JPH0149827B2 - - Google Patents
Info
- Publication number
- JPH0149827B2 JPH0149827B2 JP62193137A JP19313787A JPH0149827B2 JP H0149827 B2 JPH0149827 B2 JP H0149827B2 JP 62193137 A JP62193137 A JP 62193137A JP 19313787 A JP19313787 A JP 19313787A JP H0149827 B2 JPH0149827 B2 JP H0149827B2
- Authority
- JP
- Japan
- Prior art keywords
- aminophosphazene
- fibers
- flame
- flame retardant
- aqueous solution
- 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
- 239000003063 flame retardant Substances 0.000 claims description 30
- 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 29
- 238000000034 method Methods 0.000 claims description 27
- 239000000835 fiber Substances 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 229920000742 Cotton Polymers 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003377 acid catalyst Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 238000003672 processing method Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- PMZIUAOBHNJYQT-UHFFFAOYSA-N (1-hydroxy-2-methylpropan-2-yl)azanium;chloride Chemical compound Cl.CC(C)(N)CO PMZIUAOBHNJYQT-UHFFFAOYSA-N 0.000 claims description 3
- 229920000297 Rayon Polymers 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000002964 rayon Substances 0.000 claims description 3
- 210000002268 wool Anatomy 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- 244000025254 Cannabis sativa Species 0.000 claims 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims 1
- 235000009120 camo Nutrition 0.000 claims 1
- 235000005607 chanvre indien Nutrition 0.000 claims 1
- 239000011487 hemp Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 239000004744 fabric Substances 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000013256 coordination polymer Substances 0.000 description 4
- 239000002657 fibrous material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- 230000037303 wrinkles Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BSBSDQUZDZXGFN-UHFFFAOYSA-N cythioate Chemical compound COP(=S)(OC)OC1=CC=C(S(N)(=O)=O)C=C1 BSBSDQUZDZXGFN-UHFFFAOYSA-N 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000985 reactive dye Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000012757 flame retardant agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 101100420769 Drosophila melanogaster scaf gene Proteins 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- CBPKIOGAUWKEFT-UHFFFAOYSA-N bis(2,3-dibromopropyl) hydrogen phosphate Chemical compound BrCC(Br)COP(=O)(O)OCC(Br)CBr CBPKIOGAUWKEFT-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- -1 etc. Chemical compound 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WLKALBXHGZQMSK-UHFFFAOYSA-N n-dimethoxyphosphoryl-n-(hydroxymethyl)propanamide Chemical compound CCC(=O)N(CO)P(=O)(OC)OC WLKALBXHGZQMSK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Description
〔産業上の利用分野〕
本発明は、繊維の難燃加工法に関するものであ
る。
〔従来の技術〕
糸や布などの繊維材料を難燃化する方法とし
て、テトラキス（ハイドロキシメチル）ホスフオ
ニウムサルフエート等と尿素の縮合物を用いたプ
ロバン加工法やＮ−メチロールジメチルホスホノ
プロピオンアミド（チバガイギー社のピロバテツ
クスCP）を用いた方法（以下、「ピロバテツクス
CP法」とのみ記す）などが従来より行われてい
る。
〔発明が解決しようとする問題点〕
上記した方法のうち、プロバン加工法は、綿繊
維のフイブリルの中でプロバン・ポリマーを形成
させることにより耐久性を持たせるようにしてい
るため、耐洗濯性と強力の向上があるが、ポリマ
ー形成のためにアンモニアキユアを行う特殊装置
を必要とし、かつ、H2O2による酸化工程が必要
であるため、綿繊維の風合の劣化をきたす。しか
も、染色物の変色、耐光性が悪化するため、反応
染料などが用いられず、高価なバツト染料のみし
か使用できない。バツト染料は色合が悪いと言う
問題もある。加工布から多量のホルムアルデヒド
が遊離発生する欠点もある。
他方、ピロバテツクスCP法においては、トリ
メチロールメラミンを併用するため、繊維の強度
低下、特に、引裂強度の低下が大きく、強度保持
率が50％程度に低下する（東京都立繊維工業試験
場研究報告第32号p.51（1984）斉藤 晋、秋山
勝男著 参照）、ホルムアルデヒドを多量に発生
する等の問題がある。
また、綿繊維用難燃加工剤としてトリス（１−
アジリジニル）ホスフインオキシドを用いる方
法、ポリエステル繊維用難燃加工剤としてトリス
（２，３−ジブロモプロピル）ホスフエート、ビ
ス（２，３−ジブロモプロピル）ホスフエート等
を用いる方法等が有つたが、これらの難燃加工剤
は、厚生省の「有害物質を含有する家庭用品の規
制に関する法律」により現在使用が禁止されてい
る。同法においては、ホルムアルデヒドの発生量
も規制されている。
しかも、ポリエステル／綿混紡（以下、「Ｅ／
Ｃ」と記す）布の場合、いわゆる枠組効果
（Scaf fold effect）のためにポリエステル繊維
の溶融滴下が妨げられる。そのため、燃焼性が、
ポリエステル繊維、綿繊維各単独の場合と比べて
増大し、難燃加工がより困難となつており、Ｅ／
Ｃ布等においては、充分な耐洗濯性を有する難燃
加工剤がないのが現状である〔大江 昭二朗著
高分子加工 23、76（1976）、勝浦 嘉久次著 化
繊月報 12(4)、58（1974）参照〕。
〔問題を解決するための手段〕
上記の問題を解決するために、本発明者らは、
アミノホスフアゼンを原料繊維に含浸させ乾燥後
キユアすれば、原料繊維に難燃性を付与できるこ
とを見出した。しかし、アミノホスフアゼンは、
一般にクロロホスフアゼンとアンモニアから合成
される。このような方法で合成されたアミノホス
フアゼンは、58重量％程度の塩化アンモニウムを
含有しており、キユアを行つた場合、この塩化ア
ンモニウムが酸触媒として働くため、引裂強度の
低下を起こしたり、染料の変色が起きたり、中温
ワツシヤー法による洗濯後では難燃効果が低下す
る等の問題や、経時的に難燃性の低下が著しいと
言う問題があることが判り、鋭意検討した結果、
本発明を完成するに至つた。
したがつて、本発明は、塩化アンモニウムを多
量に含む粗製のアミノホスフアゼン水溶液を多量
のアルコール中に投入し、沈澱させて得た精製ア
ミノホスフアゼンを水に溶解させるとともに、こ
の水溶液に、リン酸、硝酸亜鉛、ホウフツ化亜
鉛、塩化亜鉛、２−アミノ−２−メチルプロパノ
ール塩酸塩、リン酸水素二アンモニウム、およ
び、塩化マグネシウムからなる群より選ばれた少
なくとも一種の酸触媒を0.1〜10重量％の割合で
添加して処理液を作製したのち、この処理液を、
原料繊維に含浸乾操させて、キユアすることを特
徴とする繊維の難燃加工法を要旨としている。
〔作用〕
本発明にかかる繊維の難燃加工法によれば、引
裂強度にすぐれ、防皺性、とくに、湿防皺性が向
上し風合も柔らかい耐洗濯性等の耐久性に優れた
難燃性繊維が得られる。しかも、アンモニアキユ
ア法および酸化工程を用いる必要がないため、反
応染料の変色といつた問題もなくなる。また、ホ
ルムアルデヒドの発生も全くない。
〔実施例〕
以下に、この発明をその実施例を参照しつつ詳
しく説明する。
この発明にかかる繊維の難燃加工法で用いられ
るアミノホスフアゼンは、精製されていて、とく
に、三量体あるいは四量体になつていることが好
ましい。もちろん、五量体以上のものでも構わな
い。
精製アミノホスフアゼンは、粗製のアミノホス
フアゼンを約５倍量の水に溶解し、この水溶液を
５倍のメタノール等のアルコール中に投入し、ア
ミノホスフアゼンのみを沈澱させる方法で得る。
上記した方法によると、アミノホスフアゼンが、
アミノホスフアゼン・HC1の形になる。アミノ
ホスフアゼン・HC1は、水への溶解度が著しく
大きい。したがつて、高濃度の加工浴をつくるこ
とがきる。しかも、使用したアルコールは、蒸溜
によつて回収して繰り返し使用できるため経済的
でもある。精製する方法は、上記の方法以外に、
液体アンモニアを用いるアンモニア水中に粗製の
アミノホスフアゼンを溶解させて、この溶液をア
ルコール中に投入してアミノホスフアゼンを沈澱
させる方法等がある。しかし、これらの方法は、
たとえば、液体アンモニアを用いる方法では、−
33℃の低温にする必要があり、空気とアンモニア
の混合によつて爆発する危険性もあり、アンモニ
ア水を使用する方法では、アミノホスフアゼンが
アミノホスフアゼン・H2Oの形となつているた
め、溶解度が小さく（12.1ｇ／水100ｇ・25℃）
高馬度の溶液を得ることができないと言う問題が
ある。
水溶液中のアミノホスフアゼン濃度は、５〜50
重量％が好ましい。５重量％を下回ると、難燃効
果が不足する傾向がある。50重量％を越えると難
燃効果は十分であるが、風合が損なわれる傾向が
ある。
上記のようにして得た水溶液に、酸触媒を0.1
〜10重量％の割合で添加して処理液を作製する。
酸触媒としては、リン酸、硝酸亜鉛、ホウフツ
化亜鉛、塩化亜鉛、２−アミノ−２−メチルプロ
パノール塩酸塩、リン酸水素二アンモニウム、塩
化マグネシウムのうち少なくとも一種を用いる
が、この中でもリン酸が特に好ましい。
酸触媒が0.1重量％以下であると、難燃効果の
耐洗濯性が低下する。また、10重量％以上である
と、引裂強度が低下したり、加工布が変色したり
する。
この発明にかかる加工法によつて、難燃化でき
る繊維としては、綿、絹、麻、レーヨン、羊毛等
が挙げられる。なお、一般に、これらの繊維が糸
や布などの繊維材料の状態で難燃加工される。繊
維材料は、混紡繊維や交織織物などでも構わな
い。
含浸、乾燥、キユアの各工程は、とくに限定さ
れないが、通常のパツド−ドライ−キユア法を用
いて、連続的に行うことができる。
乾燥時の温度は、80〜120℃程度が好ましい。
80℃を下回ると乾燥時間が長くなる傾向がある。
キユアは空中で行われ、キユア時の温度は80〜
200℃程度が好ましい。80℃を下回ると処理時間
が長くなり、難燃効果の耐洗濯性が低下する傾向
がある。200℃を越えると強度低下や変色する傾
向がある。
つぎに、実施例について詳しく説明する。
実施例
繊維材料として、綿サテン捺染布、ポリエステ
ル／綿（65／35）ブロード、絹羽二重、レーヨン
スフモスリン、ウールモスリンを用意した。これ
らの布をそれぞれアミノホスフアゼン三量体と酸
触媒とが所定量含有されている難燃加工剤に２デ
イツプ２ニツプして含浸させた。含浸後、100℃
で３分間乾燥を行つた。乾燥後、150℃または160
℃で３分間加熱を行い、キユアしたのち、65℃で
５分間湯洗いして乾燥を行い、難燃加工された繊
維を得た。
比較例 １
綿サテン捺染布を粗製のアミノホスフアゼン三
量体（塩化アンモニウム58重量％含有）の30重量
％水溶液に２デイツプ２ニツプして実施例と同様
にして難燃加工した。
比較例 ２
繊維材料として綿サテン捺染布を用意し、この
布に本発明の方法で精製されたアミノホスフアゼ
ン三量体が20wt％と酸触媒としてのリン酸が
0.05wt％含まれる難燃加工剤を含浸させ、実施例
と同様にして難燃加工された繊維を得た。
比較例 ３
リン酸濃度を11wt％にした以外は、比較例２
と同様にして難燃加工された繊維を得た。
上記の実施例および比較例で得られた難燃加工
された各布の難燃加工剤の付着率、限界酸素指数
（LOI）、45゜ミクロンバーナー法１分間加熱によ
る炭化面積、および、中温（60℃）ワツシヤ法に
よる５回洗濯後の難燃加工剤の付着率、限界酸素
指数（LOI）、45゜ミクロンバーナー法１分間によ
る炭化面積を調べ、その結果を第１表に示した。
なお、第１表には、酸触媒の種類、水溶液中のア
ミノホスフアゼン（表では「AP」と略している）
および酸触媒の濃度および含浸時の２デイツプ２
ニツプ後の水溶液の絞り率も併せて示した。
[Industrial Application Field] The present invention relates to a flame retardant processing method for fibers. [Prior art] As a method for making fiber materials such as yarn and cloth flame retardant, there is a proban processing method using a condensate of urea with tetrakis(hydroxymethyl)phosphonium sulfate, etc., and N-methyloldimethylphosphonopropionamide. (Ciba Geigy's Pyrobatex CP) (hereinafter referred to as "Pyrobatex CP")
Conventionally, methods such as "CP method" have been used. [Problems to be solved by the invention] Among the above methods, the proban processing method provides durability by forming a proban polymer in the fibrils of cotton fibers, so it has poor washing resistance. However, since it requires special equipment for ammonia curing to form a polymer and an oxidation process using H 2 O 2 , the feel of the cotton fiber deteriorates. In addition, since the dyed product changes color and its light fastness deteriorates, reactive dyes and the like cannot be used, and only expensive vat dyes can be used. Butt dyes also have the problem of poor color. Another drawback is that a large amount of formaldehyde is liberated from the processed cloth. On the other hand, in the Pyrobatex CP method, since trimethylolmelamine is used in combination, the strength of the fibers decreases, especially the tear strength, and the strength retention rate decreases to about 50% (Tokyo Metropolitan Textile Industry Research Institute Research Report No. 32) Issue p.51 (1984) Susumu Saito, Akiyama
(Refer to Katsuo), there are problems such as generating large amounts of formaldehyde. Tris (1-
There are methods using aziridinyl) phosphine oxide, and methods using tris(2,3-dibromopropyl) phosphate, bis(2,3-dibromopropyl) phosphate, etc. as a flame retardant for polyester fibers. The use of flame retardants is currently prohibited by the Ministry of Health and Welfare's ``Act on the Regulation of Household Products Containing Hazardous Substances.'' The law also regulates the amount of formaldehyde generated. Moreover, polyester/cotton blend (hereinafter referred to as "E/
In the case of fabrics (denoted as "C"), melt dripping of the polyester fibers is prevented due to the so-called Scaf fold effect. Therefore, the flammability is
Compared to polyester fibers and cotton fibers alone, flame retardant processing becomes more difficult, and E/
Currently, there is no flame retardant agent with sufficient washing resistance for C fabrics etc. [Written by Shojiro Oe]
See Polymer Processing 23 , 76 (1976), Katsuura Yoshitsugu Kasei Monthly Report 12 (4), 58 (1974)]. [Means for solving the problem] In order to solve the above problem, the present inventors
We have discovered that flame retardancy can be imparted to raw fibers by impregnating them with aminophosphazene, drying and curing them. However, aminophosphazene
It is generally synthesized from chlorophosphazene and ammonia. Aminophosphazene synthesized in this way contains about 58% by weight of ammonium chloride, and when cured, this ammonium chloride acts as an acid catalyst, causing a decrease in tear strength. After careful consideration, we discovered that there were problems such as the dye discoloring, the flame retardant effect decreasing after washing using the medium-temperature washer method, and the flame retardant deterioration being significant over time.
The present invention has now been completed. Therefore, in the present invention, a crude aminophosphazene aqueous solution containing a large amount of ammonium chloride is poured into a large amount of alcohol, and the purified aminophosphazene obtained by precipitation is dissolved in water, and phosphorus is added to this aqueous solution. 0.1 to 10% by weight of at least one acid catalyst selected from the group consisting of acid, zinc nitrate, zinc borofluoride, zinc chloride, 2-amino-2-methylpropanol hydrochloride, diammonium hydrogen phosphate, and magnesium chloride. % to create a treatment solution, and then add this treatment solution to
The gist of this paper is a method for flame-retardant processing of fibers, which is characterized by impregnating raw fibers, drying them, and curing them. [Function] According to the method for flame retardant processing of fibers according to the present invention, it is possible to produce fibers with excellent tear strength, wrinkle resistance, especially moisture wrinkle resistance, soft texture, and excellent durability such as washing resistance. A combustible fiber is obtained. Moreover, since there is no need to use an ammonia cure method or an oxidation step, problems such as discoloration of the reactive dye are also eliminated. Furthermore, no formaldehyde is generated. [Examples] The present invention will be described in detail below with reference to Examples. The aminophosphazene used in the flame retardant processing method for fibers according to the present invention is preferably purified, particularly in the form of a trimer or a tetramer. Of course, it may be a pentamer or more. Purified aminophosphazene is obtained by dissolving crude aminophosphazene in about 5 times the amount of water, and pouring this aqueous solution into 5 times the amount of alcohol such as methanol to precipitate only the aminophosphazene.
According to the method described above, aminophosphazene is
Forms aminophosphazene HC1. Aminophosphazene HC1 has extremely high solubility in water. Therefore, a highly concentrated processing bath can be created. Furthermore, the alcohol used can be recovered by distillation and used repeatedly, making it economical. In addition to the above methods, there are other purification methods.
There is a method in which crude aminophosphazene is dissolved in ammonia water using liquid ammonia, and this solution is poured into alcohol to precipitate the aminophosphazene. However, these methods
For example, in the method using liquid ammonia, -
The temperature needs to be as low as 33℃, and there is a risk of explosion due to mixing air and ammonia.In the method using ammonia water, aminophosphazene is in the form of aminophosphazene/H 2 O. Therefore, solubility is low (12.1g/100g of water, 25℃)
There is a problem in that it is not possible to obtain a high-quality solution. The concentration of aminophosphazene in aqueous solution is 5-50
Weight percent is preferred. If it is less than 5% by weight, the flame retardant effect tends to be insufficient. If it exceeds 50% by weight, the flame retardant effect is sufficient, but the feel tends to be impaired. Add 0.1 of the acid catalyst to the aqueous solution obtained as above.
A treatment liquid is prepared by adding it at a ratio of ~10% by weight. As the acid catalyst, at least one of phosphoric acid, zinc nitrate, zinc borofluoride, zinc chloride, 2-amino-2-methylpropanol hydrochloride, diammonium hydrogen phosphate, and magnesium chloride is used. Among these, phosphoric acid is used. Particularly preferred. If the acid catalyst is less than 0.1% by weight, the flame retardant effect and washing resistance will be reduced. Furthermore, if the content is 10% by weight or more, the tear strength may decrease or the processed fabric may become discolored. Examples of fibers that can be made flame retardant by the processing method according to the present invention include cotton, silk, linen, rayon, and wool. Note that these fibers are generally subjected to flame retardant treatment in the form of fiber materials such as threads and cloth. The fiber material may be a blended fiber, a mixed woven fabric, or the like. The steps of impregnation, drying, and curing are not particularly limited, but can be performed continuously using a normal pad-dry-cure method. The temperature during drying is preferably about 80 to 120°C.
If the temperature is below 80°C, drying time tends to be longer. The cure is performed in the air, and the temperature during the cure is 80 ~
About 200°C is preferable. When the temperature is lower than 80°C, the treatment time becomes longer and the washing resistance of the flame retardant effect tends to decrease. When the temperature exceeds 200℃, there is a tendency for strength to decrease and discoloration. Next, examples will be described in detail. Examples As textile materials, cotton satin printed cloth, polyester/cotton (65/35) broadcloth, silk habutae, rayon muslin, and wool muslin were prepared. Each of these fabrics was impregnated with a flame retardant agent containing a predetermined amount of aminophosphazene trimer and an acid catalyst in two dips and two nips. After impregnation, 100℃
It was dried for 3 minutes. After drying, 150℃ or 160℃
After curing by heating at 65°C for 3 minutes, the fibers were washed with hot water at 65°C for 5 minutes and dried to obtain flame-retardant fibers. Comparative Example 1 A cotton satin printed fabric was added in 2 dips and 2 nips to a 30% by weight aqueous solution of crude aminophosphazene trimer (containing 58% by weight of ammonium chloride) and subjected to flame retardant treatment in the same manner as in Example. Comparative Example 2 A cotton satin printed cloth was prepared as a fiber material, and 20 wt% of the aminophosphazene trimer purified by the method of the present invention and phosphoric acid as an acid catalyst were added to the cloth.
Fibers were impregnated with a flame retardant containing 0.05 wt% and flame retardant treated in the same manner as in the example. Comparative Example 3 Comparative Example 2 except that the phosphoric acid concentration was 11wt%
A flame-retardant treated fiber was obtained in the same manner as above. The adhesion rate of the flame retardant, the limiting oxygen index (LOI), the carbonized area by heating for 1 minute using a 45° micron burner method, and the carbonized area of each flame retardant fabric obtained in the above Examples and Comparative Examples, and the medium temperature ( The adhesion rate of the flame retardant, the limiting oxygen index (LOI), and the carbonized area after 5 washes using the washer method (60°C) for 1 minute using the 45° micron burner method were investigated, and the results are shown in Table 1.
Furthermore, Table 1 shows the type of acid catalyst and the aminophosphazene in the aqueous solution (abbreviated as "AP" in the table).
and acid catalyst concentration and impregnation depth 2
The reduction ratio of the aqueous solution after nipping is also shown.
【表】【table】
【表】【table】
本発明にかかる難燃性繊維の製法は、以上のよ
うに構成されているので、アミノホスフアゼン濃
度の高い難燃加工処理用水溶液を得ることがで
き、引裂強度にすぐれ、防皺性、とくに、湿防皺
性が向上し、風合も柔らかい耐洗濯性等の耐久性
に優れた難燃性繊維が得られる。しかも、通常の
パツド−ドライ−キユア法により、加工でき、反
応染料の変色がなく、ホルムアルデヒドの発生も
ない。
Since the method for producing flame-retardant fibers according to the present invention is configured as described above, it is possible to obtain an aqueous solution for flame-retardant treatment with a high concentration of aminophosphazene, which has excellent tear strength, wrinkle resistance, and especially A flame-retardant fiber with improved moisture wrinkle resistance, soft texture, and excellent durability such as wash resistance can be obtained. Moreover, it can be processed by the usual pad-dry-cure method, and there is no discoloration of the reactive dye and no generation of formaldehyde.
Claims (1)
ホスフアゼン水溶液を多量のアルコール中に投入
し、沈澱させて得た精製アミノホスフアゼンを水
に溶解させるとともに、この水溶液に、リン酸、
硝酸亜鉛、ホウフツ化亜鉛、塩化亜鉛、２−アミ
ノ−２−メチルプロパノール塩酸塩、リン酸水素
二アンモニウム、および、塩化マグネシウムから
なる群より選ばれた少なくとも一種の酸触媒を
0.1〜10重量％の割合で添加して処理液を作製し
たのち、この処理液を、原料繊維に含浸乾燥させ
て、キユアすることを特徴とする繊維の難燃加工
法。 ２ キユア時の処理温度が80〜200℃である特許
請求の範囲第１項記載の繊維の難燃加工法。 ３ 繊維が綿、麻、レーヨン、絹、羊毛からなる
群より選ばれた少なくとも一種である特許請求の
範囲第１項または第２項記載の繊維の難燃加工
法。[Claims] 1. A crude aminophosphazene aqueous solution containing a large amount of ammonium chloride is poured into a large amount of alcohol, and the purified aminophosphazene obtained by precipitation is dissolved in water, and phosphoric acid is added to this aqueous solution. ,
At least one acid catalyst selected from the group consisting of zinc nitrate, zinc borofluoride, zinc chloride, 2-amino-2-methylpropanol hydrochloride, diammonium hydrogen phosphate, and magnesium chloride.
A method for flame-retardant processing of fibers, which comprises adding a treatment liquid in a proportion of 0.1 to 10% by weight, and then impregnating and drying raw material fibers with this treatment liquid to cure them. 2. The method for flame-retardant processing of fibers according to claim 1, wherein the treatment temperature during curing is 80 to 200°C. 3. The flame retardant processing method for fibers according to claim 1 or 2, wherein the fiber is at least one type selected from the group consisting of cotton, hemp, rayon, silk, and wool.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19313787A JPS6440673A (en) | 1987-07-31 | 1987-07-31 | Fire retardant processing of fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19313787A JPS6440673A (en) | 1987-07-31 | 1987-07-31 | Fire retardant processing of fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6440673A JPS6440673A (en) | 1989-02-10 |
| JPH0149827B2 true JPH0149827B2 (en) | 1989-10-26 |
Family
ID=16302893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19313787A Granted JPS6440673A (en) | 1987-07-31 | 1987-07-31 | Fire retardant processing of fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6440673A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0643666B2 (en) * | 1988-04-21 | 1994-06-08 | 日東紡績株式会社 | Method for processing protein fiber-based cloth and cloth processed by the method |
| JPH0689506B2 (en) * | 1989-04-21 | 1994-11-09 | 日東紡績株式会社 | Processing agent and processing method for cellulosic cloth |
| CN101974849A (en) * | 2010-09-17 | 2011-02-16 | 浙江千圣禧服饰有限公司 | Production technology for flame-retardant and antistatic woolen sweater |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5242759A (en) * | 1975-09-29 | 1977-04-02 | Bendix Corp | Fluid level indicator |
| JPS61183383A (en) * | 1985-02-08 | 1986-08-16 | Nitto Boseki Co Ltd | Water-insoluble flame retarder |
| JPS61215687A (en) * | 1985-03-20 | 1986-09-25 | Gunze Ltd | Method of flameproofing free from occurrence of formaldehyde and capable of providing excellent washing fastness |
| JPS61266669A (en) * | 1985-05-15 | 1986-11-26 | 日東紡績株式会社 | Novel flame-proof processing method |
| JPS61266670A (en) * | 1985-05-15 | 1986-11-26 | 日東紡績株式会社 | Flame-proof processing agent and method |
| JPS61266668A (en) * | 1985-05-15 | 1986-11-26 | 日東紡績株式会社 | Flame-proof processing method |
| JPS61296177A (en) * | 1985-06-25 | 1986-12-26 | 新技術事業団 | Method for applying fire retardant property to cellulosic fiber |
| JPS6278271A (en) * | 1985-10-02 | 1987-04-10 | 日東紡績株式会社 | Flame-proof processing of woven/knitted fabric containing cellulose fiber |
| JPS63120173A (en) * | 1986-06-13 | 1988-05-24 | 日東紡績株式会社 | Method for processing knitted fabric |
-
1987
- 1987-07-31 JP JP19313787A patent/JPS6440673A/en active Granted
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5242759A (en) * | 1975-09-29 | 1977-04-02 | Bendix Corp | Fluid level indicator |
| JPS61183383A (en) * | 1985-02-08 | 1986-08-16 | Nitto Boseki Co Ltd | Water-insoluble flame retarder |
| JPS61215687A (en) * | 1985-03-20 | 1986-09-25 | Gunze Ltd | Method of flameproofing free from occurrence of formaldehyde and capable of providing excellent washing fastness |
| JPS61266669A (en) * | 1985-05-15 | 1986-11-26 | 日東紡績株式会社 | Novel flame-proof processing method |
| JPS61266670A (en) * | 1985-05-15 | 1986-11-26 | 日東紡績株式会社 | Flame-proof processing agent and method |
| JPS61266668A (en) * | 1985-05-15 | 1986-11-26 | 日東紡績株式会社 | Flame-proof processing method |
| JPS61296177A (en) * | 1985-06-25 | 1986-12-26 | 新技術事業団 | Method for applying fire retardant property to cellulosic fiber |
| JPS6278271A (en) * | 1985-10-02 | 1987-04-10 | 日東紡績株式会社 | Flame-proof processing of woven/knitted fabric containing cellulose fiber |
| JPS63120173A (en) * | 1986-06-13 | 1988-05-24 | 日東紡績株式会社 | Method for processing knitted fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6440673A (en) | 1989-02-10 |
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