JPS63203821A - Production of molded article of heat-resistant and flame-retardant acrylic fiber - Google Patents
Production of molded article of heat-resistant and flame-retardant acrylic fiberInfo
- Publication number
- JPS63203821A JPS63203821A JP3241687A JP3241687A JPS63203821A JP S63203821 A JPS63203821 A JP S63203821A JP 3241687 A JP3241687 A JP 3241687A JP 3241687 A JP3241687 A JP 3241687A JP S63203821 A JPS63203821 A JP S63203821A
- Authority
- JP
- Japan
- Prior art keywords
- acrylic fiber
- flame
- molded article
- resistant
- article
- 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
- 229920002972 Acrylic fiber Polymers 0.000 title claims abstract description 22
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 5
- 239000003063 flame retardant Substances 0.000 title claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000835 fiber Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 6
- 239000012770 industrial material Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- 239000004745 nonwoven fabric Substances 0.000 description 7
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 102000009123 Fibrin Human genes 0.000 description 1
- 108010073385 Fibrin Proteins 0.000 description 1
- BWGVNKXGVNDBDI-UHFFFAOYSA-N Fibrin monomer Chemical compound CNC(=O)CNC(=O)CN BWGVNKXGVNDBDI-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012773 agricultural material Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- -1 carbon fibers Chemical compound 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 229950003499 fibrin Drugs 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Inorganic Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は主として工業資材、土木建築資材、農業資材等
に用いられる耐熱、難燃性アクリル繊維成形物の製造方
法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a heat-resistant, flame-retardant acrylic fiber molded product mainly used for industrial materials, civil engineering and construction materials, agricultural materials, etc.
（従来の技術）
従来アクリル繊維に難燃性を付与する手段としては炭素
繊維のように窒素中で高温焼成する方法や重合体中のア
クリロニトリルに塩化ビニルや塩化ビニリデンを共重合
する方法が知られている。(Prior art) Conventional methods for imparting flame retardancy to acrylic fibers include a method of high-temperature firing in nitrogen like carbon fibers, and a method of copolymerizing vinyl chloride or vinylidene chloride with acrylonitrile in a polymer. ing.
（発明が解決しようとする問題点）
しかるに、窒素中で焼成する方法は高温の焼成を施こす
ための設備が必要であシ、又焼成時間が長時間必要とな
り製造コストが高くなるという問題があり、又塩化ビニ
ルや塩化ビニリデンを共重合する方法は耐熱性に劣シ、
例えば塩化ビニリデンｆ ４０ ｗｔ％共重合させたア
クリル繊維からなる不織布では２５０℃の乾熱下に放置
しておくと縦、横の収量率がそれぞれ８０％にもなり脆
化するという欠点を有する。(Problems to be Solved by the Invention) However, the method of firing in nitrogen requires equipment for high-temperature firing, and also requires a long firing time, which increases manufacturing costs. However, the method of copolymerizing vinyl chloride and vinylidene chloride has poor heat resistance.
For example, a nonwoven fabric made of acrylic fibers copolymerized with vinylidene chloride f 40 wt% has the disadvantage that if left under dry heat at 250°C, the yield rate in both the vertical and horizontal directions will be as high as 80%, resulting in brittleness.
本発明の目的はこれらの問題点全解決し耐熱性及び難燃
性に優れたアクリル繊維成形物の製造方法を提供するこ
とにある。The object of the present invention is to solve all of these problems and provide a method for producing an acrylic fiber molded product that has excellent heat resistance and flame retardancy.
（問題点を解決するための手段）
本発明はアクリロニトリル４０〜８０ ｗｔ％と塩化ビ
ニリデン６０５２０ｗｔ％を含む共重合体からなるアク
リル繊維成形物を加水分解処理しカルボキシル基を５〜
２０ ｍｏｌ ／ ｋｇｇ維生酸生成めた後、水洗し２
００〜３００℃の温度で乾熱処理することを特徴とする
耐熱、難燃性アクリル繊維成形物の製造方法にある。(Means for Solving the Problems) The present invention hydrolyzes an acrylic fiber molded product made of a copolymer containing 40 to 80 wt% of acrylonitrile and 60520 wt% of vinylidene chloride to remove 5 to 5 carboxyl groups.
After generating 20 mol/kg of fibrin acid, wash with water 2
The present invention provides a method for producing a heat-resistant and flame-retardant acrylic fiber molded article, which is characterized by dry heat treatment at a temperature of 00 to 300°C.
本発明でいう繊維成形物とは不織布、織布、編物等任意
のＭ！維構造物を指す。本発明で用いられるアクリル繊
維としてはアクリロニトリル４０へ８０ ａｔ％ト塩化
ビニリデン６０へ２゜ｗｔ％を含んで重合された共重合
体からなるものであれば任意の紡糸方法に依ったもので
もよい。In the present invention, the fiber molded product is any M! such as non-woven fabric, woven fabric, knitted fabric, etc. Refers to fiber structures. The acrylic fibers used in the present invention may be produced by any spinning method as long as they are made of a copolymer containing 80 at% of acrylonitrile 40 and 2% by weight of vinylidene chloride 60.
共重合体中の塩化ビニリデンが６０ ｗｔ％を超えると
重合、紡糸が困難となり、又耐熱性を付与することも難
かしくな夛、又塩化ビニリデンが２０ ｗｔ％未満であ
ると加水分解処理に際し、アクリル線維の溶解又は繊維
間の溶着を生じ好ましくない。なお、本発明に用いられ
るアクリル繊維はその共重合体中に第三成分として酢酸
ビニル、アクリルアミド、アクリル酸メチル等のビニル
モノマーの少量が共重合されていても差し支えない。If the vinylidene chloride content in the copolymer exceeds 60 wt%, it will be difficult to polymerize and spin, and it will also be difficult to impart heat resistance. This is undesirable because it causes the acrylic fibers to dissolve or the fibers to weld to each other. Note that the acrylic fiber used in the present invention may have a small amount of a vinyl monomer such as vinyl acetate, acrylamide, or methyl acrylate copolymerized as a third component in the copolymer.
本発明のアクリル繊維の加水分解処理においてはカルボ
キシル基を繊維中に５ Ａ−２０ｍｏｌ／ｋｇの範囲で
生成させることが必要であり、２０ｍｏ１／ ｋｙ ｋ
超えると繊維間の溶着が起き、又強伸度も著しく低下す
る。一方カルボキシル基が５０ｍｏｌ ／ ｋｇ未満で
あると耐熱性を付与することができず、２５０℃以上の
温度の乾熱処理での収縮、脆化が著しい。In the hydrolysis treatment of the acrylic fiber of the present invention, it is necessary to generate carboxyl groups in the fiber in a range of 5 A-20 mol/kg, and 20 mol/ky k
If it exceeds this, welding between fibers will occur, and the strength and elongation will also drop significantly. On the other hand, if the carboxyl group is less than 50 mol/kg, heat resistance cannot be imparted, and shrinkage and embrittlement are significant during dry heat treatment at a temperature of 250° C. or higher.
本発明における加水分解処理の具体的な方法としては水
酸化カリウム、水酸化ナトリウム等の強アルカリ溶液に
前記アクリル繊維成形物を浸漬し８０−１００℃の温度
で所定のカルボキシル基が生成するに充分な時間浸漬処
理する。A specific method for the hydrolysis treatment in the present invention is to immerse the acrylic fiber molded product in a strong alkaline solution such as potassium hydroxide or sodium hydroxide at a temperature of 80 to 100°C, which is sufficient to generate the desired carboxyl groups. Soak for a certain amount of time.
加水分解反応を中止させるため水洗し、引き続き２００
−５００℃の温度乾熱処理する。Washed with water to stop the hydrolysis reaction, and then washed for 200 min.
Dry heat treatment at -500°C.
又本発明での加水分解処理はアクリル繊維成形物を強ア
ルカリ溶液に浸漬後直ちに取シ出しスチーム処理する方
法でもよい。乾熱処理は加水分解されたアクリル繊維成
形物が黒色化するまでの時間実施するのが好ましい。Further, the hydrolysis treatment in the present invention may be carried out by immersing the acrylic fiber molded article in a strong alkaline solution, immediately taking it out, and treating it with steam. The dry heat treatment is preferably carried out for a period of time until the hydrolyzed acrylic fiber molding becomes black.
以下、本発明を実施例によシ説明する。 The present invention will be explained below using examples.
実施例１
アクリロニトリル６０ｗｔ％、塩化ビニリデン３５ ｗ
ｔ％、酢酸ビニル５ ｗｔ％の共重合体を湿式紡糸して
得アクリル線維からなり、エンボッシング法で製造され
た目付が４３１ ／ ｍ２ の不織布を水酸化ナトリ
ウム１０ｗｔ％水溶液中に８０〜９０℃の温度で１時間
浸漬処理したのち水洗し、乾燥後２５５℃で１０分間乾
熱処理した。Example 1 Acrylonitrile 60wt%, vinylidene chloride 35w
A nonwoven fabric made of acrylic fiber obtained by wet spinning a copolymer containing 5 wt% of vinyl acetate and 5 wt% of vinyl acetate and having a basis weight of 431/m2 and produced by an embossing method was placed in a 10 wt% aqueous solution of sodium hydroxide at 80 to 90°C. After being immersed at a high temperature for 1 hour, it was washed with water, dried, and then subjected to a dry heat treatment at 255° C. for 10 minutes.
得られた不織布は黒色をなし２５０℃の乾熱下でも縦、
横の収縮率は２％であった。又得られた不織布ｔ−１０
５℃で１時間乾燥しシリカゲル入りのデシケータ−に２
時間放置した後ミクロバーナーで着火したが全く着火し
なかった。The obtained nonwoven fabric has a black color and is stable even under dry heat at 250°C.
The lateral shrinkage was 2%. Moreover, the obtained nonwoven fabric T-10
Dry at 5℃ for 1 hour and place in a desiccator containing silica gel.
After leaving it for a while, I ignited it with a micro burner, but it did not ignite at all.
実施例２
アクリロニトリル６０ ｗ疼、塩化ビニリデン３５ ｗ
ｔ％、酢酸ビニルＳ ｗｔ％の共重合体からなるアクリ
ル繊維よシエンボッシング法で作られた目付が４５９／
１ｍ の不織布を水酸化ナトリウム２０育ｔ％水溶液に
浸漬してマングルで搾液し引続き９５℃の飽和水蒸気中
でスチーム処理を１０分間行なった。水洗後、乾燥し２
５５℃で１時間乾熱処理した。得られた不織布は黒色全
なし、２５０℃の乾熱下でも縦横の収縮率が２％であっ
た。又実施例１と同様に着火テス）１−実施したが全く
着火しなかった。Example 2 Acrylonitrile 60w, vinylidene chloride 35w
Acrylic fiber made of a copolymer of vinyl acetate S wt% and vinyl acetate S wt% has a fabric weight of 459/
A 1 m 2 nonwoven fabric was immersed in a 20% sodium hydroxide aqueous solution, squeezed out with a mangle, and then steamed in saturated steam at 95° C. for 10 minutes. After washing with water, dry 2
Dry heat treatment was performed at 55° C. for 1 hour. The obtained nonwoven fabric had no black color at all and had a longitudinal and transverse shrinkage of 2% even under dry heat at 250°C. Further, an ignition test (1) was carried out in the same manner as in Example 1, but no ignition occurred.
比較例
アクリロニトリル９０ ｗｔ％、塩化ビニリデン５ ｗ
ｔ％、酢酸ビニルＳ ｗｔ％の共重合体からなるアクリ
ル繊維を水酸化ナトリクム１０ｗｔ％水溶液中で９０℃
で１時間浸漬処理したところ溶解溶着がはなはだしく生
じた。Comparative example Acrylonitrile 90 wt%, vinylidene chloride 5 w
t%, vinyl acetate S wt% copolymer was heated at 90°C in a 10 wt% aqueous solution of sodium hydroxide.
When immersed in water for 1 hour, a significant amount of melting and welding occurred.
（発明の効果）
本発明方法によるアクリル繊維成形物は耐熱、難燃性に
優れ、従来のアクリロニトリル−塩化ビニリデン共重合
体繊維のような耐熱性の低下がなくむしろ大巾に上回る
性能を有するものであシ、シかも簡便な方法で得ること
ができる。(Effects of the Invention) The acrylic fiber molded product produced by the method of the present invention has excellent heat resistance and flame retardancy, and does not suffer from a decrease in heat resistance like conventional acrylonitrile-vinylidene chloride copolymer fibers, and in fact has significantly superior performance. You can get it in a simple way.
Claims (1)
０〜２０ｗｔ％を含む共重合体からなるアクリル繊維成
形物を加水分解処理しカルボキシル基を５〜２０ｍｏｌ
／ｋｇ繊維生成せしめた後、水洗し２００〜３００℃の
温度で乾熱処理することを特徴とする耐熱、難燃性アク
リル繊維成形物の製造方法。Acrylonitrile 40-80wt% and vinylidene chloride 6
An acrylic fiber molded product made of a copolymer containing 0 to 20 wt% is hydrolyzed to remove 5 to 20 mol of carboxyl groups.
1. A method for producing a heat-resistant and flame-retardant acrylic fiber molded article, which comprises forming fibers, washing with water, and dry-heating them at a temperature of 200 to 300°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3241687A JPS63203821A (en) | 1987-02-17 | 1987-02-17 | Production of molded article of heat-resistant and flame-retardant acrylic fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3241687A JPS63203821A (en) | 1987-02-17 | 1987-02-17 | Production of molded article of heat-resistant and flame-retardant acrylic fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63203821A true JPS63203821A (en) | 1988-08-23 |
Family
ID=12358345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3241687A Pending JPS63203821A (en) | 1987-02-17 | 1987-02-17 | Production of molded article of heat-resistant and flame-retardant acrylic fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63203821A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102953151A (en) * | 2011-08-25 | 2013-03-06 | 中国石油化工股份有限公司 | Preparation method for polyacrylonitrile-based carbon fiber |
| CN102953142A (en) * | 2011-08-25 | 2013-03-06 | 中国石油化工股份有限公司 | Manufacturing method for polyacrylonitrile-based carbon fiber protofilament |
| CN102953141A (en) * | 2011-08-25 | 2013-03-06 | 中国石油化工股份有限公司 | Manufacturing method for polyacrylonitrile-based carbon fiber protofilament |
| CN102953158B (en) * | 2011-08-25 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of method of manufacture polyacrylonitrile-based carbon fibre |
-
1987
- 1987-02-17 JP JP3241687A patent/JPS63203821A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102953151A (en) * | 2011-08-25 | 2013-03-06 | 中国石油化工股份有限公司 | Preparation method for polyacrylonitrile-based carbon fiber |
| CN102953142A (en) * | 2011-08-25 | 2013-03-06 | 中国石油化工股份有限公司 | Manufacturing method for polyacrylonitrile-based carbon fiber protofilament |
| CN102953141A (en) * | 2011-08-25 | 2013-03-06 | 中国石油化工股份有限公司 | Manufacturing method for polyacrylonitrile-based carbon fiber protofilament |
| CN102953142B (en) * | 2011-08-25 | 2016-06-29 | 中国石油化工股份有限公司 | A kind of method manufacturing polyacrylonitrile base carbon fiber precursors |
| CN102953158B (en) * | 2011-08-25 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of method of manufacture polyacrylonitrile-based carbon fibre |
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