JPH0827620A - Production of acrylic synthetic fiber - Google Patents
Production of acrylic synthetic fiberInfo
- Publication number
- JPH0827620A JPH0827620A JP18083694A JP18083694A JPH0827620A JP H0827620 A JPH0827620 A JP H0827620A JP 18083694 A JP18083694 A JP 18083694A JP 18083694 A JP18083694 A JP 18083694A JP H0827620 A JPH0827620 A JP H0827620A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- dispersion
- spinning
- synthetic fiber
- weight
- 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、酸化チタンを含有する
アクリル系合成繊維の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an acrylic synthetic fiber containing titanium oxide.
【０００２】[0002]
【従来の技術】繊維中に酸化チタン，硫酸バリウム等の
艶消し剤を分散せしめ艶消し効果を持たせることは、ポ
リアミド，ポリエステル，アクリル等の合成繊維の製造
において広く行われている。そして、艶消し剤の中でも
酸化チタンは屈折率が高く有用であるが、粒子表面の活
性のために分散性、特に極性有機溶媒中への分散性が悪
い。そのため酸化チタンを各種有機溶媒に分散させ、こ
れをアクリロニトリル系重合体紡糸原液に添加して紡糸
する際、原液中に分散した酸化チタンが凝集し、フィル
ターに沈着し、フィルターの目詰りを起して濾過性が低
下し、操業効率が向上しないという問題があった。2. Description of the Related Art Dispersing a matting agent such as titanium oxide or barium sulfate in a fiber so as to have a matting effect is widely used in the production of synthetic fibers such as polyamide, polyester and acrylic. Among the matting agents, titanium oxide has a high refractive index and is useful, but its dispersibility, particularly dispersibility in polar organic solvents, is poor due to the activity of the particle surface. Therefore, titanium oxide is dispersed in various organic solvents, and when this is added to an acrylonitrile polymer spinning stock solution and spun, the titanium oxide dispersed in the stock solution agglomerates and deposits on the filter, causing clogging of the filter. Therefore, there is a problem that the filterability is lowered and the operation efficiency is not improved.
【０００３】そこで、酸化チタンの分散剤として界面活
性剤を添加し分散性を向上せしめる方法が試みられてき
たが、界面活性剤が凝固浴中へ溶出し、溶剤回収時に界
面活性剤の分離に手間がかかるという問題があった。ま
た、酸化チタンの表面活性をＳｉＯ2 やＡｌ2 Ｏ3 等で
処理することにより抑え、分散性を向上せしめる方法が
試みられてきたが、酸化チタンの製造工程が複雑になる
ばかりでなく、ＳｉＯ2 やＡｌ2 Ｏ3 が凝固浴中へ溶出
し、紡浴が汚染され工業的生産に関して大きな問題があ
った。Therefore, a method of adding a surfactant as a dispersant for titanium oxide to improve the dispersibility has been attempted, but the surfactant is eluted into the coagulation bath to separate the surfactant during solvent recovery. There was a problem that it took time. Further, a method of suppressing the surface activity of titanium oxide by treating it with SiO 2 or Al 2 O 3 to improve the dispersibility has been tried, but not only the manufacturing process of titanium oxide becomes complicated, but also SiO 2 2 and Al 2 O 3 were eluted into the coagulation bath, and the spinning bath was contaminated, causing a serious problem in industrial production.
【０００４】[0004]
【発明が解決しようとする課題】このように、酸化チタ
ンを含むアクリロニトリル系重合体を紡糸する際に、紡
糸性を向上せしめる手段は種々提案されているものの、
紡糸性に優れ、安定性に優れた酸化チタンを含むアクリ
ル系合成繊維の製造方法は今だ得られていない。Thus, although various means have been proposed for improving the spinnability when spinning an acrylonitrile polymer containing titanium oxide,
A method for producing an acrylic synthetic fiber containing titanium oxide, which has excellent spinnability and stability, has not yet been obtained.
【０００５】本発明は上述の問題点に鑑みてなされたも
のであって、その目的は紡糸性に優れた酸化チタンを含
むアクリル系合成繊維を得うる製造方法を提供するにあ
る。The present invention has been made in view of the above problems, and an object thereof is to provide a method for producing an acrylic synthetic fiber containing titanium oxide which is excellent in spinnability.
【０００６】[0006]
【課題を解決するための手段】上述の目的は、酸化チタ
ンを含むアクリロニトリル系重合体を紡糸するに際し、
有機溶媒中に酸化チタンと酸化チタンに対して０．０１
〜３重量％の塩化カルシウムを均一分散させ分散液とな
し、次いで該分散液をアクリロニトリル系重合体の紡糸
原液に添加し、これを紡糸する事を特徴とするアクリル
系合成繊維の製造方法により達成される。Means for Solving the Problems The above-mentioned object is to spin an acrylonitrile polymer containing titanium oxide,
0.01 for titanium oxide and titanium oxide in organic solvent
-3% by weight of calcium chloride is uniformly dispersed to form a dispersion, which is then added to a spinning stock solution of an acrylonitrile polymer, which is then spun to achieve a method for producing an acrylic synthetic fiber. To be done.
【０００７】以下、本発明を詳細に説明する。The present invention will be described in detail below.
【０００８】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４０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物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４０重量％以上と他の共重合性の単量体、例えば
アクリル酸メチル，アクリル酸エチル等のアクリル酸ア
ルキルエステル、メタクリル酸メチル，メタクリル酸エ
チル等のメタクリル酸アルキルエステル、スチレン，酢
酸ビニル，塩化ビニリデン，塩化ビニル，ビニルエチル
エーテル，メタクリロニトリル等の中性単量体、アクリ
ル酸，メタクリル酸，アリルスルホン酸，メタリルスル
ホン酸，スチレンスルホン酸，２−アクリルアミド−２
−メチルプロパンスルフォン酸等の酸性単量体及びこれ
ら単量体のアンモニウム塩，アルカリ金属塩等などを適
宜組合せたものを６０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％以下の中性単量体及びスルホン酸基含
有単量体の共重合体が好ましい。このアクリロニトリル
系重合体は通常の懸濁重合，溶液重合，乳化重合等の如
何なる方法によって製造されたものでも良い。The acrylonitrile polymer used in the present invention contains at least 40% by weight of acrylonitrile, and any polymer having a fiber-forming ability can be used. That is, 40% by weight or more of acrylonitrile and other copolymerizable monomers such as alkyl acrylates such as methyl acrylate and ethyl acrylate, methacrylic acid alkyl esters such as methyl methacrylate and ethyl methacrylate, styrene and acetic acid. Neutral monomers such as vinyl, vinylidene chloride, vinyl chloride, vinyl ethyl ether, methacrylonitrile, acrylic acid, methacrylic acid, allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2
Examples thereof include those obtained by copolymerizing acidic monomers such as methyl propane sulfonic acid and ammonium salts of these monomers, alkali metal salts and the like as appropriate in a proportion of 60% by weight or less. Especially 80% by weight of acrylonitrile
A copolymer of the above-mentioned and 20% by weight or less of a neutral monomer and a sulfonic acid group-containing monomer is preferable. The acrylonitrile polymer may be produced by any method such as ordinary suspension polymerization, solution polymerization and emulsion polymerization.
【０００９】紡糸原液の溶媒としては、アクリロニトリ
ル系重合体を溶解しうる溶媒ならばいずれを使用しても
良い。例えば、ジメチルホルムアミド，ジメチルアセト
アミド，ジメチルスルホキシド，アセトン等の有機溶媒
が挙げられ、少量の水を含むことも差支えない。As the solvent of the spinning dope, any solvent can be used so long as it can dissolve the acrylonitrile polymer. Examples thereof include organic solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, and acetone, and they may contain a small amount of water.
【００１０】アクリロニトリル系重合体に酸化チタンと
塩化カルシウムの混合物を添加，混合する方法として
は、アクリロニトリル系重合体をジメチルスルホアミド
等の溶媒に溶解した紡糸原液に、酸化チタンと塩化カル
シウムとの混合物を有機溶媒に均一分散させた分散液を
紡糸直前に添加，混合すれば良い。As a method for adding and mixing a mixture of titanium oxide and calcium chloride to an acrylonitrile-based polymer, a spinning stock solution prepared by dissolving the acrylonitrile-based polymer in a solvent such as dimethylsulfamide is mixed with titanium oxide and calcium chloride. A dispersion liquid in which is uniformly dispersed in an organic solvent may be added and mixed immediately before spinning.
【００１１】酸化チタンの分散液を紡糸原液に添加，混
合するための機器としては、通常の混合機が使用される
が、均一に分散させるという点で、ホモミキサーが好ま
しく使用される。また、さらに分散性を向上させる事を
目的として、超音波分散濾過機を用いる事が好ましい。As a device for adding and mixing the titanium oxide dispersion to the spinning dope, a normal mixer is used, but a homomixer is preferably used from the viewpoint of uniform dispersion. Further, it is preferable to use an ultrasonic dispersion filter for the purpose of further improving the dispersibility.
【００１２】アクリロニトリル系重合体に艶消剤として
酸化チタンを添加することは良く知られているが、添加
量が多くなると分散性が悪くなる。しかしながら、塩化
カルシウムを酸化チタンと併用することにより、特に塩
化カルシウムを酸化チタンに対して０．０１〜３重量
％、特に０．１〜１重量％用いることにより分散性の大
幅な向上が見られる。塩化カルシウムの酸化チタンに対
する量が０．０１重量％以下であると分散性の向上がみ
られず、一方３重量％を越えると分散性の向上が飽和に
達し、繊維の品質が落ちるので好ましくない。It is well known that titanium oxide is added to an acrylonitrile polymer as a matting agent, but the dispersibility deteriorates as the amount of addition increases. However, by using calcium chloride in combination with titanium oxide, especially by using calcium chloride in an amount of 0.01 to 3% by weight, particularly 0.1 to 1% by weight, based on titanium oxide, a significant improvement in dispersibility is observed. . If the amount of calcium chloride with respect to titanium oxide is 0.01% by weight or less, the dispersibility is not improved. On the other hand, if it exceeds 3% by weight, the improvement of the dispersibility reaches saturation and the quality of the fiber is deteriorated. .
【００１３】尚、本発明に使用する酸化チタンは通常に
使用できるものであればルチル型でもアナターゼ型でも
よく、結晶型を特に問題としない。酸化チタンの粒子径
は通常繊維に適用可能な大きさならば特に問題はない
が、０．０５〜０．２μｍが好ましい。尚、分散液中の
酸化チタンの含有量は５〜２５重量％が好ましく、５重
量％未満の場合は分散液が希薄となり生産面で好ましく
なく、２５重量％を越えると、十分な分散性が得られな
くなる。The titanium oxide used in the present invention may be of the rutile type or the anatase type as long as it can be used normally, and the crystal type is not a particular problem. The particle diameter of titanium oxide is not particularly limited as long as it is a size that can be usually applied to fibers, but is preferably 0.05 to 0.2 μm. The content of titanium oxide in the dispersion liquid is preferably 5 to 25% by weight, and when the content is less than 5% by weight, the dispersion liquid becomes thin, which is not preferable in terms of production. When it exceeds 25% by weight, sufficient dispersibility is obtained. You won't get it.
【００１４】酸化チタンと塩化カルシウムを分散させる
有機溶媒としては特に限定されず、例えば、ジメチルホ
ルムアミド，ジメチルアセトアミド，ジメチルスルホキ
シド，アセトン等の有機溶媒が挙げられ、一般的には紡
糸原液の溶媒と同じものが用いられる。The organic solvent in which titanium oxide and calcium chloride are dispersed is not particularly limited, and examples thereof include organic solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, and acetone, which are generally the same as the solvent of the spinning dope. Things are used.
【００１５】紡糸方法は通常のアクリル系合成繊維の製
造に用いられる方法、即ち、湿式，乾湿式のいずれでも
実施できる。紡糸したのち、公知の方法で洗浄，延伸，
乾燥，熱処理等を行う。The spinning method can be carried out by a method generally used for producing acrylic synthetic fibers, that is, a wet method or a dry-wet method. After spinning, washing, stretching, and
Dry and heat treatment.
【００１６】[0016]
【実施例】次に実施例を示し本発明を具体的に説明す
る。分散保持率は、ビーカーに所定量の塩化カルシウ
ム、ジメチルホルムアミド及び二酸化チタンを添加し、
１０分間４０００ｒｐｍで攪拌し、この液を必要本数分
２００ｍｌのメスシリンダーに分注し、各経時時間ごと
に液面より上部１ｃｍのところの液をスポイドで採取
し、蒸発乾固させ、その固形分を測定することにより求
めた。EXAMPLES Next, the present invention will be specifically described by showing examples. Dispersion retention rate, adding a predetermined amount of calcium chloride, dimethylformamide and titanium dioxide to the beaker,
Stir at 4000 rpm for 10 minutes, dispense this liquid into a 200 ml graduated cylinder for the required number of tubes, collect the liquid 1 cm above the liquid surface with a spoid at each elapsed time, evaporate to dryness, and then remove the solid content. Was determined by measuring.
【００１７】実施例１〜３，比較例１〜３ 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、塩
化カルシウムを二酸化チタン（チタン工業社製，ＫＡ−
３０Ａ）に対して所定量ＤＭＦに溶解させ、これに二酸
化チタンの所定量をホモミキサーを使用して分散させ分
散液とした。この分散液の二酸化チタンの分散性（その
分散液の１，３，５，２４ｈｒ後の静置安定性）を表１
に示す。Examples 1 to 3, Comparative Examples 1 to 3 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. . Next, calcium chloride was added to titanium dioxide (manufactured by Titanium Industry Co., Ltd., KA-
A predetermined amount of 30A) was dissolved in DMF, and a predetermined amount of titanium dioxide was dispersed in this using a homomixer to obtain a dispersion liquid. Table 1 shows the dispersibility of titanium dioxide in this dispersion (stability of the dispersion after 1, 3, 5, 24 hours).
Shown in
【００１８】次いで、この分散液を紡糸原液中のポリマ
ー量に対して酸化チタン量が１．５重量％となるように
添加した紡糸原液を、ノズル孔径０．０６μｍ，４００
０Ｈの口金を用いて２０℃、６０％のＤＭＦ水溶液に紡
糸し、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１
１５℃でクリンプのセットを行い、３ｄの白色ダル繊維
を得た。このときの１時間後の口金圧上昇を表１に示
す。Next, this spinning solution was added so that the amount of titanium oxide was 1.5% by weight with respect to the amount of the polymer in the spinning solution, and the nozzle hole diameter was 0.06 μm, 400.
Spin to a 60% DMF aqueous solution at 20 ° C. using a 0H spinneret, stretch while desolvating and wash with water, apply a fiber oil agent, and then dry and densify at 150 ° C. using a roller dryer. I went. Wet heat after applying mechanical crimp 1
The crimp was set at 15 ° C. to obtain 3d white dull fiber. Table 1 shows the rise of the die pressure after 1 hour at this time.
【００１９】[0019]
【表１】 [Table 1]
【００２０】表１から明らかな様に、塩化カルシウムを
添加することによりきわめて安定した分散性と優れた紡
糸性が得られることがわかる。As is clear from Table 1, it is understood that by adding calcium chloride, extremely stable dispersibility and excellent spinnability can be obtained.
【００２１】[0021]
【発明の効果】以上詳述したように、本発明方法によれ
ば安価でしかも取り扱い易い塩化カルシウムを用いてい
るので、酸化チタンを含むアクリル系合成繊維を工業的
に有利に製造しうる。また、酸化チタンを紡糸原液に添
加した際にも二次凝集を起こす事がなく、紡糸性，品質
ともに良好で安定した生産が可能であり頗る有用であ
る。また得られたアクリル系合成繊維は艶消し効果にす
ぐれたものであり、衣料用，資材用等他の多くの用途に
利用可能であり、産業上極めて有意義なものである。As described above in detail, according to the method of the present invention, calcium chloride which is inexpensive and easy to handle is used, so that the acrylic synthetic fiber containing titanium oxide can be industrially advantageously manufactured. Further, even when titanium oxide is added to the spinning dope, secondary aggregation does not occur, spinnability and quality are good, and stable production is possible, which is extremely useful. Further, the obtained acrylic synthetic fiber has an excellent matting effect and can be used for many other purposes such as clothing and materials, and is extremely significant industrially.
Claims (2)
合体を紡糸するに際し、有機溶媒中に酸化チタンと酸化
チタンに対して０．０１〜３重量％の塩化カルシウムを
均一分散させ分散液となし、次いで該分散液をアクリロ
ニトリル系重合体の紡糸原液に添加し、これを紡糸する
事を特徴とするアクリル系合成繊維の製造方法。1. When spinning an acrylonitrile polymer containing titanium oxide, 0.01 to 3% by weight of calcium chloride based on titanium oxide and titanium oxide is uniformly dispersed in an organic solvent to form a dispersion liquid. A method for producing an acrylic synthetic fiber, which comprises adding the dispersion to a spinning stock solution of an acrylonitrile polymer and spinning the solution.
５重量％であることを特徴とする請求項１記載のアクリ
ル系合成繊維の製造方法。2. The content of titanium oxide in the dispersion is 5 to 2
It is 5 weight%, The manufacturing method of the acrylic synthetic fiber of Claim 1 characterized by the above-mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18083694A JPH0827620A (en) | 1994-07-08 | 1994-07-08 | Production of acrylic synthetic fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18083694A JPH0827620A (en) | 1994-07-08 | 1994-07-08 | Production of acrylic synthetic fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0827620A true JPH0827620A (en) | 1996-01-30 |
Family
ID=16090213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18083694A Pending JPH0827620A (en) | 1994-07-08 | 1994-07-08 | Production of acrylic synthetic fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0827620A (en) |
Cited By (5)
| 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 |
| CN104846459A (en) * | 2015-05-27 | 2015-08-19 | 宜宾丝丽雅集团有限公司 | Extinction type high-strength low-elongation viscose fiber and preparation method thereof |
| CN104846454A (en) * | 2015-05-27 | 2015-08-19 | 宜宾丝丽雅集团有限公司 | Delustering high-strength low-elongation viscose fiber and preparation method thereof |
| CN104846456A (en) * | 2015-05-27 | 2015-08-19 | 宜宾丝丽雅集团有限公司 | Semi-dull low-elongation viscose fiber and preparation method and application thereof |
| KR20230046152A (en) * | 2021-09-29 | 2023-04-05 | 인하대학교 산학협력단 | Method for producing flame-retardant modacrylic spinning solution and flame-retardant modacrylic fiber containing inorganic flame retardant particles and inorganic salts |
-
1994
- 1994-07-08 JP JP18083694A patent/JPH0827620A/en active Pending
Cited By (5)
| 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 |
| CN104846459A (en) * | 2015-05-27 | 2015-08-19 | 宜宾丝丽雅集团有限公司 | Extinction type high-strength low-elongation viscose fiber and preparation method thereof |
| CN104846454A (en) * | 2015-05-27 | 2015-08-19 | 宜宾丝丽雅集团有限公司 | Delustering high-strength low-elongation viscose fiber and preparation method thereof |
| CN104846456A (en) * | 2015-05-27 | 2015-08-19 | 宜宾丝丽雅集团有限公司 | Semi-dull low-elongation viscose fiber and preparation method and application thereof |
| KR20230046152A (en) * | 2021-09-29 | 2023-04-05 | 인하대학교 산학협력단 | Method for producing flame-retardant modacrylic spinning solution and flame-retardant modacrylic fiber containing inorganic flame retardant particles and inorganic salts |
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