JPH07216640A - Acrylic synthetic yarn having excellent yellowing resistance - Google Patents
Acrylic synthetic yarn having excellent yellowing resistanceInfo
- Publication number
- JPH07216640A JPH07216640A JP3192194A JP3192194A JPH07216640A JP H07216640 A JPH07216640 A JP H07216640A JP 3192194 A JP3192194 A JP 3192194A JP 3192194 A JP3192194 A JP 3192194A JP H07216640 A JPH07216640 A JP H07216640A
- Authority
- JP
- Japan
- Prior art keywords
- yellowing resistance
- acrylic synthetic
- weight
- acrylonitrile
- phosphaphenanthrene
- Prior art date
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は高温時の耐黄変性に優れ
たアクリル系合成繊維に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic synthetic fiber excellent in yellowing resistance at high temperatures.
【０００２】[0002]
【従来の技術】アクリル系合成繊維は、風合や染色性が
優れるため衣料用，寝装用に幅広く使われている。しか
しながら熱に対する耐黄変性が不良で、例えばダストコ
ントロールマット分野においては、パイルを編成した後
に１５０℃で２０分間乾燥するというバッキング工程を
通すため、加工中に黄変しやすく、加工上種々な制約を
受けているのが現状である。このためヒンダートフェノ
ール系の酸化防止剤，硫黄系酸化防止剤を用いることが
検討されてきたが、これらの方法はオレフィン系合成繊
維には有効であるが、アクリル系合成繊維に対しては効
果が少なく、耐黄変性に優れたアクリル系合成繊維は得
られていないのが現状である。2. Description of the Related Art Acrylic synthetic fibers are widely used for clothing and bedding because of their excellent texture and dyeability. However, the yellowing resistance to heat is poor. For example, in the field of dust control mats, the pile is knitted and then dried at 150 ° C. for 20 minutes, which is followed by a backing process. The current situation is that they are receiving it. For this reason, the use of hindered phenolic antioxidants and sulfur-based antioxidants has been investigated, but these methods are effective for olefinic synthetic fibers but effective for acrylic synthetic fibers. The present situation is that no acrylic synthetic fiber having a high level of yellowing resistance and excellent yellowing resistance has been obtained.
【０００３】[0003]
【発明が解決しようとする課題】上記したようにアクリ
ル系合成繊維に対して耐黄変性を向上せしめる手段は種
々提案されているものの、染色性，操業性が良好で、耐
黄変性に優れたアクリル系合成繊維は得られていない。Although various means for improving the yellowing resistance of acrylic synthetic fibers have been proposed as described above, they have excellent dyeing properties and operability and are excellent in yellowing resistance. No acrylic synthetic fibers have been obtained.
【０００４】本発明は上述の問題点に鑑みてなされたも
のであって、その目的は染色性，操業性が良好で、耐黄
変性に優れたアクリル系合成繊維を提供するにある。The present invention has been made in view of the above problems, and an object thereof is to provide an acrylic synthetic fiber having good dyeability and operability and excellent yellowing resistance.
【０００５】[0005]
【課題を解決するための手段】上述の目的は、アクリロ
ニトリル系重合体に対して、９−１０−ジヒドロ−９−
オキサ−１０−フォスファフェナンスレン−１０−オキ
サイドを０．０１重量％以上含有してなる事を特徴とす
る耐黄変性に優れたアクリル系合成繊維により達成され
る。SUMMARY OF THE INVENTION The above-mentioned object is to provide an acrylonitrile polymer with 9-10-dihydro-9-
It is achieved by an acrylic synthetic fiber excellent in yellowing resistance, which is characterized by containing 0.01% by weight or more of oxa-10-phosphaphenanthrene-10-oxide.
【０００６】以下、本発明を詳細に説明する。The present invention will be described in detail below.
【０００７】本発明に使用するアクリロニトリル系重合
体は少なくとも３０重量％のアクリロニトリルを含有す
るもので繊維形成能を有するものならばいかなる重合体
をも用いることが可能である。すなわちアクリロニトリ
ルを３０重量％以上と他のビニル系モノマー、例えばア
クリル酸、メタクリル酸、或いはこれらのアルキルエス
テル類、酢酸ビニル、塩化ビニル、塩化ビニリデン、ア
リルスルホン酸ソーダ、メタリルスルホン酸ソーダ、ビ
ニルスルホン酸ソーダ、スチレンスルホン酸ソーダ、２
−アクリルアミド−２−メチルプロパンスルホン酸ソー
ダなどを適宜組合せたものを７０重量％以下の割合で共
重合せしめたものが挙げられる。特にアクリロニトリル
８０重量％以上と２０重量％以下のビニル系モノマー及
びスルホン酸基含有モノマーの共重合体、又はアクリロ
ニトリル３０〜８０重量％と塩化ビニル及び／又は塩化
ビニリデン２０〜７０重量％及びスルホン酸基含有モノ
マーを０〜１０重量％含有する共重合体が好ましい。The acrylonitrile-based polymer used in the present invention contains at least 30% by weight of acrylonitrile, and any polymer having a fiber-forming ability can be used. That is, 30% by weight or more of acrylonitrile and other vinyl monomers such as acrylic acid, methacrylic acid, or alkyl esters thereof, vinyl acetate, vinyl chloride, vinylidene chloride, sodium allyl sulfonate, sodium methallyl sulfonate, vinyl sulfone. Acid soda, sodium styrene sulfonate, 2
-Acrylic-2-methylpropane sulfonic acid soda and the like are appropriately combined and copolymerized at a ratio of 70% by weight or less. Particularly, a copolymer of acrylonitrile of 80% by weight or more and 20% by weight or less of a vinyl-based monomer and a sulfonic acid group-containing monomer, or 30-80% by weight of acrylonitrile and 20-70% by weight of vinyl chloride and / or vinylidene chloride and a sulfonic acid group. A copolymer containing 0 to 10% by weight of the contained monomer is preferable.
【０００８】本発明に使用される重合体は、水系懸濁重
合，乳化重合，溶液重合などの公知の重合方法によって
作られ特に限定するものではない。The polymer used in the present invention is prepared by a known polymerization method such as aqueous suspension polymerization, emulsion polymerization and solution polymerization, and is not particularly limited.
【０００９】本発明に使用する９−１０−ジヒドロ−９
−オキサ−１０−フォスファフェナンスレン−１０−オ
キサイドは下記構造式（１）で示される物である。9-10-dihydro-9 used in the present invention
-Oxa-10-phosphaphenanthrene-10-oxide is represented by the following structural formula (1).
【００１０】[0010]
【化１】 [Chemical 1]
【００１１】かかる９−１０−ジヒドロ−９−オキサ−
１０−フォスファフェナンスレン−１０−オキサイドは
アクリロニトリル系重合体に対して０．０１重量％以
上、好ましくは０．０１〜２．０重量％、更に好ましく
は０．０５〜１．０重量％含有されることが必要であ
る。０．０１重量％未満では着色防止効果が得られず、
一方多量に用いると逆に着色が増す場合があり好ましく
ない。Such 9-10-dihydro-9-oxa-
The content of 10-phosphaphenanthrene-10-oxide is 0.01% by weight or more, preferably 0.01 to 2.0% by weight, more preferably 0.05 to 1.0% by weight, based on the acrylonitrile polymer. It is necessary to be contained. If it is less than 0.01% by weight, the effect of preventing coloration cannot be obtained,
On the other hand, if used in a large amount, coloring may increase, which is not preferable.
【００１２】次に本発明の耐黄変性に優れたアクリル系
合成繊維の製造方法の一例について説明する。本発明の
アクリル系合成繊維は、アクリロニトリル系共重合体の
有機溶剤溶液に、９−１０−ジヒドロ−９−オキサ−１
０−フォスファフェナンスレン−１０−オキサイドを添
加し紡糸することによって、繊維中に９−１０−ジヒド
ロ−９−オキサ−１０−フォスファフェナンスレン−１
０−オキサイドを均一に含有せしめる。紡糸方法は通常
の湿式，乾式，乾・湿式いずれもが可能である。そし
て、例えば湿式紡糸の場合には通常のアクリル系合成繊
維と同様の条件で行えば良く、数段の浴槽を通し、順次
延伸，水洗，乾燥，後処理を行う。Next, an example of the method for producing an acrylic synthetic fiber excellent in yellowing resistance of the present invention will be described. The acrylic synthetic fiber of the present invention is prepared by adding 9-10-dihydro-9-oxa-1 to an organic solvent solution of an acrylonitrile copolymer.
By adding 0-phosphaphenanthrene-10-oxide and spinning, 9-10-dihydro-9-oxa-10-phosphaphenanthrene-1 was added to the fiber.
It contains 0-oxide uniformly. The spinning method can be normal wet, dry, or dry / wet. Then, for example, in the case of wet spinning, it may be carried out under the same conditions as in the case of ordinary acrylic synthetic fiber, and the drawing, washing, drying and post-treatment are sequentially carried out through a bath of several stages.
【００１３】尚、９−１０−ジヒドロ−９−オキサ−１
０−フォスファフェナンスレン−１０−オキサイドの添
加方法は、紡糸原液に直接添加してもよく、有機溶剤に
溶解し原液に添加してもよく、特に制限されるものでは
ない。また、場合によっては紡糸後ゲル膨潤状態の繊維
に乳化剤を用いたエマルジョン状態で付与し、乾熱及び
緻密化を行う方法で添加しても良い。Incidentally, 9-10-dihydro-9-oxa-1
The method of adding 0-phosphaphenanthrene-10-oxide may be either directly added to the spinning stock solution or dissolved in an organic solvent and added to the stock solution, and is not particularly limited. In some cases, the fibers may be added in a gel swollen state after spinning in the form of an emulsion using an emulsifier, followed by dry heat and densification.
【００１４】[0014]
【実施例】次に実施例を示し本発明を具体的に説明す
る。尚、実施例中の部とあるのは重量部を、％とあるの
は重量％を示す。耐黄変性の測定評価は、得られたアク
リル系合成繊維を常法により紡績して３０番単糸となし
た後丸編したものを、１５０℃で２０分、乾熱熱処理機
において処理し、処理前後の比較を変退色（グレースケ
ール）で評価を行った。EXAMPLES Next, the present invention will be specifically described by showing examples. In the examples, “part” means “part by weight” and “%” means “% by weight”. The yellowing resistance was measured and evaluated by spinning the obtained acrylic synthetic fiber into a No. 30 single yarn and then circular knitting, and treating it at 150 ° C. for 20 minutes in a dry heat treatment machine, The comparison before and after the treatment was evaluated by discoloration (gray scale).
【００１５】実施例１〜３ アクリロニトリル（ＡＮ）／塩化ビニリデン（ＶＣ
ｌ2 ）／２−アクリルアミド−２−メチルプロパンスル
ホン酸ソーダ（ＳＡＭ）＝５３／４４／３からなるアク
リロニトリル系重合体のジメチルホルムアミド（ＤＭ
Ｆ）溶液を準備し、紡糸原液とした。そして、９−１０
−ジヒドロ−９−オキサ−１０−フォスファフェナンス
レン−１０−オキサイド（商品名 ＨＣＡ：三光化学
（株）製）１５重量％をＤＭＦに均一分散した後、重合
体に対して所定量になるように分散液を添加し紡糸原液
とした。その後紡糸原液を２０℃、６０％ＤＭＦ水溶液
中に紡出し、脱溶媒させながら延伸、水洗工程を経た
後、繊維油剤を付与し、次にローラー式乾燥機を用い１
５０℃で乾燥緻密化を行った。次に機械クリンプを付与
後湿熱１１５℃でクリンプのセットを行った。得られた
繊維をカットし、次いで紡績をした後丸編布を作製し
た。この繊維をさきに述べた方法により評価をした。結
果を表１に示す。Examples 1 to 3 Acrylonitrile (AN) / vinylidene chloride (VC)
l 2 ) / 2-acrylamido-2-methylpropanesulfonic acid sodium (SAM) = 53/44/3, an acrylonitrile polymer dimethylformamide (DM)
F) A solution was prepared and used as a spinning dope. And 9-10
15% by weight of -dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (trade name HCA: manufactured by Sanko Chemical Co., Ltd.) was uniformly dispersed in DMF, and then, a predetermined amount was obtained with respect to the polymer. The dispersion was added as described above to prepare a spinning dope. After that, the spinning solution was spun into a 60% DMF aqueous solution at 20 ° C., stretched while being desolvated, washed with water, added with a fiber oil, and then dried with a roller dryer.
Dry densification was performed at 50 ° C. Next, after the mechanical crimp was applied, the crimp was set at 115 ° C. under moist heat. The obtained fiber was cut and then spun to make a circular knit fabric. The fiber was evaluated by the method described above. The results are shown in Table 1.
【００１６】比較例１ 実施例１〜３において９−１０−ジヒドロ−９−オキサ
−１０−フォスファフェナンスレン−１０−オキサイド
を用いなかった以外は、実施例１〜３と同様に行った。
結果を表１に示す。Comparative Example 1 The same procedure as in Examples 1 to 3 was repeated except that 9-10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was not used in Examples 1 to 3. .
The results are shown in Table 1.
【００１７】比較例２〜４ 実施例１〜３において９−１０−ジヒドロ−９−オキサ
−１０−フォスファフェナンスレン−１０−オキサイド
に代えてトリエチレングリコール−ビス（３−（３−ｔ
−ブチル−５メチル−４−ヒドロキシフェニル）プロピ
オネート）（商品名 Ｉｒｇａｎｏｘ ２４５：チバガ
イギー（株）製）を用いた以外は、実施例１〜３と同様
に行った。結果を表１に示す。Comparative Examples 2 to 4 In Examples 1 to 3, triethylene glycol-bis (3- (3-t) was used instead of 9-10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
-Butyl-5-methyl-4-hydroxyphenyl) propionate) (trade name Irganox 245: manufactured by Ciba-Geigy Co., Ltd.) was used and performed in the same manner as in Examples 1 to 3. The results are shown in Table 1.
【００１８】[0018]
【表１】 [Table 1]
【００１９】表１から明らかなように、実施例品は比較
例品に比べて優れた耐黄変性を有していることがわか
る。As can be seen from Table 1, the products of Examples have excellent yellowing resistance as compared with the products of Comparative Examples.
【００２０】[0020]
【発明の効果】本発明の耐黄変性に優れたアクリル系合
成繊維は、優れた高温時の耐黄変性を有し、また通常の
染色性，操業性等を有しており頗る有用である。また、
本発明によって得られた繊維は、通常のアクリル系合成
繊維，ポリエステル，ナイロン，木綿，レーヨン，羊毛
等他の繊維と混用して使用することも可能であり、耐黄
変性を必要とするカーペット，カーテン等の用途に使用
することが出来るため、産業上極めて有意義なものであ
る。INDUSTRIAL APPLICABILITY The acrylic synthetic fiber excellent in yellowing resistance of the present invention has excellent yellowing resistance at high temperature, and has ordinary dyeability, operability, etc., and thus is very useful. . Also,
The fiber obtained by the present invention can also be used by mixing with other fibers such as ordinary acrylic synthetic fiber, polyester, nylon, cotton, rayon, and wool, and a carpet requiring yellowing resistance, Since it can be used for applications such as curtains, it is extremely meaningful industrially.
Claims (1)
−１０−ジヒドロ−９−オキサ−１０−フォスファフェ
ナンスレン−１０−オキサイドを０．０１重量％以上含
有してなる事を特徴とする耐黄変性に優れたアクリル系
合成繊維。1. With respect to an acrylonitrile-based polymer, 9
An acrylic synthetic fiber excellent in yellowing resistance, which comprises 0.01% by weight or more of -10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3192194A JPH07216640A (en) | 1994-02-02 | 1994-02-02 | Acrylic synthetic yarn having excellent yellowing resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3192194A JPH07216640A (en) | 1994-02-02 | 1994-02-02 | Acrylic synthetic yarn having excellent yellowing resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07216640A true JPH07216640A (en) | 1995-08-15 |
Family
ID=12344446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3192194A Pending JPH07216640A (en) | 1994-02-02 | 1994-02-02 | Acrylic synthetic yarn having excellent yellowing resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07216640A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781451A (en) * | 2010-03-16 | 2010-07-21 | 南通星辰合成材料有限公司 | Polyphenyl ether resin composition and method for preparing same |
| JP2011001526A (en) * | 2009-06-22 | 2011-01-06 | Asahi Kasei Chemicals Corp | Resin composition obtained by heat-stabilizing low-birefringence acrylic copolymer |
-
1994
- 1994-02-02 JP JP3192194A patent/JPH07216640A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011001526A (en) * | 2009-06-22 | 2011-01-06 | Asahi Kasei Chemicals Corp | Resin composition obtained by heat-stabilizing low-birefringence acrylic copolymer |
| CN101781451A (en) * | 2010-03-16 | 2010-07-21 | 南通星辰合成材料有限公司 | Polyphenyl ether resin composition and method for preparing same |
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