior products such as
[0004]
The para-type wholly aromatic polyamide fiber has a pale yellow color, but turns brown when exposed to ultraviolet rays. Ultraviolet rays are contained in large amounts in direct sunlight. If para-type wholly aromatic polyamide fibers are exposed outdoors, they will turn pale brown in a few hours. Ultraviolet rays are also included in daytime shade light, and are also contained in trace amounts in incandescent and fluorescent light. Discoloration is a major problem in the distribution and use stages.
[0005]
In particular, unlike industrial materials such as tires, belts, and ropes, when para-type wholly aromatic polyamide fibers are applied to clothing and interior products that require aesthetics, the problem of discoloration due to ultraviolet rays is significant.
[0006]
On the other hand, there is a method in which the para-type wholly aromatic polyamide fiber is covered with other fibers to conceal the para-type wholly aromatic polyamide fiber, thereby improving the influence of discoloration due to light. For example, JP-A-3-830 discloses a core-sheath type composite yarn in which the main component of the core component is an aromatic polyamide, the main component of the sheath component is a short fiber or a long fiber of polyester fiber, and the core component is 10 A core-sheath type composite yarn composed of ˜50% by weight and a sheath component of 90-50% by weight has been proposed. In textile products including clothing, a thin thread of 20 s / 1 or less is required, but at this thickness, it is difficult to completely cover the core component with the sheath component. This is not a solution to the problem because part of the color is exposed or ultraviolet rays enter through the sheath component, causing discoloration.
[0007]
Japanese Patent Application Laid-Open No. 01-174680 proposes to heat-treat at 130 to 250 ° C. after attaching a polyethyleneimine compound to para-type wholly aromatic polyamide fiber. However, since a resin film of a polyethyleneimine-based compound is formed on the surface of the fiber, the flexibility of the fiber is impaired, and the application to clothing and interior use is practically impossible.
[0008]
When para-type wholly aromatic polyamide fibers are treated with sodium chlorite or aqueous sodium hypochlorite solution, the color changes to brown and is difficult to discolor thereafter, so the influence of discoloration due to light is reduced. However, treatment with sodium chlorite or sodium hypochlorite aqueous solution is not practical because it significantly deteriorates the para-type wholly aromatic polyamide fiber and lowers the strength.
[0009]
Japanese Patent Application Laid-Open No. 62-97967 discloses a completely aromatic polyamide molded product that is treated in an aqueous solution of metal hypochlorite with improved adhesion to an organic polymer matrix. A method for producing an aromatic polyamide molded product is described, but the problem of strength reduction due to this treatment and a method for improving the strength are not described.
[0010]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for improving light resistance of wholly aromatic polyamides for producing fabrics such as wholly aromatic polyamide fibers, spun yarns, knitted fabrics, felts, nonwoven fabrics, and papers that are excellent in light resistance. It is in.
[0011]
[Means for Solving the Problems]
In order to achieve the above object, the method for improving the light resistance of a wholly aromatic polyamide according to the present invention comprises (1) a para-based wholly aromatic polyamide fiber (2) and a strength retention of 65% or more. The color difference ΔE * ab before and after the para-type wholly aromatic polyamide fiber test piece was exposed until the blue scale grade 3 was standardly faded according to the dyeing fastness test method for JIS L 0842 carbon arc lamp. Thus, (3) the method is characterized in that the treatment is performed with a treatment solution comprising an aqueous solution of an oxidizing agent and sodium sulfate.
[0012]
In this light resistance improving method, the oxidizing agent is preferably a chlorine-based oxidizing agent. Moreover, it is preferable to use sodium chlorite (NaClO 2 ) as the oxidizing agent. Further, sodium chlorate (NaClO 3 ) or sodium hypochlorite (NaClO) is preferably used as the oxidizing agent. Furthermore, it is preferable to add a surfactant made of a sulfonated compound to the treatment liquid.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the para-type wholly aromatic polyamide fiber used in the present invention include para-type wholly aromatic polyamide fibers such as polyparaphenylene terephthalamide.
[0014]
A method for improving the light resistance of para-type wholly aromatic polyamide fibers against light including ultraviolet rays is obtained by treating para-type wholly aromatic polyamide fibers with an aqueous solution of an oxidizing agent such as sodium chlorite (NaClO 2 ) and sodium sulfate. By treating with a liquid, this is achieved by changing the color of the para-type wholly aromatic polyamide fiber from light yellow to light brown without reducing the strength. Furthermore, the addition of a sulfonated surfactant such as lauryl sulfate to the treatment liquid is more effective in preventing the strength of the fiber from being lowered.
[0015]
The para-type wholly aromatic polyamide fiber can be changed from light yellow to brown only by an oxidizing agent such as sodium chlorite, but the strength is remarkably lowered and is not practical.
[0016]
In the oxidation treatment of the present invention, sodium chlorate (NaClO 3 ) or sodium hypochlorite (NaClO) may be used as the oxidizing agent. However, considering the strength retention and the degree of discoloration due to the oxidation treatment, chlorous acid The use of sodium is preferred.
[0017]
When sodium chloride was added instead of sodium sulfate, the effect of preventing strength reduction was not observed. From this, it is considered that the action of sodium sulfate is due to the effect as a sulfate, not the effect of a neutral salt.
[0018]
Sulfonated surfactants include, for example, sodium lauryl sulfate, sodium linear alkylbenzene sulfonate, sodium alkene monosulfonate, sodium castor oil sulfonate, sodium alkane monodisulfonate, sodium salt of sulfosuccinic acid mono-dialkyl ester, poly Examples include oxyethylene coconut fatty acid amide ether sulfate sodium salt, coconut fatty acid sodium methyl taurate, and polyoxyethylene lauryl ether sulfate sodium salt.
[0019]
In the treatment method, the above chlorine-based oxidizer and sodium sulfate are dissolved in water in appropriate amounts, the para-type wholly aromatic polyamide fiber is immersed in this, heat-treated, washed with water and dried. At this time, the combined use of a sulfonated surfactant is extremely effective in preventing the strength of the fiber from being lowered. The treatment temperature is preferably 50 to 100 ° C, but preferably 60 to 95 ° C is efficient.
[0020]
The processing time may be 1 to 40 minutes, but 20 to 35 minutes is desirable in consideration of processing uniformity and efficiency.
[0021]
When the staple is oxidized before spinning, the processing conditions are stronger than the oxidized processing of the spun yarn, that is, the amount of the oxidizing agent is slightly higher and the processing temperature needs to be slightly higher. This is because staples are less susceptible to the influence of an oxidizing agent because they have fewer flaws on the fiber surface than a spun yarn that is combed up to one fiber at a time in the spinning process and has fine flaws on the fiber surface.
[0022]
The ratio of the tensile strength before the treatment to the tensile strength of the para-type wholly aromatic polyamide fiber after the treatment is expressed as a strength retention. The strength retention is preferably 65% or more. If it is 65% or less, it is impossible to take advantage of the inherent high strength properties of para-type wholly aromatic polyamide fibers.
[0023]
The degree of processing is determined by the color difference ΔE * ab before and after the para-type wholly aromatic polyamide fiber test piece was exposed until the blue scale class 3 was standardly faded according to the dyeing fastness test method for JIS L 0842 carbon arc lamp. It is desirable to process so that it may become 12 or less. When the color difference ΔE * ab is 12 or more, the product using the para-type wholly aromatic polyamide fiber is significantly discolored by light, that is, ultraviolet rays, and the color tone is not stable.
[0024]
Examples of the para-type wholly aromatic polyamide fiber to which the present invention is applied include filaments, staples, chopped fibers, spun yarns, woven fabrics, knitted fabrics, felts, non-woven fabrics, and papers. These may be processed through post-processing steps suitable for each after the treatment of the present invention. For example, a filament can be twisted, woven or the like after the treatment of the present invention, and can be processed into a spun yarn, a spun yarn fabric, a braid and the like through a post-processing step such as stapling. The staple can be processed into a spun yarn of 100% para-type wholly aromatic polyamide fiber after the treatment of the present invention or a blended yarn with other materials such as nylon, polyester and cotton. In the spun yarn, after the treatment of the present invention, knitting and weaving with a single material or other materials can be performed. These can also be subjected to dyeing, water repellency, softening and the like after the treatment of the present invention.
[0025]
The present invention can also be applied to a mixed product, a blended product, and a woven product of para-type wholly aromatic polyamide fibers and other materials such as polyester, nylon, and cotton.
[0026]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples. The evaluation items used in this example are based on the following test method.
[0027]
Strength retention The strength retention (%) of the para-type wholly aromatic polyamide fiber is calculated as follows.
Strength retention (%) = (Tensile strength after treatment × 100) / (Tensile strength before treatment)
Tensile strength is measured by a JIS L 1013 chemical fiber filament test method when the fiber is a filament, a JIS L 1015 chemical fiber staple test method when the fiber is a staple, and a JIS L 1095 general spun yarn test method when the fiber is a spun yarn. In the case of a woven fabric, the measurement was performed according to a JIS L1096 general woven fabric test method.
[0028]
The color difference of the color difference para-type wholly aromatic polyamide fiber is expressed by the color difference ΔE * ab according to the L * a * b color system according to JIS Z 8730 color display method—object color difference. The measurement is performed using a spectrophotometer Macbeth ColorEye 3000 manufactured by Sumika Chemical Analysis Co., Ltd., using a D65-10 light source, and L * , a * , b * are obtained, and the difference between the two values to be compared is ΔL * , Δa * And Δb * were calculated according to the following formula.
(ΔEab) 2 = (ΔL * ) 2 + (Δa * ) 2 + (Δb * ) 2
[0029]
Light fastness to light dyeing JIS L 0842 Dye fastness to carbon arc lamp light was used.
[0030]
Examples 1-6, Comparative Examples 1-13
A spun yarn (cotton count 20/2) of para-type wholly aromatic polyamide fiber (trade name: Kevlar, manufactured by Toray DuPont Co., Ltd.), oxidizing agent A (sodium chlorite NaClO2), sodium sulfate (Na 2 SO) 4 ) A treatment liquid in which the pure component of surfactant B (lauryl sulfate C 12 H 25 OSO 3 Na) is blended as shown in Table 1 is treated at a bath ratio of 1:20 at 80 ° C. for 30 minutes. did. Rinse thoroughly and dry in the dark. The tenacity of the spun yarn after the treatment was measured, and the tenacity retention was calculated in comparison with the tenacity of the spun yarn before the treatment. The spun yarn was exposed with a carbon arc lamp type dyeing fastness tester until the blue scale grade 3 was standardly faded, and the color difference ΔE * ab before and after exposure was measured with the tester.
[0031]
These results are shown in Table 1. In Examples 1 to 6, the strength retention ratio by treatment is 65% or more and the characteristics as a high strength fiber are maintained, and ΔE * ab is 12 or less, which is much larger than the untreated ΔE * ab18.3 of Comparative Example 13. Has been improved.
[0032]
Comparative Examples 7 to 12 treated only with the oxidizing agent (A) could not satisfy the conditions of a strength retention of 65% or more and ΔE * ab or less.
[0033]
Examples 7-8
Except for the use of oxidizing agent C (sodium chlorate NaClO 3 ) and oxidizing agent D (sodium hypochlorite NaClO), treatment was carried out in the same manner as in Example 3, and the strength retention and color difference ΔE * ab were measured. .
[0034]
Examples 9-11
It was treated in the same manner as in Example 4 except that surfactant D (sodium linear alkylbenzene sulfonate), E (sodium alkene monosulfonate), and F (sodium castor oil sulfonate) were used. And the color difference ΔE * ab was measured.
These results are shown in Table 2.
[0035]
Example 12
Para-type wholly aromatic polyamide fiber (trade name: Kevlar) staple (1.5d, fiber length 51 mm), oxidizing agent A (sodium chlorite NaClO 2 ), sodium sulfate (Na 2 SO 4 ), surfactant A treatment liquid formulated so that the pure content of B (lauryl sulfate C 12 H 25 OSO 3 Na) is 2 (% owf), 88 (g / l), and 2 (% owf), respectively, is a bath ratio of 1: 20 at 80 ° C. for 60 minutes. Rinse thoroughly and dry in the dark. The strength of the para-type wholly aromatic polyamide fiber staples after the treatment was 34.5 (g) before the treatment, 29.3 (g) after the treatment, and the strength retention was 85.0%. The spun yarn was exposed with a carbon arc lamp dyeing fastness tester until the blue scale grade 3 was standardly faded. The color difference ΔE * ab before and after exposure measured by the tester was 7.0.
[0036]
Example 13
A blend of para-type wholly aromatic polyamide fiber staples (trade name; Kevlar) treated with an oxidant obtained in Example 12 and polyester fiber having a fineness of 1.5 d and a fiber length of 51 mm, and 10% Kevlar, A 90% polyester cotton count 20/1 blended yarn was made with a ring spinning machine. This was double-tipped to a cotton count of 20/2.
[0037]
This blended yarn was dispersed in a dye bath in which the disperse dye Cl Disperse Blue 56, Kayalon Polyester Blue EBL-E (manufactured by Nippon Explosives) 1.2% owf and a dye bath adjusted to PH 5.5 with acetic acid at a bath ratio of 1:20. And dyed at 130 ° C. for 60 minutes. It was thoroughly rinsed and dried to obtain a blue dyed yarn mainly dyed with polyester fibers. The dyeing light fastness of this dyed yarn was evaluated by a dyeing fastness test method against a JIS L 0842 carbon arc lamp. The dyeing light fastness was grade 4, which is a level that is not a problem as a yarn for weaving and knitting used in interior goods. Met.
[0038]
Comparative Example 14
A mixed yarn was prepared in the same manner as in Example 13 except that para-type wholly aromatic polyamide fiber staples not treated with an oxidizing agent were used, and a dyed yarn dyed by the same method as in Example 13 was obtained.
The fastness to light dyeing of this pre-dyed yarn is grade 2-3, and the fastness to light is insufficient as the pre-dyed yarn used for the fabric for interior.
[0039]
Example 14
A spun yarn fabric (cotton count 20/2, density 58 × 47 / in, structure 2/2 twill weave) of para-type wholly aromatic polyamide fiber (trade name; Kevlar, manufactured by Toray DuPont Co., Ltd.) was used. The other processes were performed in the same manner as in Example 3. Rinse thoroughly and dry in the dark. Tensile strength of para-type wholly aromatic polyamide fiber fabric after treatment is 143 x 128 (kg / in) after treatment versus 175 x 160 (kg / in) before treatment. It was 81.7 × 80 (%). The treated fabric was exposed with a carbon arc lamp type dyeing fastness tester until the blue scale grade 3 was standardly faded. The color difference ΔE * ab before and after exposure was 7.0.
[0040]
[Table 1]
[Table 2]
【The invention's effect】
According to the method of the present invention, para-type wholly aromatic polyamide fibers and spun yarns with improved light resistance, knitted fabrics, felts, nonwoven fabrics, papers, and the like can be produced. In particular, it becomes easy to apply para-type wholly aromatic polyamide fibers to clothing that requires aesthetics and to interior products.
Claims (5)
（３）酸化剤と硫酸ナトリウムの水溶液からなる処理液で処理することを特徴とする全芳香族ポリアミドの耐光性改善方法。(1) Para-type wholly aromatic polyamide fiber is para-type wholly aromatic so that the strength retention is 65% or more according to (2) and the dyeing fastness test method for JIS L 0842 carbon arc lamp. The polyamide fiber test piece was exposed until the blue scale grade 3 was standardly faded so that the color difference ΔE * ab before and after exposure was 12 or less.
(3) A method for improving light resistance of a wholly aromatic polyamide, characterized in that the treatment is carried out with a treatment liquid comprising an aqueous solution of an oxidizing agent and sodium sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34523398A JP3753407B2 (en) | 1997-12-22 | 1998-12-04 | Method for improving light resistance of wholly aromatic polyamide |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36587397 | 1997-12-22 | ||
| JP9-365873 | 1997-12-22 | ||
| JP34523398A JP3753407B2 (en) | 1997-12-22 | 1998-12-04 | Method for improving light resistance of wholly aromatic polyamide |
Publications (2)
| Publication Number | Publication Date |
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| JPH11241272A JPH11241272A (en) | 1999-09-07 |
| JP3753407B2 true JP3753407B2 (en) | 2006-03-08 |
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| JP34523398A Expired - Lifetime JP3753407B2 (en) | 1997-12-22 | 1998-12-04 | Method for improving light resistance of wholly aromatic polyamide |
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| JP4804262B2 (en) * | 2006-08-08 | 2011-11-02 | 帝人テクノプロダクツ株式会社 | Heat resistant fabric with excellent light resistance |
| JP5713304B1 (en) * | 2014-07-24 | 2015-05-07 | 三信製織株式会社 | Striped camouflage fabric |
| JP7133167B2 (en) * | 2018-06-20 | 2022-09-08 | 国立大学法人大阪大学 | Modified fabric production method |
| JP6777347B1 (en) * | 2019-09-13 | 2020-10-28 | 竹本油脂株式会社 | Synthetic fiber processing agent for spinning process and synthetic fiber |
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