JPH06101176A - Durable flame-resistant treatment of cellulose-based fiber material - Google Patents
Durable flame-resistant treatment of cellulose-based fiber materialInfo
- Publication number
- JPH06101176A JPH06101176A JP6095692A JP6095692A JPH06101176A JP H06101176 A JPH06101176 A JP H06101176A JP 6095692 A JP6095692 A JP 6095692A JP 6095692 A JP6095692 A JP 6095692A JP H06101176 A JPH06101176 A JP H06101176A
- Authority
- JP
- Japan
- Prior art keywords
- water
- cellulose
- mol
- fiber
- based fiber
- 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
- 239000002657 fibrous material Substances 0.000 title claims abstract description 14
- 229920002678 cellulose Polymers 0.000 title claims abstract description 8
- 239000001913 cellulose Substances 0.000 title claims abstract description 8
- 239000000835 fiber Substances 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 17
- 229920000728 polyester Polymers 0.000 claims abstract description 16
- 239000012209 synthetic fiber Substances 0.000 claims abstract description 15
- 229920002994 synthetic fiber Polymers 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 4
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims abstract description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 47
- 238000012545 processing Methods 0.000 claims description 21
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical class CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims description 3
- 239000004744 fabric Substances 0.000 abstract description 19
- 238000002156 mixing Methods 0.000 abstract description 10
- -1 methylphosphonic acid ester Chemical class 0.000 abstract description 3
- 239000004753 textile Substances 0.000 abstract description 3
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 239000000047 product Substances 0.000 description 25
- 238000012360 testing method Methods 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 12
- 229920000742 Cotton Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005452 bending Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000003763 carbonization Methods 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 229940045872 sodium percarbonate Drugs 0.000 description 5
- 239000002759 woven fabric Substances 0.000 description 5
- 229920003043 Cellulose fiber Polymers 0.000 description 4
- 238000005108 dry cleaning Methods 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 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 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- ZGTNBBQKHJMUBI-UHFFFAOYSA-N bis[tetrakis(hydroxymethyl)-lambda5-phosphanyl] sulfate Chemical compound OCP(CO)(CO)(CO)OS(=O)(=O)OP(CO)(CO)(CO)CO ZGTNBBQKHJMUBI-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 1
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- ANHAEBWRQNIPEV-UHFFFAOYSA-N 2-chloroethyl dihydrogen phosphate Chemical compound OP(O)(=O)OCCCl ANHAEBWRQNIPEV-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000011511 Diospyros Nutrition 0.000 description 1
- 244000055850 Diospyros virginiana Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- UJSSNDKVUQJEGE-UHFFFAOYSA-N dichloro propyl phosphate Chemical compound CCCOP(=O)(OCl)OCl UJSSNDKVUQJEGE-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-L ethenyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-L 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、風合いの改良されたセ
ルロース系繊維材料の耐久性防炎加工法に関する。更に
詳しくは、セルロース系繊維もしくはセルロース系繊維
と他の繊維との混用品に風合いの優れた、耐久性のある
防炎加工法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a durable flameproofing method for a cellulosic fiber material having an improved texture. More specifically, it relates to a flameproofing method having excellent texture and durability for cellulosic fibers or a mixed product of cellulosic fibers and other fibers.
【０００２】[0002]
【従来の技術】従来から、セルロース系繊維材料に耐久
性のある防炎性能を付与する方法として、テトラキスヒ
ドロキシメチルホスホニウム塩と尿素との反応物を用い
る方法、Ｎ−ヒドロキシメチルジアルキルホスホノプロ
ピオンアミドとメチロールメラミンを用いる方法、ビニ
ルホスホネートオリゴマーとＮ−メチロールアクリルア
ミドを用いる方法等が知られている。また、ポリエステ
ル繊維等に対しては、ヘキサブロモシクロドデカンの水
分散液を使用して、吸尽法又はサーモゾル法によって繊
維に付着させる方法、トリスジクロロプロピルホスフェ
ート、トリクレジルホスフェートを吸尽法又はサーモゾ
ル法によって繊維に付着させる方法が知られている。2. Description of the Related Art Conventionally, as a method for imparting durable flameproof performance to a cellulosic fiber material, a method using a reaction product of a tetrakishydroxymethylphosphonium salt and urea, N-hydroxymethyldialkylphosphonopropionamide. And a method using methylol melamine, a method using a vinylphosphonate oligomer and N-methylol acrylamide, and the like are known. Further, for polyester fibers and the like, using an aqueous dispersion of hexabromocyclododecane, a method of adhering to the fibers by an exhaust method or a thermosol method, trisdichloropropyl phosphate, tricresyl phosphate is an exhaust method or A method of attaching to fibers by a thermosol method is known.
【０００３】[0003]
【発明が解決しようとする課題】しかし、ポリエステル
繊維等の合成繊維とセルロース系繊維との混用品につい
ては、セルロース系繊維の混率が高い場合には、セルロ
ース系繊維用の防炎剤による防炎加工法が一部試みられ
てきたが、風合いが優れ、更に耐久性のある防炎加工法
を達成することは困難であった。また、ポリエステル繊
維等の合成繊維及びセルロース系繊維のそれぞれに最適
な防炎剤を使用しても、それぞれの単品では防炎性能を
示すが、混用品については防炎性能を示さないという欠
点があった。特に、ポリエステルと綿との混用品では、
混率が７０／３０〜３０／７０の素材については、耐久
性のある防炎性能及び風合いを同時に満足させることは
困難であった。However, in the case of a mixed product of synthetic fibers such as polyester fibers and cellulosic fibers, when the cellulosic fiber content is high, flameproofing by a flameproofing agent for cellulosic fibers is carried out. Although some processing methods have been tried, it has been difficult to achieve a flameproof processing method that has an excellent texture and is durable. Further, even if the optimum flameproofing agent is used for each of the synthetic fibers such as polyester fibers and the cellulosic fibers, each of them shows the flameproofing performance, but the mixed product has the drawback of not showing the flameproofing performance. there were. Especially for mixed products of polyester and cotton,
For materials having a mixing ratio of 70/30 to 30/70, it was difficult to simultaneously satisfy durable flameproof performance and texture.
【０００４】合成繊維、特にポリエステル繊維とセルロ
ース繊維との混用品の防炎加工が困難な理由は明らかで
はないが、下記の３つの可能性が考えられる。 （１）一方の繊維に付与された防炎剤の本来の作用が、
他方の成分又はその分解物との化学反応等によって阻害
される。 （２）ポリエステル繊維等の合成繊維とセルロース系繊
維との混用品の熱分解生成物の種類、生成速度等が、合
成繊維及びセルロース系繊維それぞれ単独の場合とは異
なる。 （３）熱溶融性成分と非溶融性成分との混合の結果、溶
融成分系からの脱落が抑えられる一般にscafolding eff
ect と言われる現象が起こる。 以上の理由で、従来合成繊維、特にポリエステル繊維と
セルロース系繊維との混用品に、風合いの優れた耐久性
防炎加工を施することは非常に困難であった。Although it is not clear why the flameproofing of a synthetic fiber, in particular, a mixed product of polyester fiber and cellulose fiber is difficult, the following three possibilities are considered. (1) The original action of the flameproofing agent applied to one fiber is
It is inhibited by a chemical reaction or the like with the other component or its decomposition product. (2) The type and rate of thermal decomposition products of a mixed product of synthetic fibers such as polyester fibers and cellulosic fibers are different from those of the synthetic fibers and cellulosic fibers alone. (3) As a result of the mixing of the heat-meltable component and the non-meltable component, it is generally possible to suppress the falling out of the melted component system.
A phenomenon called ect occurs. For the above reasons, it has been very difficult to subject a conventional synthetic fiber, particularly a mixed product of polyester fiber and cellulosic fiber, to a durable flameproofing treatment having an excellent texture.
【０００５】本発明者は、鋭意研究の結果、従来不可能
とされていた合成繊維、特にポリエステル繊維とセルロ
ース系繊維との混用品の風合いの優れた、耐久性のある
防炎加工法を完成したものである。また、セルロースの
みの繊維に対しても従来の方法に比較して、風合いの優
れた、耐久性を有する防炎加工法を完成した。As a result of diligent research, the present inventor has completed a durable flameproofing method which is conventionally impossible and has excellent texture of a mixed product of synthetic fibers, particularly polyester fibers and cellulosic fibers. It was done. In addition, even with respect to fibers made of only cellulose, a flameproofing method having excellent texture and durability as compared with the conventional method has been completed.
【０００６】[0006]
【課題を解決するための手段】本発明は、一般式 （ＨＯＣＨ2)4ＰＸ （式中ＸはＣｌ、1/2 ＳＯ4 又はＯＨを表す）で示され
るテトラキスヒドロキシメチルホスホニウム塩１モルと
尿素０．２〜３．０モルとの反応（固形分として）１０
０重量部に、水溶性メチルホスホン酸エステル誘導体５
〜１００重量部を配合した加工液を用いて、セルロース
系繊維材料を処理することを特徴とする、風合いの改良
されたセルロース系繊維材料の耐久性防炎加工法であ
る。本発明の方法により、従来困難であったセルロース
系繊維材料に風合いの優れた、耐久性のある防炎性能を
付与し、更に従来不可能であったセルロース系繊維と合
成繊維、特にポリエステル繊維との混用品に、風合いの
優れた耐久性のある防炎性能を付与することができる。
更に、本発明の方法により、このような優れた性能を有
する防炎性繊維製品を製造することができる。The present invention provides a tetrakishydroxymethylphosphonium salt represented by the general formula (HOCH 2 ) 4 PX (wherein X represents Cl, 1/2 SO 4 or OH) and urea. Reaction with 0.2-3.0 mol (as solids) 10
0 parts by weight of water-soluble methylphosphonate derivative 5
A durable flameproofing method for a cellulosic fiber material having an improved texture, which comprises treating the cellulosic fiber material with a processing liquid containing 100 to 100 parts by weight. By the method of the present invention, it is possible to impart a durable, flameproof property to a cellulosic fiber material that has been difficult in the past, and to impart a durable flameproofing property. It is possible to impart durable and flameproof performance with excellent texture to the mixed product of.
Furthermore, the method of the present invention makes it possible to produce a flameproof fiber product having such excellent performance.
【０００７】本発明においてセルロース系繊維材料と
は、セルロース繊維及びセルロース繊維と合成繊維の混
用品であり、更に詳しくは、木綿、麻等のセルロース繊
維、酢酸セルロース、レーヨン等の半合成セルロース繊
維、及びこれらとポリエステル、ポリアミド、アクリル
等の合成繊維との混用品を指す。合成繊維とセルロース
繊維との混率は、０／１００〜８０／２０であり、これ
らの繊維は難燃化されていてもよい。In the present invention, the cellulosic fiber material is a cellulosic fiber or a mixed product of cellulosic fiber and synthetic fiber. More specifically, cellulosic fiber such as cotton and hemp, semi-synthetic cellulosic fiber such as cellulose acetate and rayon, And a mixed product of these and synthetic fibers such as polyester, polyamide and acrylic. The mixing ratio of the synthetic fiber and the cellulose fiber is 0/100 to 80/20, and these fibers may be flame-retarded.
【０００８】混用とは、混紡、交織、交編、交撚等をい
う。またその形状は、糸状、綿状、生地、織物、編物、
不織布等いずれであってもよく、その用途は、工業用資
材、工業用及び家庭用繊維製品、衣料、衣服、寝装寝具
類、インテリア用品、エクステリア用品、スポーツ用
品、日用雑貨品等で、例えば帆布、シート、テント、ロ
ープ、カーテン、カーペット、壁張地、椅子張地、寝装
品布団、毛布、敷布、作業服、パジャマ、リボン、組
紐、起毛品等いかなるものであってもよい。"Mixed" means mixed spinning, mixed weaving, mixed knitting, mixed twisting and the like. In addition, its shape is thread, cotton, cloth, woven fabric, knitted fabric,
It may be any of non-woven fabrics and the like, and its uses are industrial materials, industrial and household textile products, clothing, clothes, bedding, bedding, interior goods, exterior goods, sports goods, daily necessities, etc. For example, canvas, sheets, tents, ropes, curtains, carpets, wall upholstery, chair upholstery, bedding duvets, blankets, bedspreads, work clothes, pajamas, ribbons, braids, and raised fabrics may be used.
【０００９】本発明に用いられる防炎剤加工液は、テト
ラキスヒドロキシメチルホスホニウム塩１モルに尿素
０．２〜３．０モル、好ましくは０．５〜２．０モルを
加え、２０〜１００℃好ましくは３０〜９０℃で反応さ
せた反応物１００重量部（固形分として）に対して水溶
性メチルホスホン酸エステル誘導体５〜１００重量部、
好ましくは１０〜５０重量部を加えて混合することによ
り調製できる。水溶性メチルホスホン酸エステル誘導体
の添加量が５重量部未満では風合いの改良が充分ではな
く好ましくない。また１００重量部より多い場合は、格
別の風合いの向上は認められないばかりか、ソーピング
によって水溶性メチルホスホン酸エステル誘導体が除去
されるため無駄になり好ましくない。The flameproofing agent processing liquid used in the present invention is obtained by adding 0.2 to 3.0 moles, preferably 0.5 to 2.0 moles of urea to 1 mole of tetrakishydroxymethylphosphonium salt, and 20 to 100 ° C. Preferably, 5 to 100 parts by weight of the water-soluble methylphosphonate derivative relative to 100 parts by weight (as a solid content) of the reaction product reacted at 30 to 90 ° C,
Preferably, it can be prepared by adding 10 to 50 parts by weight and mixing. If the amount of the water-soluble methylphosphonate derivative added is less than 5 parts by weight, the texture is not sufficiently improved, which is not preferable. On the other hand, when the amount is more than 100 parts by weight, not only the improvement of the special texture is not recognized, but also the water-soluble methylphosphonate derivative is removed by soaping, which is not preferable.
【００１０】テトラキスヒドロキシメチルホスホニウム
塩１モルに対する尿素の使用量は０．２〜３．０モルで
ある。尿素０．２モル未満の場合又は３．０モルより多
い場合は、防炎性能、特に耐洗濯性が悪くなり好ましく
ない。防炎剤加工液の濃度は特に限定されないが、５〜
８５％特に１０〜７５％が使用し易く好ましい。The amount of urea used is 0.2 to 3.0 mol with respect to 1 mol of the tetrakishydroxymethylphosphonium salt. When the amount of urea is less than 0.2 mol or more than 3.0 mol, the flameproof performance, especially the washing resistance is deteriorated, which is not preferable. Although the concentration of the flameproofing agent processing liquid is not particularly limited,
85% and particularly 10 to 75% are preferable because they are easy to use.
【００１１】本発明に用いられる水溶性メチルホスホン
酸エステル誘導体は、特開昭５８−１１７２７２号及び
特公昭６０−３８４２０号公報に記載の方法により製造
することができる。これらは、ジメチルメチルホスホネ
ート（１モル）、五酸化リン（０．４〜１．０モル）エ
チレングリコール（０．１〜１．０モル）及びエチレン
オキサイド（１．５〜５．０モル）の反応物又はトリメ
チロールプロパンホスファイトとメチルホスホン酸ジメ
チルエステルの反応物で、一般式The water-soluble methylphosphonate derivative used in the present invention can be produced by the method described in JP-A-58-117272 and JP-B-60-38420. These are dimethyl methylphosphonate (1 mol), phosphorus pentoxide (0.4 to 1.0 mol) ethylene glycol (0.1 to 1.0 mol) and ethylene oxide (1.5 to 5.0 mol). A reaction product or a reaction product of trimethylolpropane phosphite and methylphosphonic acid dimethyl ester, represented by the general formula
【化２】 （式中ｎは０又は１）で示される化合物であり、市販品
を使用することもできる。[Chemical 2] (In the formula, n is 0 or 1), and a commercially available product can be used.
【００１２】本発明に用いられる防炎剤加工液は、必要
に応じて水、アルコール等の溶剤を加えて希釈してもよ
い。また界面活性剤、浸透剤、揆水剤、揆油剤、柔軟
剤、着色剤、硬化剤、樹脂類、ラテックス類、耐光剤、
安定剤、他の薬剤等を併用してもよい。The flameproofing agent processing liquid used in the present invention may be diluted by adding a solvent such as water or alcohol, if necessary. In addition, surfactants, penetrants, water repellents, oil repellents, softeners, colorants, curing agents, resins, latexes, light resistance agents,
You may use together a stabilizer, another chemical | medical agent, etc.
【００１３】本発明の防炎加工法は、防炎剤加工液を従
来の方法例えば浸漬、スプレー、コーティング等で繊維
材料に付着させ予備乾燥後、１１０℃以上好ましくは１
３０℃以上でキュアリングを行う。マイクロ波または高
圧スチーマーによる蒸熱処理によりキュアリングを行な
ってもよい。その後ソーピングを行い未固着の薬剤及び
水溶性メチルホスホン酸エステル誘導体を除去すればよ
い。ソーピングはバッチソーピング、連続ソーピングな
どの方法により行なうことができるが、消臭を目的とし
て過酸化水素、過炭酸ソーダ等を含む４０〜７０℃の温
水で行ない、更に湯洗浄を行なうことが好ましい。その
後、必要に応じて柔軟加工、カムフィット加工等を行な
ってもよい。In the flameproofing method of the present invention, the flameproofing agent processing liquid is applied to the fiber material by a conventional method such as dipping, spraying or coating and pre-dried.
Curing is performed at 30 ° C or higher. Curing may be performed by steaming with a microwave or a high-pressure steamer. Thereafter, soaping may be performed to remove the unfixed drug and the water-soluble methylphosphonate derivative. The soaping can be carried out by a method such as batch soaping or continuous soaping, but for the purpose of deodorizing, it is preferable to carry out hot water containing 40 to 70 ° C. containing hydrogen peroxide, sodium percarbonate and the like, and further wash with hot water. Then, you may perform a soft process, a cam fitting process, etc. as needed.
【００１４】加工液及び薬剤の付着量は、加工液の濃
度、目標とする防炎性能、繊維材料の種類、合成繊維と
セルロース繊維との混用の割合等によって調製すること
ができる。ソーピング、乾燥後の難燃剤付着量（固形
分）は、１〜４０％好ましくは３〜３５％である。付着
量が１％未満では防炎性能が弱く、４０％より多いと風
合いが悪くなり好ましくない。The deposition amount of the processing liquid and the chemical agent can be adjusted by the concentration of the processing liquid, the target flameproof performance, the kind of the fiber material, the mixing ratio of the synthetic fiber and the cellulose fiber, and the like. The amount of the flame retardant attached (solid content) after soaping and drying is 1 to 40%, preferably 3 to 35%. If the adhered amount is less than 1%, the flameproof performance is weak, and if the adhered amount is more than 40%, the texture becomes unfavorable.
【００１５】[0015]
【実施例】次に実施例で更に詳細に説明する。なお実施
例で行なった評価方法は次の通りである。 水洗い洗濯方法 粉末洗濯石けん（ＪＩＳＫ３３０３第１種）水１リット
ル当り１ｇを使用し、６０℃の水を給水し、洗剤を投入
し、試験体を投入し、次いで６０℃の液で１５分間洗浄
する。次いで排水、給水、４０℃の水で５分間のすすぎ
３回及び排水脱水２分間を行ない、これを１サイクルと
して供試布を５回、３０回及び５０回洗濯処理した。 ドライクリーニング方法 消防庁告示第１号（昭和６１年）に定めるドライクリー
ニング方法によった。但し、ドライクリーニングを行う
前に試料を温水処理（４０℃×３０分）し、通常の乾燥
を行うものとする。EXAMPLES Next, examples will be described in more detail. The evaluation method used in the examples is as follows. Washing with water Washing method Washing powder soap (JIS K3303 type 1) Using 1 g per 1 liter of water, supplying water at 60 ° C, adding detergent, adding test sample, and then washing with liquid at 60 ° C for 15 minutes . Next, drainage, water supply, rinsing with water at 40 ° C. for 5 minutes 3 times and drainage dehydration 2 minutes were performed, and this was taken as one cycle, and the test cloth was washed 5, 30, and 50 times. Dry-cleaning method The dry-cleaning method specified by the Fire Service Agency Notification No. 1 (1986) was used. However, the sample is subjected to warm water treatment (40 ° C. × 30 minutes) before being subjected to dry cleaning, and is then subjected to normal drying.
【００１６】消炎性能試験方法 （財）日本防炎協会認定委員会の防炎製品の性能試験基
準によって行なった。 (1) 垂直法 試験体の寸法： 各８９mm×２５４mm 試験体の状態調節： ５０±２℃恒温乾燥器で２４時間
乾燥後、シリカゲル入りデシケータ中で２時間以上乾燥
する。 鉛直バーナー法： 炎の長さをバーナーの最も高い点か
ら上方へ測って３８mmとなるように調節し、炎が安定し
ていることを確認する。バーナーを移動して試験体に
３．０±０．２秒間接炎する。試験体からバーナーの炎
を取り去った後に試験体支持枠上で燃焼する状態及び炎
滴着火性を確認する。 判定： 布地の５試験体については平均炭化長が１７８
mm以下であり、かつ最大炭化長は２５４mm未満であるこ
と。炎滴着火性の無いこと。Flame-extinguishing performance test method The test was carried out according to the performance test standards for flame-proof products of the Japan Flame-proof Association Certification Committee. (1) Vertical method Specimen size: 89mm x 254mm Condition adjustment of specimen: 50 ± 2 ℃ Dry in a desiccator containing silica gel for 24 hours and then for 2 hours or more in a desiccator containing silica gel. Vertical burner method: Adjust the flame length so that it is 38 mm, measured upwards from the highest point of the burner, and confirm that the flame is stable. Move the burner and indirect flame on the test piece for 3.0 ± 0.2 seconds. After removing the burner flame from the test piece, check the state of burning on the test piece support frame and the flame drop ignitability. Judgment: The average carbonization length is 178 for the five fabric test pieces
mm or less and the maximum carbonization length is less than 254 mm. No flame ignitability.
【００１７】(2) ４５度メセナミン法 試験体を試験体支持枠の金網の上に重ねて試験体支持枠
にゆるみなく固定し、試験体支持枠の内側の下辺中央部
より５cm上部の位置にメセナミン（エリー・リリー社製
品番号１５８８ 商品名メセナミン）を容易に移動しな
い方法で置く。点火はマッチにより行い、点火後はすみ
やかに燃焼試験箱のガラス窓を閉じて燃焼が終了するま
で放置する。 判定： 炭化長とし、試験体の炭化部分の縦方向の最大
の長さとし、試験体３体について、最大の長さが７０mm
以下で、かつその平均値が５０mm以下であること。(2) 45 ° Mesenamin Method The test body is superposed on the wire mesh of the test body support frame and fixed to the test body support frame without loosening, and placed 5 cm above the center of the lower side of the inside of the test body support frame. Place mecenamin (Erie Lilly product number 1588, trade name mesenamine) in a manner that does not easily move. Ignition is performed by match, and after ignition, immediately close the glass window of the combustion test box and leave it until the combustion ends. Judgment: The carbonized length is the maximum length in the longitudinal direction of the carbonized portion of the test body, and the maximum length of the three test bodies is 70 mm.
Below, and the average value is 50 mm or less.
【００１８】(3) ４５度ミクロバーナー法 自治省消防庁防炎試験基準、４５度ミクロバーナー法に
従って防炎性の合否を判定した。この場合の合格基準値
は炭化面積３０cm2 以下、残炎時間３秒以下、残じん時
間５秒以下である。 風合いの判定方法 ＪＩＳ Ｌ−１０９６、一般織物試験方法の４５度カン
チレバー法による剛軟性の測定及び手の感触により判定
した。(3) 45-degree micro-burner method The flame-proof property was judged according to the 45-degree micro-burner method in accordance with the Ministry of Internal Affairs and Communications Fire Agency fire-retardant test standard. In this case, the pass standard values are a carbonization area of 30 cm 2 or less, an afterflame time of 3 seconds or less, and a dusting time of 5 seconds or less. Judgment method of texture Judgment was made by measuring the bending resistance and the feel of the hand by the 45 ° cantilever method of JIS L-1096, the general woven fabric test method.
【００１９】製造例１ テトラキスヒドロキシメチルホスホニウムサルフェート
の８０％水溶液７００ｇ（２．７６モル）に水１００ｇ
及び尿素２００ｇ（３．３３モル）を加える。攪拌しな
がら４０℃に加温して尿素を溶解させる。徐々に温度を
上げて６５〜７０℃で６０分間反応させる。固形分約７
５％の透明な水溶液１０００ｇが得られた。Production Example 1 100 g of water was added to 700 g (2.76 mol) of an 80% aqueous solution of tetrakishydroxymethylphosphonium sulfate.
And 200 g of urea (3.33 mol) are added. Warm to 40 ° C. with stirring to dissolve urea. The temperature is gradually raised and reacted at 65 to 70 ° C. for 60 minutes. Solid content about 7
1000 g of a 5% clear aqueous solution was obtained.
【００２０】製造例２ テトラキスヒドロキシメチルホスホニウムサルフェート
の８０％水溶液７００ｇ（２．７６モル）に水１６０ｇ
及び尿素３３１ｇ（５．５２モル）を加える。攪拌しな
がら４０℃に加温して尿素を溶解させる。徐々に温度を
上げて６５〜７０℃で６０分間反応させる。固形分約７
５％の透明な水溶液１１９１ｇが得られた。Production Example 2 160 g of water was added to 700 g (2.76 mol) of an 80% aqueous solution of tetrakishydroxymethylphosphonium sulfate.
And 331 g (5.52 mol) urea. Warm to 40 ° C. with stirring to dissolve urea. The temperature is gradually raised and reacted at 65 to 70 ° C. for 60 minutes. Solid content about 7
1191 g of a 5% clear aqueous solution was obtained.
【００２１】製造例３ テトラキスヒドロキシメチルホスホニウムクロライドの
８０％水溶液２３８ｇ（１．０モル）に水酸化ナトリウ
ムの５０％水溶液８０ｇを攪拌しながら４５〜５０℃で
徐々に加えた。次に、減圧（１５mmＨｇ）下、５０〜７
０℃で水分を留去した後、生成した塩化ナトリウムの結
晶を濾過して製造したテトラキスヒドロキシメチルホス
ホニウムヒドロキサイド１３８ｇ（０．８モル）に水１
０６ｇ及び尿素６０ｇ（１．０モル）を加え、４０℃に
加温して尿素を溶解させる。徐々に温度を上げて６５〜
７０℃で６０分間反応させる。固形分約６５％の透明な
水溶液３０４ｇが得られた。Production Example 3 To 238 g (1.0 mol) of an 80% aqueous solution of tetrakishydroxymethylphosphonium chloride, 80 g of a 50% aqueous solution of sodium hydroxide was gradually added with stirring at 45 to 50 ° C. Next, under reduced pressure (15 mmHg), 50 to 7
After water was distilled off at 0 ° C, 138 g (0.8 mol) of tetrakishydroxymethylphosphonium hydroxide produced by filtering the formed sodium chloride crystals was added to 1 part of water.
Add 06 g and 60 g (1.0 mol) of urea and heat to 40 ° C. to dissolve the urea. Gradually raise the temperature to 65
Incubate at 70 ° C. for 60 minutes. 304 g of a transparent aqueous solution having a solid content of about 65% were obtained.
【００２２】製造例４ 特開昭５８−１１７２７２号公報の実施例３に記載の方
法に準じて、ジメチルメチルホスホネート１２４ｇ
（１．０モル）に五酸化リン１２３．５ｇ（０．８７モ
ル）を２０〜６０℃で徐々に加えた後、９０℃で６０分
間反応させる。次に、４０〜５０℃でエチレングリコー
ル２７．９ｇ（０．４５モル）を少量ずつ加え、６０℃
で６０分間反応させる。その後、エチレンオキサイド１
５０ｇ（３．４モル）を６０〜６５℃で反応させると、
水溶性メチルホスホン酸エステル誘導体４１８ｇが得ら
れた。淡褐色・粘稠液体、酸価１１．２、燐含有率２
０．１％。Production Example 4 124 g of dimethyl methylphosphonate was prepared according to the method described in Example 3 of JP-A-58-117272.
123.5 g (0.87 mol) of phosphorus pentoxide was gradually added to (1.0 mol) at 20 to 60 ° C., and then reacted at 90 ° C. for 60 minutes. Next, 27.9 g (0.45 mol) of ethylene glycol was added little by little at 40 to 50 ° C., and 60 ° C.
React for 60 minutes. Then ethylene oxide 1
When 50 g (3.4 mol) is reacted at 60 to 65 ° C,
418 g of a water-soluble methylphosphonate derivative was obtained. Light brown / viscous liquid, acid value 11.2, phosphorus content 2
0.1%.
【００２３】実施例１ ポリエステル５０％／綿５０％の混紡布（目付 １５０
ｇ／ｍ2 ）を下記配合の加工液を用いて加工を行なっ
た。 加工液の配合 ・製造例１の化合物 ７０ｇ ・ 水 ２０ｇ ・製造例４の化合物 １０ｇ 混紡布を加工液に浸漬し、マングルで絞り（絞り率９０
％）、予備乾燥１２０℃×２分後、キュアリング１７０
℃×３分行った。次に過炭酸ソーダ０．５％の溶液でソ
ーピング、湯水洗を行ない乾燥した。防炎剤付着量固形
分３０％Example 1 Mixed fabric of 50% polyester / 50% cotton (with a fabric weight of 150)
g / m 2 ) was processed using a processing liquid having the following composition. Blending of processing liquid-Compound of Production Example 1 70 g-Water 20 g-Compound of Production Example 4 10 g Immerse the mixed spinning cloth in the processing liquid and squeeze with a mangle (drawing ratio 90
%), Pre-drying after 120 ° C x 2 minutes, curing 170
It was carried out at ℃ × 3 minutes. Then, the product was soaped with a 0.5% sodium percarbonate solution, washed with hot water and dried. Amount of flameproofing agent solid content 30%
【００２４】比較例１ 製造例１の化合物７０ｇ、水３０ｇの溶液を用いて実施
例１と同様の方法で加工した。防炎剤付着量（固形分）
３０％。防炎性能は、防炎製品分類項目中の「衣料」用
途の燃焼試験（垂直法、３秒接炎）により評価した。 実施例１． 比較例１． 防炎加工布の風合い（感触） 良好 ○ 硬い × （剛軟度・縦） ４３mm ７０mm （剛軟度・横） ４３mm ７８mm 防炎性能・加工上り ６．８cm ７．０cm （平均炭化長） （合格） （合格） ５０回洗濯 ７．５cm ８．０cm （合格） （合格）Comparative Example 1 The same process as in Example 1 was carried out using a solution of the compound of Preparation Example 1 (70 g) and water (30 g). Amount of flameproofing agent attached (solid content)
30%. The flameproof performance was evaluated by a combustion test (vertical method, 3 seconds flame contact) for "clothing" use in the flameproof product classification item. Example 1. Comparative Example 1. Good texture (feel) of flameproof fabric ○ Hard x (Bending / vertical) 43mm 70mm (Bending / width) 43mm 78mm Flameproofing / finished 6.8cm 7.0cm (average carbonization length) (Pass) ) (Pass) Wash 50 times 7.5cm 8.0cm (Pass) (Pass)
【００２５】実施例２ ポリエステル３０％／綿７０％の交織布（目付 ２００
ｇ／ｍ2 ）を下記配合の加工液を用いて加工を行なっ
た。 加工液の配合 ・製造例２の化合物 ６４ｇ ・ 水 ２０ｇ ・製造例４の化合物 １６ｇ 交織布を加工液に浸漬し、マングルで絞り（絞り率９６
％）、予備乾燥１２０℃×３分後、キュアリング１７０
℃×３分行なった。次に過炭酸ソーダ０．５％溶液でソ
ーピング、湯水洗を行ない乾燥した。防炎剤付着量固形
分２８％。Example 2 30% polyester / 70% cotton mixed woven fabric (weight of 200
g / m 2 ) was processed using a processing liquid having the following composition. Compounding of working liquid-Compound of Production Example 2 64 g-Water 20 g-Compound of Production Example 4 16 g Dip the woven cloth in the working liquid and squeeze with a mangle (drawing ratio 96
%), Pre-drying 120 ° C. × 3 minutes, curing 170
It was carried out at 3 ° C for 3 minutes. Next, it was soaped with a 0.5% sodium percarbonate solution, washed with hot water and dried. The amount of flameproofing agent attached is 28% solids.
【００２６】比較例２ 製造例２の化合物６４ｇ及び水３６ｇの溶液を用いて、
実施例２と同様の方法にて加工した。防炎剤付着量固形
分２６％。防炎性能は、防炎製品分類項目中の「衣料」
用途の燃焼試験（垂直法、３秒接炎）により評価した。 実施例２． 比較例２． 防炎加工布の風合い（感触） 良好 ○ 硬い × （剛軟度・縦） ４７mm ７８mm （剛軟度・横） ４５mm ７４mm 防炎性能・加工上り ７．０cm ７．５cm （平均炭化長） （合格） （合格） ５０回洗濯 ８．０cm １０．０cm （水洗い洗濯） （合格） （合格）Comparative Example 2 Using a solution of 64 g of the compound of Preparation Example 2 and 36 g of water,
Processing was performed in the same manner as in Example 2. Amount of flameproofing agent is 26% solids. Flameproof performance is "clothing" in the category of flameproof products
It was evaluated by a combustion test for application (vertical method, 3 seconds flame contact). Example 2. Comparative example 2. Good texture (feel) of flameproof fabric ○ Hard x (Bending flexibility / length) 47mm 78mm (Bending flexibility / width) 45mm 74mm Flameproof performance / finished finish 7.0cm 7.5cm (average carbonization length) (Pass) ) (Pass) Wash 50 times 8.0cm 10.0cm (Wash in water) (Pass) (Pass)
【００２７】実施例３ ポリエステル６５％／綿３５％の交織布（目付２２０ｇ
／ｍ2 ）を下記配合の加工液を用いて加工を行なった。 加工液の配合 ・製造例１の化合物 ６０ｇ ・ 水 ３０ｇ ・ファイロール５１ １０ｇ （アクゾ社製の水溶性メチルホスホン酸エステル誘導
体） 交織布を加工液に浸漬しマングルで絞り（絞り率９７
％）予備乾燥１２０℃×３分後、キュアリング１５０℃
×２分行なった。次に過炭酸ソーダ０．５％の溶液でソ
ーピング、湯水洗を行ない乾燥した。防炎剤付着量固形
分２０％。Example 3 Mixed woven fabric of 65% polyester / 35% cotton (220 g of basis weight)
/ M 2 ) was processed using a processing liquid having the following composition. Blending of processing liquid-Compound of Production Example 1 60g-Water 30g-Phiroll 51 10g (water-soluble methylphosphonate derivative manufactured by Akzo) Dip a woven cloth in the processing liquid and squeeze with mangle (squeeze ratio 97
%) Pre-drying after 120 ℃ × 3 minutes, curing 150 ℃
× 2 minutes. Then, the product was soaped with a 0.5% sodium percarbonate solution, washed with hot water and dried. 20% solid content of flameproofing agent.
【００２８】比較例３ 製造例１の化合物６０ｇ及び水４０ｇの溶液を用いて、
同様の方法で加工した。防炎剤付着量固形分１８％。防
炎性能は、防炎物品分類項目中の「カーテン用途、
（イ）ラベル」の燃焼試験（４５度ミクロバーナー法１
分及び３秒加熱）により評価した。 実施例３ 比較例３ 防炎加工布の風合い（感触） 良好 ○ 硬い × （剛軟度・縦） ５７mm ７５mm （剛軟度・横） ３８mm ５０mm 防炎性能・加工上り 合格 合格 水洗い洗濯 合格 合格 （５回洗濯） ドライクリーニング洗濯 合格 合格 （５回洗濯）Comparative Example 3 Using a solution of the compound of Preparation Example 1 (60 g) and water (40 g),
It processed by the same method. 18% solid content of flame retardant. The flameproof performance is "curtain use," in the flameproof article classification item.
(A) Label's combustion test (45 degree micro burner method 1
Minutes and heating for 3 seconds). Example 3 Comparative Example 3 Good texture (feeling) of flameproof cloth ○ Hard × (rigid softness / length) 57 mm 75 mm (rigid softness / width) 38 mm 50 mm Flameproof performance / finishing pass Pass Pass Wash-wash pass Pass ( Wash 5 times) Dry cleaning laundry Pass Pass (5 times laundry)
【００２９】実施例４ 綿１００％の平織シーツ地（目付９０ｇ／ｍ2 ）を下記
配合の加工液を用いて加工を行なった。 加工液の配合 ・製造例３の化合物 ２０ｇ ・ 水 ７８ｇ ・アンチブレーズＫ−１９Ａ ２ｇ （オルブライトウイルソン社製水溶性メチルホスホン酸
エステル誘導体） 綿布を加工液に浸漬しマングルで絞り（絞り率９０％）
予備乾燥１２０℃×２分後、キュアリング１６０℃×２
分行なった。次に過炭酸ソーダ０．３％の溶液で、ソー
ピング、湯水洗を行ない乾燥した。防炎剤付着量固形分
５％。Example 4 A plain weave sheet cloth (weight per unit area: 90 g / m 2 ) made of 100% cotton was processed using a processing liquid having the following composition. Blending of processing liquid-Compound of Production Example 3 20 g-Water 78 g-Anti-Blaze K-19A 2 g (water-soluble methylphosphonate derivative from Albright Wilson Co.) Dip cotton cloth in processing liquid and squeeze with mangle (squeeze ratio 90%)
Pre-drying 120 ℃ × 2 minutes, curing 160 ℃ × 2
Done in minutes. Next, with a solution of sodium percarbonate 0.3%, soaping, washing with hot water and drying were performed. 5% solid content of flameproofing agent.
【００３０】比較例４ 製造例３の化合物２０ｇ及び水８０ｇの溶液を用いて、
同様の方法にて加工した。防炎剤付着量固形分５％。防
炎性能は防炎製品分類項目中の「寝具類、シーツ用途」
の燃焼試験（４５度、メセナミン法）により評価した。 実施例４ 比較例４ 防炎加工布の風合い（感触） 良好 ○ 硬い × （剛軟度・縦） ３５mm ５０mm （剛軟度・横） ３３mm ４０mm 防炎性能・加工上り ２．５cm ２．５cm （平均炭化長）３０回洗濯 ２．５cm ３．０cm （水洗い洗濯） （合格） （合格）Comparative Example 4 Using a solution of 20 g of the compound of Preparation Example 3 and 80 g of water,
It processed by the same method. 5% solid content of flameproofing agent. Flameproof performance is "bedding, sheets use" in the category of flameproof products
The burning test (45 degrees, mesenamine method) was evaluated. Example 4 Comparative Example 4 Good texture (feel) of flameproof fabric ○ Hard x (Bending flexibility / length) 35mm 50mm (Bending flexibility / width) 33mm 40mm Flameproofing performance / working finish 2.5cm 2.5cm ( Average carbonization length) Wash 30 times 2.5cm 3.0cm (Wash in water) (Pass) (Pass)
【００３１】実施例５ ポリエステル４０％／綿６０％のドビー交織布（目付１
５０ｇ／ｍ2 ）を下記配合の加工液を用いて、実施例１
と同じ方法で加工した。この加工布の防炎性能は、「防
炎物品」分類項目中の「カーテン（イ）ラベル性能」の
燃焼試験（４５度ミクロバーナー法）により評価した。 加工液の配合 ・製造例１の化合物 ６０ｇ 水 ３０ｇ ・水溶性化合物又は １０ｇ ・エマルジョン（固形分） 水溶状化合物の種類 風合い 防炎性 ────────────────────────────────── （感触） （剛軟度） 製造例４の化合物 良好 ○ （縦）６０mm 合格 （横）３０mm フアイロール５１ 良好 ○ （縦）５７mm 合格 （横）３２mm アンチブレーズＫ−１９Ａ 良好 ○ （縦）６２mm 合格 （横）３５mmExample 5 Dobby woven fabric of 40% polyester / 60% cotton (Basis weight 1
50 g / m 2 ) in Example 1 using a working fluid having the following composition
Processed in the same way as. The flameproof performance of this processed cloth was evaluated by a combustion test (45 degree microburner method) of "curtain (a) label performance" in the "flameproof article" classification item. Blending of processing liquid ・ Compound of Production Example 1 60 g Water 30 g ・ Water-soluble compound or 10 g ・ Emulsion (solid content) Type of water-soluble compound Texture and flame resistance ───────────────── ────────────────── (Feeling) (Bending flexibility) Compound of Production Example 4 Good ○ (Vertical) 60 mm Pass (Horizontal) 30 mm Fiber roll 51 Good ○ (Vertical) 57 mm Pass (horizontal) 32 mm Anti-blaze K-19A Good ○ (vertical) 62 mm Pass (horizontal) 35 mm
【００３２】比較例５ 実施例５と同様にして加工布を作成して防炎性能を調べ
た。加工液中の水溶化合物又はエマルジョンとしては、
エチレングリコール、ジメチルメチルホスホネート（Ｄ
ＭＭＰ）、トリメチルホスフェート（ＴＭＰ）、トリス
クロロエチルホスフェート（ＴＣＥＰ）、トリスジクロ
ロプロピルホスフェート（ＴＤＣＰＰ）及び燐酸アンモ
ニウムを用いた。Comparative Example 5 A processed cloth was prepared in the same manner as in Example 5 and its flameproof performance was examined. As the water-soluble compound or emulsion in the processing liquid,
Ethylene glycol, dimethyl methylphosphonate (D
MMP), trimethyl phosphate (TMP), tris chloroethyl phosphate (TCEP), tris dichloropropyl phosphate (TDCPP) and ammonium phosphate were used.
【００３３】 水溶状化合物又は 風合い 防炎性 エマルジョンの種類 （感触） （剛軟度） ────────────────────────────── エチレングリコール 硬い× （縦）７４mm 合格 （横）５０mm ＤＭＭＰ 硬い× （縦）７５mm 合格 （横）５５mm ＴＭＰ 硬い× （縦）７５mm 合格 （横）５６mm ＴＣＥＰの乳化物 硬い× （縦）７３mm 合格 （横）４９mm ＴＤＣＰＰの乳化物 硬い× （縦）７２mm 合格 （横）４８mm リン酸アンモニウム 硬い× （縦）７８mm 合格 （横）５８mmWater-soluble compound or texture Flame-retardant type of emulsion (feel) (flexibility) ──────────────────────────── ── Ethylene glycol Hard × (vertical) 74mm Pass (horizontal) 50mm DMMP Hard × (vertical) 75mm Pass (horizontal) 55mm TMP Hard × (vertical) 75mm Pass (horizontal) 56mm TCEP emulsion Hard × (vertical) 73mm Pass (Horizontal) 49mm TDCPP emulsion Hard x (Vertical) 72mm Pass (Horizontal) 48mm Ammonium phosphate Hard x (Vertical) 78mm Pass (Horizontal) 58mm
【００３４】[0034]
【発明の効果】本発明方法によれば、従来困難であった
セルロース繊維材料に風合いの優れた耐久性のある防炎
性能を付与し、更に従来不可能であったセルロース系繊
維と合成繊維、特にポリエステル繊維との混用品に風合
いの優れた、耐久性のある防炎性能を付与することがで
きる。また、本発明の方法により、優れた性能を有する
防炎性繊維製品を製造することができる。EFFECTS OF THE INVENTION According to the method of the present invention, it is possible to impart a durable and flameproof performance with an excellent texture to a cellulose fiber material which has been difficult in the past, and further, a cellulose type fiber and a synthetic fiber which have been impossible in the past. In particular, it is possible to impart durable flameproof performance with excellent texture to a mixed product with polyester fibers. Further, by the method of the present invention, a flameproof fiber product having excellent performance can be manufactured.
フロントページの続き (72)発明者 田中 信 大阪府茨木市耳原３−４−１ 帝人株式会 社繊維研究所内 (72)発明者 宮本 龍雄 大阪府大阪市中央区南本町１−６−７ 帝 人株式会社大阪本社内 (72)発明者 刀根 正先 京都府八幡市男山雄徳７ (72)発明者 中村 秋義 京都府京都市左京区浄土寺上南田町１ (72)発明者 広瀬 準 京都府八幡市八幡柿木垣内９−40 (72)発明者 久田 晴彦 大阪府八尾市山本町南４−10−14Front page continuation (72) Inventor Shin Tanaka 3-4-1 Mihara, Ibaraki City, Osaka Prefecture Teijin Ltd. Textile Research Institute (72) Inventor Tatsuo Miyamoto 1-6-7 Minamihonmachi, Chuo-ku, Osaka City, Osaka Teijin Osaka Head Office (72) Inventor, Tadashi Tone, Yatsunori Otoyama, Yawata City, Kyoto Prefecture (72) Inventor, Akiyoshi Nakamura, 1 Kyonantacho, Jodoji Temple, Sakyo Ward, Kyoto City, Kyoto Prefecture (72) Associate Hirose, Yawata City, Kyoto Prefecture Hachiman Persimmon Kigarai 9-40 (72) Inventor Haruhiko Hisada 4-10-14 Minami Yamamotocho, Yao City, Osaka Prefecture
Claims (4)
るテトラキスヒドロキシメチルホスホニウム塩１モルと
尿素０．２〜３．０モルとの反応物（固形分として）１
００重量部に、水溶性メチルホスホン酸エステル誘導体
５〜１００重量部を配合した加工液を用いて、セルロー
ス系繊維材料を処理することを特徴とする風合いの改良
されたセルロース系繊維材料の耐久性防炎加工法。1. A tetrakishydroxymethylphosphonium salt represented by the general formula (HOCH 2 ) 4 PX (wherein X represents Cl, 1/2 SO 4 or OH) and 0.2 to 3.0 mol of urea. Reaction with (as solids) 1
A cellulose-based fiber material is treated with a processing liquid in which 5 to 100 parts by weight of a water-soluble methylphosphonate derivative is mixed with 00 parts by weight, and the durability of the cellulose-based fiber material with improved texture is treated. Flame processing method.
が、ジメチルメチルホスホネート（１モル）、五酸化リ
ン（０．４〜１．０モル）、エチレングリコール（０．
１〜１．０モル）及びエチレンオキサイド（１．５〜
５．０モル）の反応物又は一般式 【化１】 （式中ｎは０又は１） で示される化合物から選ばれた
１種又は２種以上の混合物である請求項１の方法。2. A water-soluble methylphosphonate derivative is dimethylmethylphosphonate (1 mol), phosphorus pentoxide (0.4 to 1.0 mol), ethylene glycol (0.
1-1.0 mol) and ethylene oxide (1.5-
5.0 mol) of the reaction product or the general formula: The method according to claim 1, wherein the compound is one or a mixture of two or more selected from compounds represented by the formula (n is 0 or 1).
維又はセルロース繊維／合成繊維混用である請求項１の
方法。3. The method of claim 1, wherein the cellulosic fiber material is a cellulosic fiber or a cellulosic fiber / synthetic fiber blend.
の方法。4. The synthetic fiber is polyester.
the method of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6095692A JPH06101176A (en) | 1992-02-18 | 1992-02-18 | Durable flame-resistant treatment of cellulose-based fiber material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6095692A JPH06101176A (en) | 1992-02-18 | 1992-02-18 | Durable flame-resistant treatment of cellulose-based fiber material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06101176A true JPH06101176A (en) | 1994-04-12 |
Family
ID=13157361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6095692A Pending JPH06101176A (en) | 1992-02-18 | 1992-02-18 | Durable flame-resistant treatment of cellulose-based fiber material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06101176A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0709518A1 (en) * | 1994-10-25 | 1996-05-01 | Albright & Wilson Limited | Flame retardant and fabric softening treatment of textile materials |
| KR100310273B1 (en) * | 1999-10-20 | 2001-09-29 | 박호군 | Nonflammable Cellulose Fiber Structures and a Process of Making Them |
| JP2003510478A (en) * | 1999-09-27 | 2003-03-18 | ユニバーシティ・オブ・ジョージア・リサーチ・ファウンデイション・インコーポレイテッド | Formaldehyde-free flame retardant treatment for cellulose-containing materials |
| CN104522915A (en) * | 2014-12-23 | 2015-04-22 | 安徽中天印染股份有限公司 | Method for making cool summer uniform fabric |
| CN107323061A (en) * | 2017-06-30 | 2017-11-07 | 常州市瑞泰物资有限公司 | A kind of preparation method of thorn-proof composite material |
-
1992
- 1992-02-18 JP JP6095692A patent/JPH06101176A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0709518A1 (en) * | 1994-10-25 | 1996-05-01 | Albright & Wilson Limited | Flame retardant and fabric softening treatment of textile materials |
| JP2003510478A (en) * | 1999-09-27 | 2003-03-18 | ユニバーシティ・オブ・ジョージア・リサーチ・ファウンデイション・インコーポレイテッド | Formaldehyde-free flame retardant treatment for cellulose-containing materials |
| KR100310273B1 (en) * | 1999-10-20 | 2001-09-29 | 박호군 | Nonflammable Cellulose Fiber Structures and a Process of Making Them |
| CN104522915A (en) * | 2014-12-23 | 2015-04-22 | 安徽中天印染股份有限公司 | Method for making cool summer uniform fabric |
| CN107323061A (en) * | 2017-06-30 | 2017-11-07 | 常州市瑞泰物资有限公司 | A kind of preparation method of thorn-proof composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7736696B2 (en) | Methods, systems, and compositions for fire retarding substrates | |
| JP3495330B2 (en) | Esterified triclosan derivatives as improved textile antimicrobial agents | |
| US3857727A (en) | Textile finishing | |
| US4776854A (en) | Method for flameproofing cellulosic fibrous materials | |
| WO2014100842A1 (en) | Non-fibrillating flame resistant cellulosic fabric, its use and method for producing the same | |
| JP2007182652A (en) | Flame retarding processing agent for polyester fiber and processing method | |
| EP2473666B1 (en) | Flame retardant coating composition for textiles and process for coating textile substrates | |
| JPH06101176A (en) | Durable flame-resistant treatment of cellulose-based fiber material | |
| CA2480283A1 (en) | Textile mill applications of cellulosic based polymers to provide appearance and integrity benefits to fabrics during laundering and in-wear | |
| JP2007131968A (en) | Flame-retardant finishing agent for polyester fiber and method for processing the same | |
| JP3862063B2 (en) | Method for dyeing polyester fabric having flame retardancy and antibacterial properties | |
| JPS6364545B2 (en) | ||
| JPS63190080A (en) | Treatment of fiber material | |
| JP2007131967A (en) | Flame-retardant finishing agent for polyester fiber and method for processing the same | |
| JPH055278A (en) | Flame proofing processing of cellulosic fiber | |
| JP2007070751A (en) | Flame retardant of polyester-based fiber and method for processing the same | |
| WO2000022222A1 (en) | Methods for reducing the flammability of cellulosic substrates | |
| US2454245A (en) | Flame-retarding material and process of making the same | |
| JPH0533269A (en) | Flame-resistant processing of cellulosic fiber web | |
| JP2005054275A (en) | Fiber structure and method for producing the same | |
| JP2000303355A (en) | Flame-retardant processing method for polyester/ cellulose blended textile structural product | |
| JPH062272A (en) | Production of antimicrobial chlorine-containing polyacrylonitrile-based yarn | |
| JPS6125829B2 (en) | ||
| Nussinovitch et al. | Textiles | |
| JPH04333657A (en) | Fire-resistant processing of cellulosic fiber fabric |