JPH07216641A - Acrylic synthetic yarn having excellent whiteness - Google Patents
Acrylic synthetic yarn having excellent whitenessInfo
- Publication number
- JPH07216641A JPH07216641A JP3192294A JP3192294A JPH07216641A JP H07216641 A JPH07216641 A JP H07216641A JP 3192294 A JP3192294 A JP 3192294A JP 3192294 A JP3192294 A JP 3192294A JP H07216641 A JPH07216641 A JP H07216641A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- acrylic synthetic
- titanium dioxide
- whiteness
- acrylonitrile
- 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
Landscapes
- Artificial Filaments (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は白色度に優れたアクリル
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 whiteness.
【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安定性が悪く、重合体の溶解,繊維
の乾燥などの加熱を伴う工程において黄変しやすく実用
上種々な制約を受けているのが現状である。このため従
来より重合体の組成を変更する方法,製造条件を変更す
る方法,紡糸原液に安定剤を添加する方法等が検討され
てきたが、白色度に優れたものが得られていないのが現
状である。また、後処理、例えば次亜塩素酸ソーダで漂
白する方法等も検討されてきたが、風合が悪くなるとい
う欠点を有する。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 present condition is that the stability against heat is poor, and yellowing easily occurs in processes involving heating such as polymer dissolution and fiber drying, and various practical restrictions are imposed. For this reason, methods for changing the composition of the polymer, methods for changing the production conditions, methods for adding a stabilizer to the spinning dope, etc. have been studied in the past, but no excellent whiteness has been obtained. The current situation. Further, a post-treatment, for example, a method of bleaching with sodium hypochlorite has been studied, but it has a drawback that the texture becomes poor.
【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白色度を向上せしめる手段は種々
提案されているものの風合,染色性,操業性が良好で、
白色度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 whiteness of acrylic synthetic fibers have been proposed as described above, they have good feeling, dyeability and operability.
Acrylic synthetic fibers with excellent whiteness have not 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、その目的は風合,染色性,操業性が良好
で、白色度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-mentioned problems, and an object thereof is to provide an acrylic synthetic fiber which is excellent in feeling, dyeability and operability and is excellent in whiteness.
【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、粒子径が0.45μm以下
でかつ珪素をSiO2 として二酸化チタン量対比で2.
0重量%以上含んだルチル型二酸化チタンを0.1〜
5.0重量%含有し、かつ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
白色度に優れたアクリル系合成繊維により達成される。Means for Solving the Problems The above object is to obtain an acrylonitrile-based polymer having a particle diameter of 0.45 μm or less and silicon of SiO 2 in terms of titanium dioxide content of 2.
0.1 to 0.1% by weight of rutile titanium dioxide
Excellent whiteness characterized by containing 5.0% by weight and 0.01% by weight or more of 9-10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. Achieved by acrylic synthetic fiber.
【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 their alkyl esters, vinyl acetate, vinyl chloride, vinylidene chloride, sodium allyl sulfonate, sodium methallyl sulfonate, vinyl sulfone. Acid soda, styrene sulfonate sodium, 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 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】本発明に使用するルチル型二酸化チタン
は、粒子径が0.45μm以下であることが必要であ
る。粒子径が0.45μmを越えると操業性が著しく落
ち、耐光性の向上にも寄与しなくなる。また、珪素(S
i)が二酸化チタン量に対してSiO2 として2.0重
量%以上含有していることが必要であり、このことによ
り分散媒に対する分散性が向上し、繊維中の二酸化チタ
ンの分散が均一化し良好な耐光性が得られ、硬度の面で
も殆んど影響を及ぼさなくなる。珪素がSiO2 として
2.0重量%未満であると分散媒に対する分散性が不良
で、繊維中への分散が不均一となり操業上問題となる。
更に、かかるルチル型酸化チタンはアクリロニトリル系
重合体に対して0.1〜5.0重量%含有されることが
必要である。ルチル型酸化チタンの量が0.1重量%未
満では、良好な耐光性が得られず、5.0重量%を越え
ると紡糸が困難となる。The rutile titanium dioxide used in the present invention must have a particle size of 0.45 μm or less. If the particle size exceeds 0.45 μm, the operability is remarkably deteriorated and it does not contribute to the improvement of light resistance. In addition, silicon (S
It is necessary for i) to be contained in an amount of 2.0% by weight or more as SiO 2 with respect to the amount of titanium dioxide, which improves the dispersibility in the dispersion medium and makes the dispersion of titanium dioxide in the fiber uniform. Good light resistance can be obtained and hardness is hardly affected. When silicon is less than 2.0% by weight as SiO 2 , dispersibility in the dispersion medium is poor and the dispersion in the fiber is non-uniform, which is a problem in operation.
Further, it is necessary that the rutile titanium oxide is contained in an amount of 0.1 to 5.0% by weight based on the acrylonitrile polymer. When the amount of rutile type titanium oxide is less than 0.1% by weight, good light resistance cannot be obtained, and when it exceeds 5.0% by weight, spinning becomes difficult.
【0010】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).
【0011】[0011]
【化1】 [Chemical 1]
【0012】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.
【0013】次に本発明の耐光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ルチル型二酸化チタン有機溶剤に均
一微分散させ、次いでアクリロニトリル系共重合体の有
機溶剤溶液に添加し、これに更に9−10−ジヒドロ−
9−オキサ−10−フォスファフェナンスレン−10−
オキサイドを添加し紡糸することによって、繊維中にル
チル型二酸化チタンと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 having excellent light resistance of the present invention will be described. The acrylic synthetic fiber of the present invention is uniformly finely dispersed in an organic solvent of rutile type titanium dioxide, and then added to a solution of an acrylonitrile copolymer in an organic solvent, and 9-10-dihydro-
9-oxa-10-phosphaphenanthrene-10-
By adding oxide and spinning, rutile type titanium dioxide and 9-10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are uniformly contained in the fiber. Spinning method is normal wet type, dry type,
Both dry and wet are possible. 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.
【0014】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、乾燥及び
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-swelled state after spinning in an emulsion state using an emulsifier, followed by drying and densification.
【0015】[0015]
【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。白色度の測定評価は、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、色差計においてハンター白度で評価
した。また耐光性の測定評価は、丸編したものを63℃
で20時間、フェードメーターにおいて露光させ、変退
色(グレースケール)で評価した。EXAMPLES Next, the present invention will be specifically described by showing examples. In the examples, “part” means “part by weight” and “%” means “% by weight”. For the measurement and evaluation of whiteness, the obtained acrylic synthetic fiber was spun by a conventional method to form No. 30 single yarn and then circular knitted, and evaluated by Hunter whiteness in a color difference meter. The light resistance was measured and evaluated by circular knitting at 63 ° C.
Exposure in a fade meter for 20 hours and evaluated by discoloration (gray scale).
【0016】実施例1〜5、比較例1〜4 アクリロニトリル(AN)/メチルアクリレート(M
A)/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)=91.2/8.0/0.8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
(DMF)溶液を準備し、紡糸原液とした。次いで、粒
子径が0.20μmでかつ珪素(Si)がSiO2 とし
て二酸化チタン量対比で所定量含んだルチル型二酸化チ
タン15重量%をDMFに均一分散した後、重合体に対
して二酸化チタンが所定量になるようにチタン分散液を
添加した。さらに、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)を重合体に対し
て所定量になるように添加し、紡糸原液とした。その後
紡績原液を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150℃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 1-5, Comparative Examples 1-4 Acrylonitrile (AN) / methyl acrylate (M
A) A solution of acrylonitrile polymer consisting of sodium acrylamido-2-methylpropanesulfonate (SAM) = 91.2 / 8.0 / 0.8 in dimethylformamide (DMF) was prepared as a spinning stock solution. . Then, 15% by weight of rutile-type titanium dioxide having a particle size of 0.20 μm and containing silicon (Si) as SiO 2 in a predetermined amount relative to the amount of titanium dioxide was uniformly dispersed in DMF. The titanium dispersion liquid was added so as to have a predetermined amount. Further, 9-10-dihydro-9-oxa-
10-phosphaphenanthrene-10-oxide (trade name HCA: manufactured by Sanko Chemical Co., Ltd.) was added to the polymer in a predetermined amount to prepare a spinning dope. After that, the spinning dope is spun into a 60% DMF aqueous solution at 20 ° C., subjected to a drawing process while being desolvated, and a water washing process, and then a fiber oil agent is applied, and then dried and densified at 150 ° C. using a roller dryer. It was Next, after the mechanical crimp was applied, the crimp was set at 115 ° C. under moist heat. Cut the resulting fiber,
Then, after spinning, a circular knit fabric was produced. The fiber was evaluated by the method described above. The results are shown in Table 1.
【0017】[0017]
【表1】 [Table 1]
【0018】表1から明らかなように、実施例品は比較
例品に比べて操業性に優れ、しかも優れた白色度を有し
ていることがわかる。また、実施例品は比較例品に比べ
て優れた耐光性を有していることがわかる。As can be seen from Table 1, the product of the example is superior to the product of the comparative example in operability and has excellent whiteness. Further, it can be seen that the product of Example has excellent light resistance as compared with the product of Comparative Example.
【0019】[0019]
【発明の効果】本発明の白色度に優れたアクリル系合成
繊維は、高度な白色度を有し、かつ耐光性にも優れ、ま
た通常の風合,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、白色度を必要とする衣料等幅広い用途に使用
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。The acrylic synthetic fiber having excellent whiteness according to the present invention has a high degree of whiteness and excellent light resistance, and has ordinary feeling, dyeability, operability, etc. Very useful. The fibers obtained by the present invention are ordinary acrylic synthetic fibers, polyester, nylon, cotton,
It can be used as a mixture with other fibers such as rayon and wool, and can be used in a wide range of applications such as clothing requiring whiteness, which is extremely useful industrially.
Claims (1)
子径が0.45μm以下でかつ珪素をSiO2 として二
酸化チタン量対比で2.0重量%以上含んだルチル型二
酸化チタンを0.1〜5.0重量%含有し、かつ9−1
0−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白色度に優れたアクリル系合成繊
維。1. A rutile-type titanium dioxide having a particle size of 0.45 μm or less and containing silicon as SiO 2 in an amount of 2.0% by weight or more based on the amount of titanium dioxide with respect to an acrylonitrile-based polymer. 0.0% by weight and 9-1
An acrylic synthetic fiber having excellent whiteness, which comprises 0.01% by weight or more of 0-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3192294A JPH07216641A (en) | 1994-02-02 | 1994-02-02 | Acrylic synthetic yarn having excellent whiteness |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3192294A JPH07216641A (en) | 1994-02-02 | 1994-02-02 | Acrylic synthetic yarn having excellent whiteness |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH07216641A true JPH07216641A (en) | 1995-08-15 |
Family
ID=12344472
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3192294A Pending JPH07216641A (en) | 1994-02-02 | 1994-02-02 | Acrylic synthetic yarn having excellent whiteness |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH07216641A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20150053898A (en) | 2012-09-13 | 2015-05-19 | 닛폰 에쿠스란 고교 가부시키가이샤 | Acrylonitrile-based fiber, manufacturing process therefor and fiber structure containing said fiber |
-
1994
- 1994-02-02 JP JP3192294A patent/JPH07216641A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20150053898A (en) | 2012-09-13 | 2015-05-19 | 닛폰 에쿠스란 고교 가부시키가이샤 | Acrylonitrile-based fiber, manufacturing process therefor and fiber structure containing said fiber |
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