JPS6336367B2 - - Google Patents
Info
- Publication number
- JPS6336367B2 JPS6336367B2 JP55156295A JP15629580A JPS6336367B2 JP S6336367 B2 JPS6336367 B2 JP S6336367B2 JP 55156295 A JP55156295 A JP 55156295A JP 15629580 A JP15629580 A JP 15629580A JP S6336367 B2 JPS6336367 B2 JP S6336367B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- acrylonitrile
- flame
- organotin compound
- organic solvent
- 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.)
- Expired
Links
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 238000009987 spinning Methods 0.000 claims description 18
- 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 claims description 16
- 239000003063 flame retardant Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 13
- 229920002994 synthetic fiber Polymers 0.000 claims description 12
- 239000012209 synthetic fiber Substances 0.000 claims description 12
- 150000003606 tin compounds Chemical class 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 2
- 229910052717 sulfur Inorganic materials 0.000 claims 2
- 239000011593 sulfur Substances 0.000 claims 2
- 239000000835 fiber Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 19
- 229920001577 copolymer Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- -1 vinyl halide Chemical class 0.000 description 7
- 238000010998 test method Methods 0.000 description 6
- OSGZEAQLLRZGHT-VGKOASNMSA-L dibutyltin(2+);(z)-4-ethoxy-4-oxobut-2-enoate Chemical compound CCOC(=O)\C=C/C(=O)O[Sn](CCCC)(CCCC)OC(=O)\C=C/C(=O)OCC OSGZEAQLLRZGHT-VGKOASNMSA-L 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- GMAAWZONVLTAMA-UHFFFAOYSA-N 2,3-dibromopropyl dihydrogen phosphate Chemical compound OP(O)(=O)OCC(Br)CBr GMAAWZONVLTAMA-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- JJPZOIJCDNHCJP-UHFFFAOYSA-N dibutyl(sulfanylidene)tin Chemical compound CCCC[Sn](=S)CCCC JJPZOIJCDNHCJP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- HGRZLIGHKHRTRE-UHFFFAOYSA-N 1,2,3,4-tetrabromobutane Chemical compound BrCC(Br)C(Br)CBr HGRZLIGHKHRTRE-UHFFFAOYSA-N 0.000 description 1
- QVOOVJHSIPCFPD-UHFFFAOYSA-N 2,3-dichloropropyl dihydrogen phosphate Chemical compound OP(O)(=O)OCC(Cl)CCl QVOOVJHSIPCFPD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- QNRSKOMEMRENSK-UHFFFAOYSA-L C(C=C/C(=O)[O-])(=O)[O-].C(CCC)[Sn+2]CCCC.C(CCCCCCCCCCC)(=O)O Chemical compound C(C=C/C(=O)[O-])(=O)[O-].C(CCC)[Sn+2]CCCC.C(CCCCCCCCCCC)(=O)O QNRSKOMEMRENSK-UHFFFAOYSA-L 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920002821 Modacrylic Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- YVHDRFKHKGNLNW-UHFFFAOYSA-L [dibutyl(octadecanoyloxy)stannyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCCCCCCCC YVHDRFKHKGNLNW-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- FAXZWVLVYZJMPC-UHFFFAOYSA-N butyl(sulfanylidene)tin Chemical compound CCCC[Sn]=S FAXZWVLVYZJMPC-UHFFFAOYSA-N 0.000 description 1
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Description
本発明は、優れた光沢、透明性を有する難燃性
に優れたアクリロニトリル系合成繊維及びその製
法に関するものである。
アクリロニトリル系合成繊維のうち、ハロゲン
化ビニルを比較的多く共重合させたいわゆるモダ
アクリル合成繊維はアクリル繊維の風合、触感を
保持しつつ、難燃性も有するという特徴のある繊
維である。しかし難燃性に対する社会的要求が近
年しだいに高度化しつつあり、より難燃性に優れ
た繊維の出現が要望されている。
難燃性繊維の製造法には、難燃性のモノマーを
共重合する方法、難燃添加剤を紡糸原液に混合し
て紡糸する方法、及び後加工によつて難燃剤を付
着させる方法の３方法があり、各々長所、短所が
あるが、比較的元の繊維物性をそこなわずに永久
的に難燃性を付与できるという点で難燃剤の紡糸
原液への添加法は有利である。難燃性を向上させ
るための添加剤としては、含ハロゲン化合物、含
燐化合物、含窒素化合物、金属化合物等がよく知
られている。しかしこれらの中でアクリロニトリ
ル系合成繊維に有効なものは少く、有効なもので
も可成り多量に添加する必要がある。例えば、含
ハロゲン系の塩化パラフイン、テトラブロムブタ
ン、含ハロゲン燐化合物のトリス２，３ジブロモ
プロピルホスフエート、トリス２，３ジブロモプ
ロピルホスフエート、トリス２，３ジクロルプロ
ピルホスフエート等は、アクリロニトリル系基材
樹脂に対して25重量％以上使用しないと効果は少
ない。さらに25重量％の如く多量に添加したもの
は物性の低下が著しく好ましくない。又、金属化
合物系の酸化アンチモン、酸化マグネシウム、錫
酸等は10重量％以下の使用で難燃性向上に有効で
あるが、アクリロニトリル系合成繊維に使用する
溶剤に不溶であるため、製造時昇圧しやすく、ま
た、ノズル詰りが生じやすい欠点を有している。
さらにこれら金属化合物は、繊維の光沢、透明性
を著しく低下させるという欠点を有している。
本発明者等は、少量の使用で難燃効果が大き
く、しかも繊維の光沢、透明性を維持する添加剤
を鋭意研究検討の結果見出し、本発明に到達し
た。即ち本発明は、アクリロニトリル30〜70重量
％、少くとも１種以上のハロゲン化含有単量体70
〜30重量％、及びこれらと共重合可能な少くとも
１種以上のオレフイン系単量体０〜10重量％で構
成される重合体に対し、有機錫化合物として、該
重合体を溶解しうる有機溶剤に可溶である有機錫
化合物のみを添加した後、これを紡糸することに
より製造できる、優れた光沢、透明性を有し、且
つ難燃性であるアクリロニトリル系合成繊維を内
容とするものである。
以下本発明について詳細に説明する。
本発明で採用する繊維基材は、アクリロニトリ
ル30〜70重量％及び少くとも１種以上のハロゲン
含有単量体70〜30重量％を主成分とするアクリロ
ニトリル系共重合体である。より具体的には、ア
クリロニトリル−塩化ビニル共重合体、アクリロ
ニトリル−塩化ビニリデン共重合体、アクリロニ
トリル−塩化ビニル−塩化ビニリデン共重合体、
アクリロニトリル−臭化ビニル共重合体、アクリ
ロニトリル−塩化ビニリデン−臭化ビニル共重合
体、アクリロニトリル−塩化ビニル−臭化ビニル
共重合体等である。また、本発明で採用される繊
維基材はアクリロニトリルと少くとも１種以上の
ハロゲン含有単量体の他に、これらと共重合可能
なオレフイン系単量体を10重量％以下含有しても
よい。共重合可能なオレフイン系単量体として
は、アクリル酸及びそのエステルメタクリル酸及
びそのエステル、アクリルアミド、メタクリルア
ミド、酢酸ビニル、ビニルスルフオン酸及びその
塩、メタリルスルフオン酸及びその塩、スチレン
スルフオン酸及びその塩などをあげることが出来
る。
次に本発明で採用する難燃剤は、アクリロニト
リルと少くとも１種以上のハロゲン含有単量体を
主成分とする共重合体を溶解する有機溶剤に可溶
である有機錫化合物である。ここでいう有機溶剤
とは、上記重合体を溶解して紡糸原液を作り得る
もので、代表的には、ジメチルホルムアミド、ジ
メチルアセトアミド、ジメチルスルフオキシド、
アセトン等を含むものが挙げられる。又、ここで
いう有機錫化合物とは、これ等有機溶剤に溶解す
るものであれば制限されるものではない。具体的
にはジブチル錫サルフアイド、モノブチル錫サル
フアイド、ジブチル錫ビス（イソオクチルチオグ
リコール酸エステル）、ジオクチル錫ビス（イソ
オクチルチオグリコール酸エステル）等の有機錫
メルカプタイド系化合物；ジブチル錫マレエー
ト、ジブチル錫ジオレイルマレエート、モノブチ
ル錫トリオクチルマレエート、ジブチル錫ラウレ
ート・マレエート等の有機錫マレエート化合物；
ジブチル錫ラウレート、ジブチル錫ステアレート
等の有機錫脂柆酸化合物である。これら有機錫化
合物の１種又は１種以上を繊維基材に対して0.2
〜10重量％、好ましくは0.3〜７重量％使用する。
02重量％未満では難燃性向上効果が期待出来ず、
10重量％以上では効果はあるが、他の繊維物性を
低下させ経済的にも好ましくない。本発明で使用
される有機錫化合物は、好ましくは有機錫メルカ
プタイド系化合物である。特に白度の強く要求さ
れる分野では有機錫メルカプタイド系化合物が適
している。
これらの有機錫化合物をアクリロニトリル系共
重合体溶液に添加して紡糸する方法は、乾式・湿
式の何れでもよいが、得られた繊維を沸騰させな
がら染色すると光沢、透明性が低下してくる。特
に有機錫化合物の添加量が多い場合、及びアクリ
ロニトリルの含有量が少ない場合、染色後の光
沢、透明性の低下が著しい。そのため着色繊維を
目的とする場合は、予め紡糸原液に顔料又は染料
を添加混合、又は溶解した後、紡糸するのが好ま
しい。このようにして得られた着色繊維は高度な
光沢、透明性を有し、かつ、難燃性に優れたアク
リロニトリル系合成繊維である。更には必要に応
じて、帯電防止剤・艶消剤・熱着色防止用安定
剤・耐光向上剤・吸湿性付与剤・有機錫化合物以
外の難燃剤をアクリロニトリル系共重合体に含有
させてもよい。
次に本発明における繊維の難燃性の評価法につ
いて説明する。一般に繊維の難燃性は織物の状態
で評価されている。しかし織物の状態では、織物
の粗密さ、均一性、糸の撚り数、太さ等により燃
焼性の差を生じ繊維自体の難燃性を評価するには
問題がある。そこで、できるだけ繊維自体の難燃
性を評価するために、フイラメントに撚りをかけ
縄状の試料を作り酸素指数法並びに縄式テスト法
により評価した。
酸素指数法は酸素と窒素の混合比を変えた中で
燃焼を継続させるのに必要な酸素の濃度を測定す
るものである。
酸素指数法は、まず３デニール300本のフイラ
メント６本に25インチ中75回撚りをかけ２組み合
わせて縄状の試料とし、さらにこれを70％収縮さ
せて、酸素指数試験器のホルダーに直立させ、こ
の試料が５cm燃えつづけるのに必要な酸素パーセ
ントの測定を行なつた。酸素指数法で示される数
字は大きい方がより難燃性である。
縄式テスト法では、まず３デニール300本のフ
イラメントを６本と木綿カタン糸（30番手、６コ
ード）４本とを合わせて25インチ中75回撚り、こ
のものを２組み合わせて縄状の試料を準備する。
この場合、木綿糸を用いるのは、アクリロニトリ
ル系繊維が燃焼中、熱溶解して燃焼している試料
が落下するのを防止するためである。次に、これ
らの試料を１つの繊維素材について５個作り、燃
焼テストの前に105℃で１時間の乾燥をする。燃
焼テストの方法は、消検法のミクロバーナーを用
い、垂直にたらした試料に12秒間接炎して１試料
につき４回まで接炎する。評価法としては、４回
の接炎での最大の残炎秒数を実測して５試料の平
均値を求めて比較する。第１表のように難燃性を
分類したが、難燃性の程度はＡ−１が最大であ
り、順次低下してＢ−５では全試料が全焼するこ
とを示している。
The present invention relates to an acrylonitrile synthetic fiber with excellent gloss and transparency and excellent flame retardancy, and a method for producing the same. Among acrylonitrile-based synthetic fibers, so-called modacrylic synthetic fibers copolymerized with a relatively large amount of vinyl halide are characterized by retaining the feel and feel of acrylic fibers while also having flame retardancy. However, social demands for flame retardancy have become increasingly sophisticated in recent years, and there is a demand for fibers with even better flame retardancy. There are three methods for producing flame-retardant fibers: a method of copolymerizing flame-retardant monomers, a method of mixing a flame-retardant additive into a spinning solution and spinning, and a method of attaching a flame retardant through post-processing. There are various methods, each with their own advantages and disadvantages, but the method of adding a flame retardant to the spinning dope is advantageous in that flame retardancy can be imparted permanently without compromising the original physical properties of the fiber. As additives for improving flame retardancy, halogen-containing compounds, phosphorus-containing compounds, nitrogen-containing compounds, metal compounds, etc. are well known. However, only a few of these are effective for acrylonitrile synthetic fibers, and even those that are effective need to be added in a fairly large amount. For example, halogen-containing chlorinated paraffin, tetrabromobutane, halogen-containing phosphorus compounds such as tris 2,3 dibromopropyl phosphate, tris 2,3 dibromopropyl phosphate, tris 2,3 dichloropropyl phosphate, etc. It will not be effective unless it is used in an amount of 25% by weight or more based on the base resin. Further, when added in a large amount such as 25% by weight, the physical properties are significantly deteriorated, which is undesirable. In addition, metal compounds such as antimony oxide, magnesium oxide, and stannic acid are effective in improving flame retardancy when used in amounts of 10% by weight or less, but because they are insoluble in the solvent used for acrylonitrile-based synthetic fibers, pressure increases during production. It also has the disadvantage that nozzle clogging occurs easily.
Furthermore, these metal compounds have the disadvantage of significantly reducing the gloss and transparency of the fibers. As a result of extensive research and study, the present inventors have discovered an additive that has a large flame retardant effect when used in small amounts and maintains the gloss and transparency of fibers, and has thus arrived at the present invention. That is, the present invention comprises 30 to 70% by weight of acrylonitrile and 70% by weight of at least one halogenated monomer.
~30% by weight and 0 to 10% by weight of at least one kind of olefinic monomer copolymerizable with these, as an organic tin compound that can dissolve the polymer. It contains an acrylonitrile-based synthetic fiber that has excellent gloss, transparency, and is flame retardant, and can be manufactured by adding only an organic tin compound that is soluble in a solvent and then spinning it. be. The present invention will be explained in detail below. The fiber base material employed in the present invention is an acrylonitrile copolymer containing 30 to 70% by weight of acrylonitrile and 70 to 30% by weight of at least one halogen-containing monomer. More specifically, acrylonitrile-vinylidene chloride copolymer, acrylonitrile-vinylidene chloride copolymer, acrylonitrile-vinyl chloride-vinylidene chloride copolymer,
These include acrylonitrile-vinyl bromide copolymer, acrylonitrile-vinylidene chloride-vinyl bromide copolymer, acrylonitrile-vinyl chloride-vinyl bromide copolymer, and the like. In addition to acrylonitrile and at least one halogen-containing monomer, the fiber base material employed in the present invention may contain 10% by weight or less of an olefinic monomer copolymerizable with these monomers. . Copolymerizable olefinic monomers include acrylic acid and its esters, methacrylic acid and its esters, acrylamide, methacrylamide, vinyl acetate, vinylsulfonic acid and its salts, methallylsulfonic acid and its salts, styrene sulfonate. Examples include acids and their salts. Next, the flame retardant employed in the present invention is an organic tin compound that is soluble in an organic solvent that dissolves a copolymer mainly composed of acrylonitrile and at least one halogen-containing monomer. The organic solvent referred to here is one that can dissolve the above polymer to create a spinning stock solution, and typically includes dimethylformamide, dimethylacetamide, dimethylsulfoxide,
Examples include those containing acetone and the like. Furthermore, the organotin compound referred to herein is not limited as long as it is soluble in an organic solvent. Specifically, organic tin mercaptide compounds such as dibutyltin sulfide, monobutyltin sulfide, dibutyltin bis(isooctylthioglycolic acid ester), and dioctyltin bis(isooctylthioglycolic acid ester); dibutyltin maleate, dibutyltin dio Organotin maleate compounds such as leyl maleate, monobutyltin trioctyl maleate, dibutyltin laurate maleate;
These are organic tin fatty acid compounds such as dibutyltin laurate and dibutyltin stearate. One or more of these organic tin compounds are added at 0.2% to the fiber base material.
-10% by weight, preferably 0.3-7% by weight.
If it is less than 02% by weight, no improvement in flame retardancy can be expected.
A content of 10% by weight or more is effective, but it degrades other fiber properties and is economically unfavorable. The organotin compound used in the present invention is preferably an organotin mercaptide compound. Particularly in fields where whiteness is strongly required, organic tin mercaptide compounds are suitable. The method of adding these organic tin compounds to an acrylonitrile copolymer solution and spinning may be either dry or wet, but if the resulting fibers are dyed while boiling, the gloss and transparency will decrease. In particular, when the amount of the organic tin compound added is large or when the content of acrylonitrile is small, the gloss and transparency after dyeing are significantly reduced. Therefore, if colored fibers are intended, it is preferable to add and mix or dissolve a pigment or dye in the spinning solution before spinning. The colored fiber thus obtained is an acrylonitrile synthetic fiber that has high gloss and transparency and is excellent in flame retardancy. Furthermore, if necessary, the acrylonitrile copolymer may contain an antistatic agent, a matting agent, a stabilizer for preventing thermal coloring, a light resistance improver, a hygroscopicity imparting agent, and a flame retardant other than the organic tin compound. . Next, a method for evaluating the flame retardance of fibers in the present invention will be explained. Generally, the flame retardancy of fibers is evaluated in the form of textiles. However, in the state of textiles, there are problems in evaluating the flame retardance of the fibers themselves, since the combustibility varies depending on the density and uniformity of the textile, the number of twists of the threads, the thickness, etc. Therefore, in order to evaluate the flame retardancy of the fiber itself as much as possible, a rope-shaped sample was made by twisting the filament and evaluated using the oxygen index method and the rope test method. The oxygen index method measures the concentration of oxygen required to continue combustion while changing the mixing ratio of oxygen and nitrogen. In the oxygen index method, first, six 3-denier 300 filaments are twisted 75 times in a 25-inch length and the two are combined to form a rope-shaped sample, which is then shrunk by 70% and placed upright in the holder of the oxygen index tester. The percentage of oxygen required for this sample to burn for 5 cm was measured. The higher the number indicated by the oxygen index method, the more flame retardant. In the rope test method, first, 6 filaments of 300 denier and 4 cotton Katan threads (30 count, 6 cords) are twisted together 75 times in 25 inches, and two of these are combined to form a rope-like sample. prepare.
In this case, the cotton thread is used to prevent the acrylonitrile fibers from melting during combustion and causing the burning sample to fall. Next, five of these samples are made for each fiber material and dried at 105°C for one hour before the combustion test. The method of the combustion test is to use a micro burner of the extinguishing method, and apply an indirect flame to the sample vertically for 12 seconds, up to 4 times per sample. As an evaluation method, the maximum number of seconds for afterflame after 4 times of flame contact is actually measured, and the average value of 5 samples is determined and compared. The flame retardance was classified as shown in Table 1, and the degree of flame retardancy was highest in A-1, and gradually decreased until B-5, where all the samples were completely burnt out.
【表】
このようにして繊維の難燃性を酸素指数法、縄
式テスト法で評価したが、これらの方法による難
燃性がいずれか一方でも悪いと、高度な難燃性を
有する織物を得ることは難しく、酸素指数法、縄
式テスト法による難燃性の共に良好なものほど織
物は高度な難燃性を有するのである。
なお、繊維の光沢、透明性の評価は肉眼で比較
した。
◎…光沢・透明性が非常に優れている。
〇… 〃 優れている。
△… 〃 かなり失なわれている。
×… 〃 ほとんどない。不良
以下に実施例を示す。
実施例 １
アクリロニトリル49.0重量％、塩化ビニル51.0
重量％よりなるアクリロニトリル系共重合物をア
セトンに樹脂濃度25.0重量％になる様に溶解し
た。次に樹脂に対して5.0重量％のジブチル錫エ
チルマレエートを添加混合して透明な紡糸原液を
調製した。この原液をノズル孔径0.08mm、孔数
300ホールのノズルを用い、30％アセトン水溶液
中へ押出し、水洗後、120℃で乾燥し、更に３倍
熱延伸して熱処理を140℃で５分間行ない試料を
得た。同時にジブチル錫エチルマレエートを添加
しないもの及びジブチル錫エチルマレエートのか
わりに、従来難燃剤として公知の三酸化アンチモ
ン3.0重量％添加混合したものを同様に紡糸し試
料を得た。結果を第２表に示す。[Table] In this way, the flame retardancy of fibers was evaluated using the oxygen index method and the rope test method, but if the flame retardance of either of these methods is poor, it is difficult to use fabrics with a high degree of flame retardancy. This is difficult to obtain, and the better the flame retardance measured by both the oxygen index method and the rope test method, the higher the flame retardance of the fabric. The gloss and transparency of the fibers were compared visually. ◎...Excellent gloss and transparency. 〇… 〃 Excellent. △… 〃 Much has been lost. ×… 〃 Hardly. Defective Examples are shown below. Example 1 Acrylonitrile 49.0% by weight, vinyl chloride 51.0%
% by weight of an acrylonitrile copolymer was dissolved in acetone to a resin concentration of 25.0% by weight. Next, 5.0% by weight of dibutyltin ethyl maleate was added to the resin and mixed to prepare a transparent spinning dope. Apply this stock solution to a nozzle with a diameter of 0.08 mm and a number of holes.
Using a 300-hole nozzle, it was extruded into a 30% acetone aqueous solution, washed with water, dried at 120°C, further hot-stretched three times, and heat-treated at 140°C for 5 minutes to obtain a sample. At the same time, samples without dibutyltin ethyl maleate and those in which 3.0% by weight of antimony trioxide, which is conventionally known as a flame retardant, was added and mixed in place of dibutyltin ethyl maleate were similarly spun to obtain samples. The results are shown in Table 2.
【表】
＊１ 酸素指数法
＊２ 縄式テスト法
第２表より本発明例は高度な光沢・透明性を有
し、かつ優れた難燃性を有しているのがわかる。
ジブチル錫エチルマレエートの添加されていない
比較例１では難燃性が充分でなく、三酸化アンチ
モンを添加した比較例２では難燃性は改善されて
いるが光沢・透明性がほとんどない。
実施例 ２
アクリロニトリル52.1重量％、塩化ビニリデン
41.9重量％、アクリルアミド6.0重量％よりなる
アクリロニトリル系共重合物をジメチルホルムア
ミドに樹脂濃度29.0重量％になる様に溶解した。
次に樹脂に対して5.0重量％のジブチル錫ビス
（イソオクチルチオグリコール酸エステル）を添
加、混合して透明な紡糸原液を調製した。この原
液をノズル孔径0.08mm、孔数300ホールのノズル
を用いて、50％ジメチルホルムアミド水溶液へ押
出し、水洗後、90℃の温水中で４倍に延伸し120
℃で乾燥、更に熱処理を140℃で５分間行ない試
料を得た。同時に前記の錫化合物を添加しないも
のを同様に紡糸し試料を得た。結果を第３表に示
す。[Table] *1 Oxygen index method *2 Rope test method From Table 2, it can be seen that the examples of the present invention have high gloss and transparency, and have excellent flame retardancy.
Comparative Example 1, in which dibutyltin ethyl maleate was not added, did not have sufficient flame retardancy, and Comparative Example 2, in which antimony trioxide was added, had improved flame retardancy but almost no gloss or transparency. Example 2 Acrylonitrile 52.1% by weight, vinylidene chloride
An acrylonitrile copolymer consisting of 41.9% by weight and 6.0% by weight of acrylamide was dissolved in dimethylformamide to a resin concentration of 29.0% by weight.
Next, 5.0% by weight of dibutyltin bis(isooctylthioglycolic acid ester) was added to the resin and mixed to prepare a transparent spinning dope. This stock solution was extruded into a 50% dimethylformamide aqueous solution using a nozzle with a nozzle diameter of 0.08 mm and 300 holes, and after washing with water, it was stretched 4 times in warm water at 90°C.
A sample was obtained by drying at 140°C and further heat treatment at 140°C for 5 minutes. At the same time, a sample without the tin compound added was similarly spun to obtain a sample. The results are shown in Table 3.
【表】
本発明例は、優れた難燃性能を有していること
がわかる。
実施例 ３
アクリロニトリル47.0重量％、塩化ビニル47.0
重量％、臭化ビニル6.0重量％よりなるアクリロ
ニトリル系共重合物をアセトンに樹脂濃度25.0重
量％になる様に溶解した。次に樹脂に対して3.0
重量％のジブチル錫ビス（イゾオクチルチオプロ
ピオン酸エステル）を添加、混合した。さらに、
樹脂に対して02重量％の顔料であるフタロシアン
ブルー（大日本インキ〓製）を添加混合し、着色
された紡糸原液を調製した。以下実施例１と同様
の方法で紡糸し、光沢の優れた鮮明な青色の試料
を得た。このものの酸素指数法による測定値は
34.1、縄式テスト法による測定値はＡ−２であり
優れた難燃性を有していた。
実施例 ４
アクリロニトリル54.0重量％、塩化ビニリデン
15重量％、塩化ビニル30.0重量％、メタリルスル
ホン酸ソーダ1.0重量％よりなるアクリロニトリ
ル系共重合物をジメチルホルムアミドに樹脂濃度
28.0重量％になる様に溶解した。次に第４表に示
される有機錫化合物を5.0重量、さらにカチロン
ブルーＫ−2GLH（保土谷化学〓製）を0.1重量％
添加、混合して着色された紡糸原液を得た。以下
実施例２と同様の方法で紡糸し光沢の優れた鮮明
な青色の各試料を得た。[Table] It can be seen that the examples of the present invention have excellent flame retardant performance. Example 3 Acrylonitrile 47.0% by weight, vinyl chloride 47.0%
An acrylonitrile copolymer containing 6.0% by weight of vinyl bromide was dissolved in acetone to a resin concentration of 25.0% by weight. then 3.0 for resin
% by weight of dibutyltin bis(isooctylthiopropionate) was added and mixed. moreover,
Phthalocyan blue (manufactured by Dainippon Ink), which is a pigment, was added and mixed in an amount of 0.2% by weight based on the resin to prepare a colored spinning dope. Thereafter, spinning was carried out in the same manner as in Example 1 to obtain a bright blue sample with excellent gloss. The measured value of this substance using the oxygen index method is
34.1, the value measured by the rope test method was A-2, and it had excellent flame retardancy. Example 4 Acrylonitrile 54.0% by weight, vinylidene chloride
Acrylonitrile copolymer consisting of 15% by weight, 30.0% by weight of vinyl chloride, and 1.0% by weight of sodium methallylsulfonate was added to dimethylformamide at a resin concentration.
It was dissolved to a concentration of 28.0% by weight. Next, add 5.0% by weight of the organotin compound shown in Table 4, and further add 0.1% by weight of Cachilon Blue K-2GLH (manufactured by Hodogaya Chemical).
A colored spinning dope was obtained by adding and mixing. Thereafter, each sample was spun in the same manner as in Example 2 to obtain bright blue samples with excellent gloss.
【表】
本発明例は、いずれも鮮明な青色の繊維であ
り、また優れた難燃性能を有していることがわか
る。比較例１及び２では、繊維の光沢・透明性が
殆んどないため不鮮明な青色の繊維しか得られず
比較例３では難燃性が不足しているのがわかる。
実施例 ５
アクリロニトリル50.0重量％、塩化ビニル35.0
重量％、塩化ビニリデン15.0重量％よりなるアク
リロニトリル系共重合物をアセトンに樹脂濃度
23.0重量％になる様に溶解した。次に樹脂に対し
てジブチル錫サルフアイドを第５表に示す量とな
る様に添加混合し、紡糸原液を調製した。以下実
施例１と同様の方法で紡糸し試料を得た。結果を
第５表に示す。[Table] It can be seen that all of the present invention examples have bright blue fibers and have excellent flame retardant performance. It can be seen that in Comparative Examples 1 and 2, the fibers had almost no gloss or transparency, so that only indistinct blue fibers were obtained, and Comparative Example 3 lacked flame retardancy. Example 5 Acrylonitrile 50.0% by weight, vinyl chloride 35.0%
% by weight, acrylonitrile-based copolymer consisting of 15.0% by weight of vinylidene chloride in acetone and resin concentration.
It was dissolved to a concentration of 23.0% by weight. Next, dibutyltin sulfide was added to the resin in an amount shown in Table 5 and mixed to prepare a spinning dope. Thereafter, a sample was obtained by spinning in the same manner as in Example 1. The results are shown in Table 5.
【表】【table】
【表】
第５表より、0.2％以上添加しなければ難燃性
が充分でないことがわかる。
比較例
アクリロニトリル80重量％、アクリル酸メチル
８重量％、塩化ビニリデン12重量％よりなるアク
リロニトリル系共重合物をジメチルホルムアミド
に樹脂濃度21.0重量％になるように溶解した。次
に樹脂に対して5.0重量％のジブチル錫エチルマ
レエート（比較例１）、あるいはジブチル錫ビス
（イソオクチルチオグリコール酸エステル）（比較
例２）を添加混合して紡糸原液を調製した。この
原液をノズル孔径0.08mm、孔数300ホールのノズ
ルを用いて、25℃の55％ジメチルホルムアミド水
溶液中へ押出し、水洗後乾燥し、更に３倍熱延伸
して熱処理を150℃で５分間行い試料を得た。同
時に錫化合物を添加しないものを同様に紡糸し材
料を得た。（比較例３）。評価結果を第６表に示
す。[Table] From Table 5, it can be seen that flame retardancy is not sufficient unless 0.2% or more is added. Comparative Example An acrylonitrile copolymer consisting of 80% by weight of acrylonitrile, 8% by weight of methyl acrylate, and 12% by weight of vinylidene chloride was dissolved in dimethylformamide to give a resin concentration of 21.0% by weight. Next, 5.0% by weight of dibutyltin ethyl maleate (Comparative Example 1) or dibutyltin bis(isooctylthioglycolic acid ester) (Comparative Example 2) was added and mixed to the resin to prepare a spinning dope. This stock solution was extruded into a 55% dimethylformamide aqueous solution at 25°C using a nozzle with a nozzle diameter of 0.08 mm and 300 holes, washed with water, dried, further hot-stretched 3 times, and heat treated at 150°C for 5 minutes. A sample was obtained. At the same time, a material without the addition of a tin compound was similarly spun to obtain a material. (Comparative Example 3). The evaluation results are shown in Table 6.
【表】
第６表より、アクリロニトリルが70重量％をこ
える重合体では難燃化の効果が小さいことがわか
る。[Table] From Table 6, it can be seen that the flame retardant effect is small in polymers containing more than 70% by weight of acrylonitrile.
Claims (1)
種以上のハロゲン含有単量体70〜30重量％、及び
これらと共重合可能な少くとも１種以上のオレフ
イン系単量体０〜10重量％よりなる重合体と有機
錫化合物として、該重合体を溶解し得る有機溶剤
に可溶である有機錫化合物のみを含有することを
特徴とする優れた光沢、透明性を有する難燃性ア
クリロニトリル系合成繊維。 ２ 有機錫化合物が、硫黄含有有機錫化合物であ
る特許請求の範囲第１項記載のアクリロニトリル
系合成繊維。 ３ 有機溶剤が、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、又はア
セトンである特許請求の範囲第１項記載のアクリ
ロニトリル系合成繊維。 ４ 有機錫化合物の量が、重合体に対して0.2〜
10重量％である特許請求の範囲第１項記載のアク
リロニトリル系合成繊維。 ５ アクリロニトリル30〜70重量％、少くとも１
種以上のハロゲン含有単量体70〜30重量％、及び
これらと共重合可能な少くとも１種以上のオレフ
イン系単量体０〜10重量％よりなる重合体と有機
錫化合物として該重合体を溶解しうる有機溶剤に
可溶である有機錫化合物のみ、及び有機溶剤を含
有する溶液から紡糸することを特徴とする優れた
光沢、透明性を有する難燃性アクリロニトリル系
合成繊維の製法。 ６ 有機錫化合物が、硫黄含有有機錫化合物であ
る特許請求の範囲第５項記載の製法。 ７ 有機溶剤が、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、又はア
セトンである特許請求の範囲第５項記載の製法。 ８ 顔料又は染料を紡糸原液に添加せしめる特許
請求の範囲第５項記載の製法。[Claims] 1 30-70% by weight of acrylonitrile, at least 1
A polymer consisting of 70 to 30% by weight of at least one halogen-containing monomer and 0 to 10% by weight of at least one olefinic monomer copolymerizable with these and an organotin compound; 1. A flame-retardant acrylonitrile-based synthetic fiber having excellent gloss and transparency, which is characterized by containing only an organic tin compound that is soluble in an organic solvent capable of dissolving. 2. The acrylonitrile synthetic fiber according to claim 1, wherein the organotin compound is a sulfur-containing organotin compound. 3. The acrylonitrile synthetic fiber according to claim 1, wherein the organic solvent is dimethylformamide, dimethylacetamide, dimethylsulfoxide, or acetone. 4 The amount of organotin compound is 0.2 to 0.2 to the polymer
10% by weight of the acrylonitrile synthetic fiber according to claim 1. 5 Acrylonitrile 30-70% by weight, at least 1
A polymer consisting of 70 to 30% by weight of halogen-containing monomers and 0 to 10% by weight of at least one olefinic monomer copolymerizable with these and an organotin compound. A method for producing a flame-retardant acrylonitrile synthetic fiber having excellent gloss and transparency, which is characterized by spinning from a solution containing only an organic tin compound soluble in a soluble organic solvent and an organic solvent. 6. The manufacturing method according to claim 5, wherein the organotin compound is a sulfur-containing organotin compound. 7. The manufacturing method according to claim 5, wherein the organic solvent is dimethylformamide, dimethylacetamide, dimethylsulfoxide, or acetone. 8. The manufacturing method according to claim 5, in which a pigment or dye is added to the spinning dope.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15629580A JPS5782516A (en) | 1980-11-05 | 1980-11-05 | Acrylonitrile synthetic fiber and preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15629580A JPS5782516A (en) | 1980-11-05 | 1980-11-05 | Acrylonitrile synthetic fiber and preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5782516A JPS5782516A (en) | 1982-05-24 |
| JPS6336367B2 true JPS6336367B2 (en) | 1988-07-20 |
Family
ID=15624686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15629580A Granted JPS5782516A (en) | 1980-11-05 | 1980-11-05 | Acrylonitrile synthetic fiber and preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5782516A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0313279U (en) * | 1989-06-27 | 1991-02-12 | ||
| JPH0462162U (en) * | 1990-10-04 | 1992-05-28 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49108324A (en) * | 1973-01-26 | 1974-10-15 | ||
| JPS5040821A (en) * | 1973-08-10 | 1975-04-14 |
-
1980
- 1980-11-05 JP JP15629580A patent/JPS5782516A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49108324A (en) * | 1973-01-26 | 1974-10-15 | ||
| JPS5040821A (en) * | 1973-08-10 | 1975-04-14 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0313279U (en) * | 1989-06-27 | 1991-02-12 | ||
| JPH0462162U (en) * | 1990-10-04 | 1992-05-28 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5782516A (en) | 1982-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5503916A (en) | Flame-retarded clothing | |
| US5208105A (en) | Flame-retarded composite fiber | |
| JP2593987B2 (en) | Manufacturing method of flame retardant fiber composite | |
| US4409350A (en) | Fire retardant acrylic fibers containing organo-tin-sulfur compound having high degree of glossiness | |
| US7351671B2 (en) | Union fabric with flame resistance | |
| US5981407A (en) | Thermal resistance-improved flame retardant cloth | |
| US20050130535A1 (en) | High flame resistant union fabric | |
| US4447568A (en) | Flame-retardant polyacrylonitrile fiber | |
| JPS6336367B2 (en) | ||
| US4101621A (en) | Method for producing flame resistant acrylic fibers | |
| US3824222A (en) | Flameproof modacrylic fibers | |
| JP4199370B2 (en) | Flame retardant fiber composite | |
| JPS5930803B2 (en) | Acrylic synthetic fiber with excellent flame retardancy | |
| US3626684A (en) | Wool-like acrylic for double knits | |
| US4007232A (en) | Acrylic synthetic fiber superior in non-inflammability | |
| JPS60110940A (en) | Composite fire retardant fiber | |
| US4022750A (en) | Process for the production of a halogen-containing arcylic synthetic fiber improved in flame retardancy | |
| JP2593989B2 (en) | Interior textile products | |
| JP2593988B2 (en) | Textile products for clothing | |
| JP2898563B2 (en) | Flame retardant method for combustible fibers | |
| JP2722254B2 (en) | Flame retardant acrylic fiber with excellent rust prevention, light stability and transparency | |
| JP2968343B2 (en) | Composite flame retardant fiber | |
| JP2812672B2 (en) | Manufacturing method of flame retardant fiber composite | |
| JPH05148728A (en) | Composite material of flame-retardant fiber | |
| JP2646375B2 (en) | Flame retardant acrylic fiber with excellent rust resistance, light stability, and transparency |