JP2002061075A - Heat-resistant polyamide fiber and method for producing the same - Google Patents
Heat-resistant polyamide fiber and method for producing the sameInfo
- Publication number
- JP2002061075A JP2002061075A JP2000243128A JP2000243128A JP2002061075A JP 2002061075 A JP2002061075 A JP 2002061075A JP 2000243128 A JP2000243128 A JP 2000243128A JP 2000243128 A JP2000243128 A JP 2000243128A JP 2002061075 A JP2002061075 A JP 2002061075A
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- Prior art keywords
- heat
- polyamide fiber
- antioxidant
- resistant polyamide
- producing
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
- Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は耐熱性に優れ、染色
品の品位を向上することができるポリアミド系繊維に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide fiber having excellent heat resistance and capable of improving the quality of a dyed product.
【０００２】[0002]
【従来の技術】ポリアミド系繊維は種々の優れた特性を
有するので、織編物等の布帛として広く利用されてい
る。ポリアミド系繊維製品では染色加工前に布帛形態を
安定化するために、１３０〜２１０℃の温度で３０秒〜
３分間の乾熱処理が行われている。しかし、この熱処理
によって染色斑および染色筋が発生する問題が生じる。
つまり、染色性が低下したり、熱処理バラツキにより染
色斑や染色筋が発生する。2. Description of the Related Art Polyamide fibers have various excellent properties and are therefore widely used as woven or knitted fabrics. In the case of polyamide-based fiber products, in order to stabilize the fabric form before dyeing, the temperature is 130 to 210 ° C for 30 seconds.
Dry heat treatment is performed for 3 minutes. However, this heat treatment causes a problem that stained spots and stained streaks occur.
That is, the stainability is reduced, and stained spots and stained streaks occur due to variations in the heat treatment.
【０００３】これは、ポリアミド系繊維製品の布帛形態
安定化の為の熱処理により、ポリアミド系繊維のアミノ
末端基が減少して、酸性染料が染着されにくくなる為と
思われる。つまり、Ties Karstensらの報文Makromol.C
hem.No.191(1990)に掲載されているように、ポリアミド
分子中のアミノ末端基が高温加熱によって減少すること
やポリマー主鎖中のアミド結合が切断されアルデヒドお
よびケトンカルボニル基が生成し、これがアミノ基と反
応し黄色の色原体を形成することが知られている。前記
の熱によるアミノ末端基の減少および熱黄変はともにア
ミノ末端基が消費され、酸性染料の染着座席の減少を生
じ、結果として染色性が低下する。This is presumably because the heat treatment for stabilizing the fabric form of the polyamide fiber product reduces the amino terminal groups of the polyamide fiber and makes it difficult for the acid dye to be dyed. In other words, the report Makromol.C of Ties Karstens et al.
As described in hem. No. 191 (1990), the amino terminal group in the polyamide molecule is reduced by heating at high temperature, the amide bond in the polymer main chain is cleaved, and aldehyde and ketone carbonyl groups are generated, It is known that this reacts with an amino group to form a yellow chromogen. Both the heat-induced reduction of the amino terminal groups and the heat yellowing consume the amino terminal groups, resulting in a reduction in the number of dyeing sites for the acid dyes and consequently the dyeability is reduced.
【０００４】かかる熱酸化劣化によるポリアミド系繊維
のアミノ末端基の減少や黄変を防ぐ方法として、通常の
ヒンダードフェノール系もしくは、ヒンダードアミン
系、セミカルバジド系化合物等の酸化防止剤を、重合時
もしくは染色加工段階（特に高温乾熱処理前）で添加す
る方法が知られているが、これらの方法であればアミノ
末端基の減少を抑え、黄変を防ぎ、結果として染色性向
上に有効であるが、前者の重合時添加方法では、原糸自
身が着色したり、最終製品で残存する酸化防止剤に起因
する各種黄変トラブル、例えば、ＮＯｘガス、プロパン
燃焼ガス等のガス黄変や光、熱での酸化防止剤自身の黄
変が問題となる場合があり、後者の染色加工段階で添加
する方法では、後加工工程が増えて効率的生産には不向
きである等の問題があった。そのため、効率的に生産さ
れ、かつ原糸自身の熱黄変を押さえたポリアミド系繊維
はいまだ得られていなかった。As a method for preventing the reduction or yellowing of the amino terminal group of the polyamide fiber due to the thermal oxidation deterioration, a conventional antioxidant such as a hindered phenol-based, hindered amine-based or semicarbazide-based compound is used during polymerization or dyeing. Methods of adding at the processing stage (especially before high-temperature dry heat treatment) are known, but these methods are effective in suppressing the decrease in amino terminal groups, preventing yellowing, and as a result, improving dyeability. In the former addition method at the time of polymerization, the raw yarn itself is colored or various yellowing troubles caused by the antioxidant remaining in the final product, such as NOx gas, gas yellowing such as propane combustion gas, light and heat. The yellowing of the antioxidant itself may be a problem, and the latter method of adding at the dyeing stage has a problem that the number of post-processing steps increases and is not suitable for efficient production. Was Tsu. Therefore, a polyamide-based fiber that is efficiently produced and suppresses the thermal yellowing of the yarn itself has not yet been obtained.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、耐熱性に優
れ、また均染性に優れたポリアミド系繊維を提供するこ
とを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a polyamide fiber having excellent heat resistance and excellent levelness.
【０００６】[0006]
【課題を解決するための手段】本発明は、１９５℃で３
分間乾熱処理した後のＣＩＥ−ＬＡＢ表色系におけるｂ
値が２．５以下である耐熱性ポリアミド系繊維である。
また、ポリアミド系繊維に対して、酸化防止剤が０．０
０１質量％以上、５％質量以下含有されていることを特
徴とする耐熱性ポリアミド系繊維である。SUMMARY OF THE INVENTION The present invention provides a method for producing
B in the CIE-LAB color system after dry heat treatment for
It is a heat-resistant polyamide fiber having a value of 2.5 or less.
Further, the antioxidant is 0.0
The heat-resistant polyamide fiber is contained in an amount of from 01% by mass to 5% by mass.
【０００７】また、酸化防止剤は、次式で示されるセミ
カルバジド系化合物である耐熱性ポリアミド系繊維であ
る。 （Ｒ）2ＮＮＨＣＯＮＨ−Ｙ−ＮＨＣＯＮＨＮ（Ｒ）2 ……（１） （一般式中、Ｒは炭素数１〜４のアルキル基、Ｙは-
（ＣＨ2）n- 又は、Ａｒ-ＣＨ2-Ａｒ （Arはフェニレン
基）、nは１〜１１の整数である。）さらには、ポリア
ミド系繊維を溶融紡糸して、未延伸糸を捲き取る以前に
紡糸油剤を付与するに際し、紡糸油剤中に酸化防止剤を
含有することを特徴とする耐熱性ポリアミド系繊維の製
造方法である。該酸化防止剤が次式で示されるセミカル
バジド系化合物である前記の耐熱性ポリアミド系繊維の
製造方法である。The antioxidant is a heat-resistant polyamide fiber which is a semicarbazide compound represented by the following formula. (R) 2 NNHCONH-Y-NHCONNHN (R) 2 (1) (In the general formula, R is an alkyl group having 1 to 4 carbon atoms, and Y is-
(CH 2) n-or, Ar-CH 2 -Ar (Ar is a phenylene group), n is an integer of 1 to 11. Further, the production of a heat-resistant polyamide-based fiber characterized in that an antioxidant is contained in the spinning oil when the polyamide-based fiber is melt-spun and the spinning oil is applied before the undrawn yarn is wound up. Is the way. The method for producing a heat-resistant polyamide fiber, wherein the antioxidant is a semicarbazide compound represented by the following formula:
【０００８】[0008]
【発明の実施の形態】以下に、本発明を詳細に説明す
る。本発明におけるポリアミド系繊維とは、ナイロン−
６、ナイロン−６６、ナイロン−４６およびポリアミド
／ポリエステル複合繊維等の合成繊維であり、好ましく
はナイロン−６を用いることができる。また、紡糸方法
としては、通常の溶融方式が適用される。また、ポリア
ミドポリマーは、通常添加される添加剤、例えば艶消
剤、安定剤、制電剤等を含んでいてもよい。繊維の断面
形状および繊度は用途に応じて適宜選択される。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The polyamide fiber in the present invention is nylon-
6, synthetic fibers such as nylon-66, nylon-46 and polyamide / polyester composite fiber, and nylon-6 can be preferably used. As a spinning method, an ordinary melting method is applied. Further, the polyamide polymer may contain additives usually added, for example, a matting agent, a stabilizer, an antistatic agent and the like. The cross-sectional shape and fineness of the fiber are appropriately selected depending on the application.
【０００９】本発明において、ポリアミド系繊維は、油
剤中に酸化防止剤を含むものであり、１９５℃で３分間
乾熱処理した後のＣＩＥ−ＬＡＢ表色系におけるｂ値は
２．５以下である。ｂ値が２．５以下であれば、後工程
で通常の乾熱処理後、染色したときの品位は良好なもの
となる。In the present invention, the polyamide fiber contains an antioxidant in an oil agent and has a b value of 2.5 or less in the CIE-LAB color system after dry heat treatment at 195 ° C. for 3 minutes. . If the b value is 2.5 or less, the quality after dyeing after ordinary dry heat treatment in the subsequent step becomes good.
【００１０】本発明における酸化防止剤の付与量は該繊
維に対して、０．００１〜５質量％の範囲の中から選択
される。付与量がこの範囲内であれば、原糸着色もな
く、また、経済的に耐熱性の良好なものが得られる。[0010] The amount of the antioxidant to be applied in the present invention is selected from the range of 0.001 to 5% by mass based on the fiber. When the applied amount is within this range, there is no coloring of the original yarn, and an economically good heat-resistant material can be obtained.
【００１１】本発明における紡糸油剤とは、合成繊維を
製造する際に通常使用されるもであり、鉱物油系、特殊
アニオン系、特殊ノニオン系、特殊カチオン系を用いる
ことができ、用途に応じて適宜選択される。[0011] The spinning oil agent in the present invention is generally used in the production of synthetic fibers. Mineral oils, special anions, special nonions, and special cations can be used. Selected as appropriate.
【００１２】本発明における酸化防止剤とは、次式で示
されるセミカルバジド系化合物である。セミカルバジド
系化合物としては限定されるものではないが、例えば下
記一般式（１）で示されるものである。 （Ｒ）2ＮＮＨＣＯＮＨ−Ｙ−ＮＨＣＯＮＨＮ（Ｒ）2 ……（１） （一般式中、Ｒは炭素数１〜４のアルキル基、Ｙは-
（ＣＨ2）n- 又は、Ａｒ-ＣＨ2-Ａｒ （Arはフェニレン
基）、nは１〜１１の整数である。）The antioxidant in the present invention is a semicarbazide compound represented by the following formula. The semicarbazide-based compound is not limited, but is, for example, a compound represented by the following general formula (1). (R) 2 NNHCONH-Y-NHCONNHN (R) 2 (1) (In the general formula, R is an alkyl group having 1 to 4 carbon atoms, and Y is-
(CH 2) n-or, Ar-CH 2 -Ar (Ar is a phenylene group), n is an integer of 1 to 11. )
【００１３】より具体的には、Ｒがメチル基で、Ｙが-
（ＣＨ2）6-の化合物等があげられる。More specifically, R is a methyl group and Y is-
(CH 2 ) 6- compounds and the like.
【００１４】具体的な酸化防止剤の付与方法としては、
通常の溶融紡糸をする際に、紡糸油剤中に酸化防止剤を
添加しておいてポリアミド系繊維に付与する方法が挙げ
られる。一般には該酸化防止剤と紡糸油剤の水溶液ある
いは水分散液を通常の油剤付与装置で付与する。As a specific method of applying the antioxidant,
When performing ordinary melt spinning, there is a method in which an antioxidant is added to a spinning oil agent and applied to polyamide fibers. In general, an aqueous solution or aqueous dispersion of the antioxidant and the spinning oil is applied by a usual oil applying device.
【００１５】[0015]
【実施例】以下に、本発明の耐熱性ポリアミド系繊維の
製造方法に関する具体例を詳細に説明するが、本発明は
実施例のみに限定されるものではない。実施例における
評価は次の評価方法によった。EXAMPLES Hereinafter, specific examples relating to the method for producing the heat-resistant polyamide fiber of the present invention will be described in detail, but the present invention is not limited to only the examples. The evaluation in the examples was based on the following evaluation method.
【００１６】(1)耐熱性 紡糸して巻き取ったポリアミド系繊維の１口編地を作成
し、定長状態で１９５℃で３分間の乾熱処理後、ＭＩＮ
ＯＬＴＡ ＳＰＥＣＴＲＯＰＨＯＴＯＭＥＴＥＲ ＣＭ
−３７００ｄでＬａｂを測色する。そのときの黄変度；
ｂ値で判定する。(1) Heat resistance A one-port knitted fabric made of a spun and wound polyamide-based fiber is prepared, and subjected to a dry heat treatment at 195 ° C. for 3 minutes in a fixed length state.
OLTA SPECTROPHOTOMETER CM
Lab is measured at -3700d. Yellowing degree at that time;
The determination is made based on the b value.
【００１７】(2)染色性 上述した耐熱性を評価したサンプルをミーリングタイプ
・ブルー系酸性染料（品名：Kayanol Mill. Turq. Blue
3G ［日本化薬社製］1%owm）で９８℃×３０分間酸性
染色した後、染色性を目視判定する。 ○；均一に染まる。 ×；多数の淡染部分がある。(2) Dyeability The sample evaluated for heat resistance described above was used as a milling type blue acid dye (product name: Kayanol Mill. Turq. Blue).
After acid staining with 3G [manufactured by Nippon Kayaku Co., Ltd. 1% owm) at 98 ° C. for 30 minutes, the staining property is visually determined. ；: Uniform dyeing. X: There are many lightly dyed portions.
【００１８】実施例１ ナイロン−６レジンを通常の溶融紡糸装置を使用して、
溶融紡糸後、未延伸糸に下記式で示す化合物（ａ）のセ
ミカルバジド系化合物を紡糸油剤（主成分が鉱物油、特
殊アニオン系油剤）に対して３質量％添加して、該紡糸
油剤を繊維に対して１質量％を付与、さらに延伸、熱処
理後捲き取った。得られた７８デシテックス２４フィラ
メントのポリアミド繊維の一口編み地を作成した。この
編地を常法により精練後、１９５℃×３分の乾熱処理を
実施した。得られた編地の黄変度、染色性は表１のよう
になり、黄変度、染色性ともに良好なものであった。Example 1 Nylon-6 resin was prepared using a conventional melt spinning apparatus.
After the melt spinning, a semicarbazide compound represented by the following formula (a) is added to the undrawn yarn at 3% by mass with respect to the spinning oil (main component is mineral oil, special anion oil). And then stretched and heat-treated. A one-piece knitted fabric of the obtained 78-decitex 24-filament polyamide fiber was prepared. After refining the knitted fabric by a conventional method, a dry heat treatment was performed at 195 ° C. for 3 minutes. The yellowing degree and the dyeing property of the obtained knitted fabric were as shown in Table 1, and both the yellowing degree and the dyeing property were good.
【００１９】 （ＣＨ3）2ＮＮＨＣＯＮＨ−（ＣＨ2）6−ＮＨＣＯＮＨＮ（ＣＨ3）2 …（ａ）(CH 3 ) 2 NNHCONH— (CH 2 ) 6 —NHCONNHN (CH 3 ) 2 (a)
【００２０】比較例１ 紡糸油剤に酸化防止剤を添加しない以外は実施例１と同
様に糸を製造し、編地をし、精練、熱処理を行った。得
られた編地の黄変度、染色性は表１のようになり、黄変
度が大きく、染色性は淡染部が目立ち、品位に欠けるも
のであった。Comparative Example 1 A yarn was produced in the same manner as in Example 1 except that no antioxidant was added to the spinning oil, knitted, scoured and heat-treated. The yellowing degree and dyeing properties of the obtained knitted fabric were as shown in Table 1, the yellowing degree was large, and the dyeing properties were conspicuous in lightly dyed portions and lacked quality.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【発明の効果】本発明により、耐熱性に優れ、また均染
性に優れたポリアミド系繊維を効率的に製造することが
できる。According to the present invention, polyamide fibers having excellent heat resistance and excellent levelness can be efficiently produced.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｄ０６Ｍ 101:34 Ｄ０６Ｍ 101:34 Ｆターム(参考） 4J002 CL001 CL011 CL031 CL081 EQ026 FD076 GK01 4L033 AA08 AB01 AC05 AC15 BA78 4L035 BB31 BB60 EE01 EE20 JJ20 4L038 AA20 BA17 CA01 DA15 DA20──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification FI theme coat ゛ (Reference) // D06M 101: 34 D06M 101: 34 F term (Reference) 4J002 CL001 CL0011 CL031 CL081 EQ026 FD076 GK01 4L033 AA08 AB01 AC05 AC15 BA78 4L035 BB31 BB60 EE01 EE20 JJ20 4L038 AA20 BA17 CA01 DA15 DA20
Claims (4)
Ｅ−ＬＡＢ表色系におけるｂ値が２．５以下である耐熱
性ポリアミド系繊維。1. CI after dry heat treatment at 195 ° C. for 3 minutes
A heat-resistant polyamide fiber having a b value of 2.5 or less in an E-LAB color system.
が０．００１〜５質量％含有されていることを特徴とす
る請求項１記載の耐熱性ポリアミド系繊維。2. The heat-resistant polyamide fiber according to claim 1, wherein an antioxidant is contained in the polyamide fiber in an amount of 0.001 to 5% by mass.
ジド系化合物である請求項２記載の耐熱性ポリアミド系
繊維。 （Ｒ）2ＮＮＨＣＯＮＨ−Ｙ−ＮＨＣＯＮＨＮ（Ｒ）2 ……（１） （一般式中、Ｒは炭素数１〜４のアルキル基、Ｙは-
（ＣＨ2）n- 又は、Ａｒ-ＣＨ2-Ａｒ （Arはフェニレン
基）、nは１〜１１の整数である。）3. The heat-resistant polyamide fiber according to claim 2, wherein the antioxidant is a semicarbazide compound represented by the following formula. (R) 2 NNHCONH-Y-NHCONNHN (R) 2 (1) (In the general formula, R is an alkyl group having 1 to 4 carbon atoms, and Y is-
(CH 2) n-or, Ar-CH 2 -Ar (Ar is a phenylene group), n is an integer of 1 to 11. )
伸糸を捲き取る以前に紡糸油剤を付与するに際し、紡糸
油剤中に酸化防止剤を含有させることを特徴とする請求
項１〜３のいずれかに記載の耐熱性ポリアミド系繊維の
製造方法。4. The method according to claim 1, wherein an antioxidant is contained in the spinning oil when the polyamide fiber is melt-spun and the spinning oil is applied before the undrawn yarn is wound up. The method for producing a heat-resistant polyamide fiber according to any one of the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000243128A JP2002061075A (en) | 2000-08-10 | 2000-08-10 | Heat-resistant polyamide fiber and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000243128A JP2002061075A (en) | 2000-08-10 | 2000-08-10 | Heat-resistant polyamide fiber and method for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002061075A true JP2002061075A (en) | 2002-02-28 |
Family
ID=18734037
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008518115A (en) * | 2004-10-28 | 2008-05-29 | ハンツマン アドバンスト マテリアルズ （スイッツァランド） ゲーエムベーハー | How to improve thermal stability |
-
2000
- 2000-08-10 JP JP2000243128A patent/JP2002061075A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008518115A (en) * | 2004-10-28 | 2008-05-29 | ハンツマン アドバンスト マテリアルズ （スイッツァランド） ゲーエムベーハー | How to improve thermal stability |
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