JP7549863B2 - Flame retardant treatment for polyester fibers - Google Patents
Flame retardant treatment for polyester fibers Download PDFInfo
- Publication number
- JP7549863B2 JP7549863B2 JP2020116034A JP2020116034A JP7549863B2 JP 7549863 B2 JP7549863 B2 JP 7549863B2 JP 2020116034 A JP2020116034 A JP 2020116034A JP 2020116034 A JP2020116034 A JP 2020116034A JP 7549863 B2 JP7549863 B2 JP 7549863B2
- Authority
- JP
- Japan
- Prior art keywords
- flame
- flame retardant
- phosphonic acid
- formula
- polyester fibers
- 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.)
- Active
Links
- 239000000835 fiber Substances 0.000 title claims description 85
- 239000003063 flame retardant Substances 0.000 title claims description 82
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 74
- 229920000728 polyester Polymers 0.000 title claims description 70
- -1 phosphonic acid compound Chemical class 0.000 claims description 80
- 239000003795 chemical substances by application Substances 0.000 claims description 42
- 239000007864 aqueous solution Substances 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000004744 fabric Substances 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 15
- 238000012545 processing Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003814 drug Substances 0.000 description 8
- 229940079593 drug Drugs 0.000 description 8
- 150000003009 phosphonic acids Chemical class 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 5
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- UOKRBSXOBUKDGE-UHFFFAOYSA-N butylphosphonic acid Chemical compound CCCCP(O)(O)=O UOKRBSXOBUKDGE-UHFFFAOYSA-N 0.000 description 3
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 3
- 229940043276 diisopropanolamine Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 208000012886 Vertigo Diseases 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- CEDDGDWODCGBFQ-UHFFFAOYSA-N carbamimidoylazanium;hydron;phosphate Chemical compound NC(N)=N.OP(O)(O)=O CEDDGDWODCGBFQ-UHFFFAOYSA-N 0.000 description 2
- 239000002781 deodorant agent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- JOLLRRMLUVEWDW-UHFFFAOYSA-N 2,2-dimethylpropylphosphonic acid Chemical compound CC(C)(C)CP(O)(O)=O JOLLRRMLUVEWDW-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- HAEFDDOAYBQRGK-UHFFFAOYSA-N 2-methylpropylphosphonic acid Chemical compound CC(C)CP(O)(O)=O HAEFDDOAYBQRGK-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- OGBVRMYSNSKIEF-UHFFFAOYSA-N Benzylphosphonic acid Chemical compound OP(O)(=O)CC1=CC=CC=C1 OGBVRMYSNSKIEF-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
- 239000004970 Chain extender Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- GJWAEWLHSDGBGG-UHFFFAOYSA-N hexylphosphonic acid Chemical compound CCCCCCP(O)(O)=O GJWAEWLHSDGBGG-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DWHMMGGJCLDORC-UHFFFAOYSA-N methoxy(methyl)phosphinic acid Chemical compound COP(C)(O)=O DWHMMGGJCLDORC-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- NJGCRMAPOWGWMW-UHFFFAOYSA-N octylphosphonic acid Chemical compound CCCCCCCCP(O)(O)=O NJGCRMAPOWGWMW-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- CKVICYBZYGZLLP-UHFFFAOYSA-N pentylphosphonic acid Chemical compound CCCCCP(O)(O)=O CKVICYBZYGZLLP-UHFFFAOYSA-N 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
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- NSETWVJZUWGCKE-UHFFFAOYSA-N propylphosphonic acid Chemical compound CCCP(O)(O)=O NSETWVJZUWGCKE-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は、新規なポリエステル系繊維用難燃処理剤に関する。 The present invention relates to a novel flame retardant treatment for polyester fibers.
ポリエステル系繊維を用いた素材（織物生地等）は、耐久性、伸縮性、汗速乾性等に優れることから、衣料、自動車内装等をはじめ、各種の産業資材に幅広く用いられている。これらの用途にポリエステル系繊維を用いるに際しては、ポリエステル系繊維に難燃性を付与するための難燃化処理が行われる。 Materials made from polyester fibers (woven fabrics, etc.) are excellent in durability, elasticity, and quick-drying properties, and are therefore widely used in a variety of industrial materials, including clothing and automobile interiors. When using polyester fibers for these purposes, they are subjected to flame-retardant treatment to give them flame retardancy.
難燃化処理する方法としては、原料樹脂に難燃成分を添加し、紡糸することにより難燃性繊維を製造する方法のほか、製造された繊維を難燃剤で処理することにより難燃性繊維を製造する方法がある。 Methods for flame retardant treatment include adding a flame retardant component to the raw resin and spinning it to produce flame retardant fibers, as well as treating the fibers produced with a flame retardant to produce flame retardant fibers.
前者の方法としては、例えばポリエステル系繊維重量に対して、リン原子の含有量が１０００～１６０００ｐｐｍとなるように下記一般式（１）で表されるリン化合物と、０．００５ｗｔ％～１．５ｗｔ％となるように鎖伸長剤が配合されているポリエステル系繊維が提案されている。このような方法では、紡糸段階で難燃成分を添加する必要があるため、既存の繊維製品に対して必要に応じて所望の難燃性を付与するということができない（特許文献１）。
これに対し、後者の方法では、既存の繊維製品に対して必要に応じて所望の難燃性を後処理工程で付与できるので、工業上利用しやすい。このような方法で用いられている難燃剤としては、水溶解性リン系難燃剤が知られている。これは、例えば（５－エチル－２－メチル－２－オキソ－１，３，２λ（５）－ジオキサホスフィナン－５－イル）メチル＝メチル＝メチルホスホナートとビス［（５－エチル－２－メチル－２－オキソ－１，３，２λ（５）－ジオキサホスフィナン－５－イル）メチル］＝メチルホスホナートの混合物(丸菱油化工業株式会社製「ノンネンＲ０３１－５」)のような環状ホスホン酸エステル類が難燃成分として含まれているものであり、広く用いられている難燃剤の一つである。しかし、前記のような難燃剤は、揮発性を有することから、例えば難燃剤を含む処理布を乾燥する際に、用いる乾燥機の内壁、処理布等を揮発成分で汚染してしまうという問題がある。また、前記のような環状ホスホン酸エステル類は、化学兵器の禁止及び特定物質の規制等に関する法律(いわゆる化兵法)の中で化学兵器の前駆物質になるものとして指定されており、使用者は使用の実績数量等を経済産業大臣に届け出をしなければならないという事務処理上の手間がかかる。 In contrast, the latter method can impart the desired flame retardancy to existing textile products as needed in a post-treatment process, making it easy to use industrially. Water-soluble phosphorus-based flame retardants are known as flame retardants used in this method. These flame retardants contain cyclic phosphonates as flame retardant components, such as a mixture of (5-ethyl-2-methyl-2-oxo-1,3,2λ(5)-dioxaphosphinan-5-yl)methyl methyl phosphonate and bis[(5-ethyl-2-methyl-2-oxo-1,3,2λ(5)-dioxaphosphinan-5-yl)methyl] methyl phosphonate ("Nonnen R031-5" manufactured by Marubishi Yuka Kogyo Co., Ltd.), and are one of the widely used flame retardants. However, since such flame retardants are volatile, there is a problem that, for example, when drying a treated cloth containing a flame retardant, the inner walls of the dryer used, the treated cloth, etc. are contaminated with volatile components. In addition, cyclic phosphonates such as those mentioned above are designated as precursors to chemical weapons under the Act on the Prohibition of Chemical Weapons and the Control of Specified Substances (the so-called Chemical Weapons Act), and users are required to notify the Minister of Economy, Trade and Industry of the actual quantities used, which is a hassle in terms of paperwork.
また、リン酸グアニジン(例えば丸菱油化工業株式会社製「ノンネン９８４」)、リン酸アンモニウム、低分子量ポリリン酸アンモニウム等の水溶性リン酸アミン塩も、ポリエステル系繊維の難燃加工剤として汎用されている。しかし、こういった水溶性リン酸塩タイプは、上記環状ホスホン酸エステル類に比較して、特にポリエステル系繊維に対しては難燃性を付与する能力が低く、被処理布に対して相当量を付与する必要がある。そのため、被処理布表面上に経時的に白色固体が析出し、その外観を低下させるおそれがある。結晶の析出を抑制する目的で酸性リン酸エステルのアミン塩等の添加も提案されているものの、これらはさらに難燃性能に劣り、被処理布に対して多量の添加が必要となる。 Water-soluble amine phosphates, such as guanidine phosphate (e.g., Nonnen 984 manufactured by Marubishi Yuka Kogyo Co., Ltd.), ammonium phosphate, and low-molecular-weight ammonium polyphosphate, are also widely used as flame retardant agents for polyester fibers. However, compared with the above-mentioned cyclic phosphonates, these water-soluble phosphate types have a lower ability to impart flame retardancy, particularly to polyester fibers, and a significant amount must be added to the treated fabric. As a result, white solids may precipitate over time on the surface of the treated fabric, degrading its appearance. The addition of amine salts of acidic phosphates and the like has also been proposed to suppress the precipitation of crystals, but these have even worse flame retardant performance and require the addition of large amounts to the treated fabric.
このようなグアニジン系化合物を用いた難燃剤としては、例えばアルキルホスホン酸及びグアニジン系化合物（特にグアニル尿素）からなる塩を水に溶解又は分散させてなる水系難燃加工剤を含む処理液が知られている（特許文献２）。しかし、アルキルホスホン酸とグアニジン系化合物との塩も、所望の難燃性を達成するためには相当量の添加が必要となる。その結果として、難燃化された布には水系の難燃剤に由来するキワツキ（際付き：繊維製品表面に出現する滲み）が発生したり、風合いが失われて硬くなったりするため、用途は限定的にならざるを得ない。 As a flame retardant using such a guanidine compound, for example, a treatment liquid containing a water-based flame retardant processing agent obtained by dissolving or dispersing a salt of an alkylphosphonic acid and a guanidine compound (particularly guanylurea) in water is known (Patent Document 2). However, a considerable amount of the salt of an alkylphosphonic acid and a guanidine compound must also be added to achieve the desired flame retardancy. As a result, the flame-retarded fabric suffers from edges (bleeds that appear on the surface of a textile product) due to the water-based flame retardant, loses texture, and becomes hard, so its uses are inevitably limited.
以上のように、ポリエステル系繊維が本来有する風合い等を維持しながら、高い難燃性を付与できる難燃処理剤の開発が切望されているが、そのような難燃処理剤の開発に至っていないのが現状である。 As described above, there is a strong demand for the development of a flame retardant treatment that can impart high flame retardancy while maintaining the texture and other characteristics inherent to polyester fibers, but such a flame retardant treatment has not yet been developed.
従って、本発明の主な目的は、ポリエステル系繊維本来の物性を実質的に維持しつつも、高い難燃性を付与することができる難燃処理剤を提供することにある。 Therefore, the main object of the present invention is to provide a flame retardant treatment agent that can impart high flame retardancy while substantially maintaining the inherent physical properties of polyester fibers.
本発明者らは、上記問題点に鑑みて鋭意研究を重ねた結果、特定の成分を含む組成物をポリエステル系繊維用の難燃処理剤として採用することによって上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of extensive research into the above problems, the inventors discovered that the above object could be achieved by using a composition containing specific components as a flame retardant treatment for polyester fibers, and thus completed the present invention.
すなわち、本発明は、下記のポリエステル系繊維用難燃処理剤に係る。
１． ポリエステル系繊維に難燃性を付与するための組成物であって、
（１）（ａ）下記式１－１及び式１－２
で示されるホスホン酸化合物の少なくとも１種及び
（ｂ）下記式２－１及び式２－２
で示される窒素含有化合物の少なくとも１種
が水に溶解してなる水溶液であって、
（２）前記水溶液のｐＨが４～８である
ことを特徴とするポリエステル系繊維用難燃処理剤。
２． ホスホン酸化合物及び窒素含有化合物のモル比（ホスホン酸化合物：窒素含有化合物）＝１：０．４～１：５である、前記項１に記載のポリエステル系繊維用難燃処理剤。
３． （ａ）下記式１－１及び式１－２
で示されるホスホン酸化合物の少なくとも１種及び
（ｂ）下記式２－１及び式２－２
で示される窒素含有化合物の少なくとも１種
がポリエステル系繊維に付着してなる難燃性ポリエステル系繊維。
４． 前記項１又は２に記載のポリエステル系繊維用難燃処理剤を用いてポリエステル系繊維を難燃処理する工程を含む、難燃性ポリエステル系繊維の製造方法。
That is, the present invention relates to the following flame retardant treatment agent for polyester fibers.
1. A composition for imparting flame retardancy to polyester-based fibers, comprising:
(1) (a) Formula 1-1 and Formula 1-2 below
and (b) at least one of phosphonic acid compounds represented by the following formulas 2-1 and 2-2:
An aqueous solution in which at least one nitrogen-containing compound represented by the formula:
(2) A flame retardant treatment agent for polyester fibers, characterized in that the pH of the aqueous solution is 4 to 8.
2. The flame retardant treatment agent for polyester fibers according to item 1, wherein the molar ratio of the phosphonic acid compound and the nitrogen-containing compound (phosphonic acid compound:nitrogen-containing compound) is 1:0.4 to 1:5.
3. (a) Formula 1-1 and Formula 1-2 below
and (b) at least one of phosphonic acid compounds represented by the following formulas 2-1 and 2-2:
The flame-retardant polyester fiber is obtained by adhering to the polyester fiber at least one nitrogen-containing compound represented by the following formula:
4. A method for producing a flame-retardant polyester fiber, comprising a step of flame-retarding a polyester fiber with the flame-retardant treatment agent for polyester fiber according to item 1 or 2.
本発明によれば、ポリエステル系繊維本来の物性を実質的に維持しつつも、高い難燃性を付与することができる難燃処理剤を提供することができる。 The present invention provides a flame retardant treatment agent that can impart high flame retardancy while substantially maintaining the inherent physical properties of polyester fibers.
特に、本発明では、特定のホスホン酸化合物と特定の窒素含有化合物とを含む水性組成物を採用していることから、難燃処理前においてポリエステル系繊維が本来的に有している性質（風合い）を保持しつつも、高い難燃性をポリエステル系繊維に付与することができる。 In particular, the present invention employs an aqueous composition containing a specific phosphonic acid compound and a specific nitrogen-containing compound, which makes it possible to impart high flame retardancy to polyester fibers while retaining the inherent properties (texture) of the polyester fibers prior to flame retardant treatment.
ホスホン酸化合物は、酸性度が非常に高いため、特に高温高湿下では繊維又は生地の脆化を進め、その風合い等を著しく低下させるおそれがある。このため、酸性度を和らげるために塩基性化合物を用いることが考えられるが、塩基性化合物の配合がホスホン酸化合物の難燃性能に悪影響を及ぼし、特にアルカリ金属塩では難燃性が極端に低下してしまう。このため、ポリエステル系繊維に対する高い難燃性の付与と、ポリエステル系繊維本来の物性の維持とを両立させることは困難とされている。 Phosphonic acid compounds are very acidic, and therefore may embrittle fibers or fabrics, especially under high temperature and humidity conditions, and significantly reduce their texture. For this reason, it is possible to use basic compounds to reduce the acidity, but the incorporation of basic compounds has a negative effect on the flame retardant performance of phosphonic acid compounds, and in particular, the flame retardant performance is drastically reduced in the case of alkali metal salts. For this reason, it is considered difficult to impart high flame retardancy to polyester fibers while maintaining the original physical properties of polyester fibers.
これに対し、本発明では、特定のホスホン酸系化合物と特定の窒素含有化合物との組み合わせを採用することにより、ポリエステル系繊維に対して高い難燃性を付与するとともに、ポリエステル系繊維本来の物性を効果的に維持することに成功したものである。より具体的には、特定のホスホン酸化合物と特定の窒素含有化合物との組み合わせにより生成する塩は、難燃成分としてのホスホン酸化合物の難燃性を阻害しないことを見出し、処理対象となるポリエステル系繊維（難燃処理前のもの）が本来有する物性（風合い等）を効果的に維持しつつも、高い難燃性をもたせることが可能となる。 In contrast, the present invention employs a combination of a specific phosphonic acid compound and a specific nitrogen-containing compound, thereby successfully imparting high flame retardancy to polyester fibers while effectively maintaining the inherent physical properties of the polyester fibers. More specifically, it has been discovered that the salt produced by the combination of a specific phosphonic acid compound and a specific nitrogen-containing compound does not inhibit the flame retardancy of the phosphonic acid compound as a flame retardant component, making it possible to impart high flame retardancy while effectively maintaining the inherent physical properties (texture, etc.) of the polyester fibers to be treated (before the flame retardant treatment).
また、本発明難燃処理剤に含まれる特定のホスホン酸化合物は、比較的少量でもポリエステル系繊維に対して高い難燃性を付与することができるので、本発明難燃処理剤が水溶液の形態であるにもかかわらず、水系難燃処理剤の使用時に発生するキワツキの発生を抑制ないしは防止することができる。 In addition, the specific phosphonic acid compound contained in the flame retardant treatment agent of the present invention can impart high flame retardancy to polyester fibers even in a relatively small amount, so even though the flame retardant treatment agent of the present invention is in the form of an aqueous solution, it can suppress or prevent the occurrence of eddying that occurs when using a water-based flame retardant treatment agent.
さらに、本発明の難燃処理剤は、環状ホスホン酸エステル類等のような揮発による問題も起こりにくいため、乾燥機の内壁、処理後の繊維の汚染等を効果的に抑制ないしは防止することができる。 Furthermore, the flame retardant treatment agent of the present invention is less likely to cause problems due to volatilization, as occurs with cyclic phosphonate esters, and can effectively suppress or prevent contamination of the inner walls of dryers and fibers after treatment.
このような特徴を有する本発明の難燃処理剤は、ポリエステル系繊維及びそれを用いた繊維製品（衣服のほか、車両、船舶、航空機等の内装材、住居用内装材等）の難燃化に好適に用いることができる。 The flame retardant treatment agent of the present invention, which has these characteristics, can be suitably used to make polyester fibers and textile products using them flame retardant (in addition to clothing, interior materials for vehicles, ships, aircraft, etc., and interior materials for homes, etc.).
１．ポリエステル系繊維用難燃処理剤
本発明のポリエステル系繊維用難燃処理剤（本発明難燃処理剤）は、ポリエステル系繊維に難燃性を付与するための組成物であって、
（１）（ａ）下記式１－１及び式１－２
で示されるホスホン酸化合物の少なくとも１種及び
（ｂ）下記式２－１及び式２－２
で示される窒素含有化合物の少なくとも１種
が水に溶解してなる水溶液であって、
（２）前記水溶液のｐＨが４～８である
ことを特徴とする。
1. Flame retardant treatment agent for polyester fibers The flame retardant treatment agent for polyester fibers of the present invention (the flame retardant treatment agent of the present invention) is a composition for imparting flame retardancy to polyester fibers,
(1) (a) Formula 1-1 and Formula 1-2 below
and (b) at least one of phosphonic acid compounds represented by the following formulas 2-1 and 2-2:
An aqueous solution in which at least one nitrogen-containing compound represented by the formula:
(2) The aqueous solution has a pH of 4 to 8.
ホスホン酸化合物は、前記の式１－１及び式１－２で示される化合物の少なくとも１種を用いることができる。 The phosphonic acid compound can be at least one of the compounds shown in formula 1-1 and formula 1-2.
前記式１－１の化合物は、１－ヒドロキシエタン－１，１－ジホスホン酸である。また、前記式１－２の化合物としては、例えばメチルホスホン酸、エチルホスホン酸、ｎ－プロピルホスホン酸、ｎ－ブチルホスホン酸、イソブチルホスホン酸、ｎ－ペンチルホスホン酸、ｎ－へキシルホスホン酸、ネオペンチルホスホン酸、ｎ－オクチルホスホン酸、フェニルホスホン酸、ベンジルホスホン酸等が挙げられる。 The compound of formula 1-1 is 1-hydroxyethane-1,1-diphosphonic acid. Examples of the compound of formula 1-2 include methylphosphonic acid, ethylphosphonic acid, n-propylphosphonic acid, n-butylphosphonic acid, isobutylphosphonic acid, n-pentylphosphonic acid, n-hexylphosphonic acid, neopentylphosphonic acid, n-octylphosphonic acid, phenylphosphonic acid, and benzylphosphonic acid.
窒素含有化合物は、前記の式２－１及び式２－２で示される化合物の少なくとも１種を用いることができる。 The nitrogen-containing compound can be at least one of the compounds represented by formula 2-1 and formula 2-2.
前記式２－１の化合物としては、例えばアンモニア、モノエタノールアミン、モノイソプロパノールアミン、ジエタノールアミン、ジイソプロパノールアミン、トリエタノールアミン等が挙げられる。また、前記式２－２の化合物としては、モルホリン、ピペラジンが挙げられる。 Examples of the compound of formula 2-1 include ammonia, monoethanolamine, monoisopropanolamine, diethanolamine, diisopropanolamine, and triethanolamine. Examples of the compound of formula 2-2 include morpholine and piperazine.
本発明では、上記のような窒素含有化合物とホスホン酸化合物とを併用することにより、ホスホン酸化合物の難燃性能を阻害することなく、本発明難燃処理剤（水溶液）のｐＨを中性付近に制御することができる結果、ポリエステル系繊維の本来の特性を効果的に維持しつつ、良好な難燃性を付与することが可能となる。前記ホスホン酸化合物の単独水溶液は通常ｐＨ１～２の強酸であるため、当該ホスホン酸化合物単独で加工された繊維材料は、特に高温高湿下で脆化するという問題が起こる。これに対し、本発明において、特定のホスホン酸化合物とともに特定の窒素含有化合物を併用することにより前記問題を解消しつつ、高度な難燃性を付与することができる。 In the present invention, by using the above-mentioned nitrogen-containing compound in combination with a phosphonic acid compound, the pH of the flame retardant treatment agent (aqueous solution) of the present invention can be controlled to near neutral without inhibiting the flame retardant performance of the phosphonic acid compound, and as a result, it is possible to impart good flame retardancy while effectively maintaining the original characteristics of polyester-based fibers. Since an aqueous solution of the phosphonic acid compound alone is usually a strong acid with a pH of 1 to 2, a problem occurs in that fiber materials processed with the phosphonic acid compound alone become embrittled, especially under high temperature and high humidity. In contrast, in the present invention, by using a specific nitrogen-containing compound in combination with a specific phosphonic acid compound, the above problem can be solved while imparting a high level of flame retardancy.
かかる見地より、ホスホン酸化合物及び窒素含有化合物のモル比は、（ホスホン酸化合物：窒素含有化合物）＝１：０．４～１：５の範囲内とすることが好ましい。これによって、より確実に難燃処理剤のｐＨを４～８程度（特に４．５～６．５）に制御することができる。ｐＨ４未満の場合は、ポリエステル系繊維の脆化が誘発されるおそれがある。また、ｐＨ８を超過した場合は、高い難燃性が得られなくなることがある。なお、本発明におけるｐＨは、温度２０℃におけるｐＨである。 From this perspective, it is preferable that the molar ratio of the phosphonic acid compound and the nitrogen-containing compound is within the range of (phosphonic acid compound:nitrogen-containing compound) = 1:0.4 to 1:5. This makes it possible to more reliably control the pH of the flame retardant treatment agent to about 4 to 8 (particularly 4.5 to 6.5). If the pH is less than 4, there is a risk that embrittlement of the polyester fiber will be induced. Also, if the pH exceeds 8, high flame retardancy may not be obtained. Note that the pH in this invention is the pH at a temperature of 20°C.
本発明難燃処理剤においては、本発明の効果を妨げない範囲内において、必要に応じて他の添加剤を添加することもできる。例えば、防腐剤、消臭剤、増粘剤、樹脂バインダー、可縫製向上剤、仕上げ剤、消臭剤、柔軟剤、撥水剤、撥油剤、架橋剤（イソシアネート系、エチレンイミン系、グリシジル系）等が挙げられる。また、本発明の効果を妨げない限り、前記ホスホン酸化合物以外の難燃処理剤（ハロゲン系難燃処理剤、リン系難燃処理剤等）、前記の窒素含有化合物以外のｐＨ調整剤を含んでいても良い。 Other additives can be added to the flame retardant treatment agent of the present invention as necessary, as long as they do not impede the effects of the present invention. Examples include preservatives, deodorants, thickeners, resin binders, sewability improvers, finishing agents, deodorants, softeners, water repellents, oil repellents, crosslinking agents (isocyanate-based, ethyleneimine-based, glycidyl-based), etc. In addition, as long as they do not impede the effects of the present invention, the flame retardant treatment agent may contain flame retardants other than the phosphonic acid compound (halogen-based flame retardants, phosphorus-based flame retardants, etc.) and pH adjusters other than the nitrogen-containing compounds.
本発明難燃処理剤の形態は、通常はホスホン酸化合物及び窒素含有化合物が水に溶解してなる水溶液の形態である。この場合の濃度は、特に限定されないが、通常はホスホン酸化合物の濃度が１０質量％以上であることが好ましく、特に３０質量％以上であることがより好ましい。なお、前記濃度の上限は、例えば７０質量％程度とすることができるが、これに限定されない。 The flame retardant treatment agent of the present invention is usually in the form of an aqueous solution in which a phosphonic acid compound and a nitrogen-containing compound are dissolved in water. In this case, the concentration is not particularly limited, but it is usually preferable that the concentration of the phosphonic acid compound is 10% by mass or more, and more preferably 30% by mass or more. The upper limit of the concentration can be, for example, about 70% by mass, but is not limited to this.
本発明難燃処理剤における水溶液のｐＨは、前記のようにｐＨ＝４～８程度とし、特に４．５～６．５とすることが好ましい。このような範囲内に設定することによって、ポリエステル系繊維の本来の性能を効果的に維持しつつ、高い難燃性をポリエステル系繊維に付与することができる。 As mentioned above, the pH of the aqueous solution of the flame retardant treatment agent of the present invention is set to about pH = 4 to 8, and preferably to 4.5 to 6.5. By setting the pH within this range, it is possible to impart high flame retardancy to the polyester fiber while effectively maintaining the inherent performance of the polyester fiber.
２．ポリエステル系繊維用難燃処理剤の製造方法
本発明難燃処理剤の製造方法は、前記のような各成分を均一に混合することによって実施することができる。特に、水溶液の形態である場合は、少なくともホスホン酸化合物及び窒素含有化合物を水に溶解させる工程を含む方法を好適に採用することができる。例えば、ホスホン酸化合物の水溶液を調製する工程及び前記ホスホン酸化合物水溶液と窒素含有化合物又はその水溶液とを混合する工程を含む方法を採用することができる。
2. Method for producing flame retardant treatment agent for polyester fiber The method for producing the flame retardant treatment agent of the present invention can be carried out by uniformly mixing each component as described above. In particular, when it is in the form of an aqueous solution, a method including at least a step of dissolving a phosphonic acid compound and a nitrogen-containing compound in water can be preferably adopted. For example, a method including a step of preparing an aqueous solution of a phosphonic acid compound and a step of mixing the aqueous solution of the phosphonic acid compound with a nitrogen-containing compound or its aqueous solution can be adopted.
３．難燃性ポリエステル系繊維の製造方法
本発明は、本発明難燃処理剤を用いてポリエステル系繊維を難燃処理する工程を含む、難燃性ポリエステル系繊維の製造方法を包含する。
3. Method for Producing Flame-Retardant Polyester Fibers The present invention includes a method for producing flame-retardant polyester fibers, which comprises a step of flame-retarding polyester fibers with the flame-retardant treatment agent of the present invention.
本発明難燃処理剤により難燃性を付与するポリエステル系繊維の種類は、限定的でなく、例えばポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリトリメチレンテレフタレート等を含む繊維が挙げられる。 The types of polyester fibers to which the flame retardant treatment agent of the present invention can impart flame retardancy are not limited, and examples include fibers containing polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, etc.
本発明の効果を妨げない範囲内において、ａ）他の合成樹脂等とポリエステル樹脂との混合樹脂、ポリマーアロイ等の繊維、ｂ）ポリエステル系繊維と他の合成繊維又は天然繊維（綿、絹、麻等）と混紡された繊維等を本発明難燃処理剤の処理対象とすることもできる。また、繊維の形態も、短繊維又は長繊維のいずれであっても良い。繊維径も、限定的でなく、例えば５～５０μｍ程度とすれば良いが、これに限定されない。 Within the scope of the present invention, the flame retardant treatment agent of the present invention can treat a) mixed resins of polyester resins and other synthetic resins, fibers of polymer alloys, and b) fibers blended with polyester fibers and other synthetic fibers or natural fibers (cotton, silk, hemp, etc.). The fiber form may be either short or long. The fiber diameter is not limited, and may be, for example, about 5 to 50 μm, but is not limited thereto.
また、本発明難燃処理剤の処理対象は、ポリエステル系繊維そのもののほか、ポリエステル系繊維により作製された生地（布地、布帛）であっても良い。生地としては、織物又は不織布のいずれであっても良い。また、生地は、ポリエステル系繊維単体からなる生地に加え、ポリエステル系繊維と他の繊維（合成繊維又は天然繊維）とを含む生地であっても良い。 The subject of treatment with the flame retardant treatment agent of the present invention may be not only polyester fibers themselves, but also fabrics (cloths, fabrics) made from polyester fibers. The fabrics may be either woven or nonwoven fabrics. The fabrics may be fabrics made of polyester fibers alone, or fabrics containing polyester fibers and other fibers (synthetic or natural fibers).
生地の場合、その目付けも限定されず、例えば３０～５００ｇ／ｍ２程度とすることができるが、これに限定されない。 In the case of fabric, the basis weight is not limited either, and can be, for example, about 30 to 500 g/ m2 , but is not limited thereto.
本発明難燃処理剤による処理方法は、特に限定されず、公知の加工方法及び加工機器を使用して実施することもできる。例えば、パディング加工、バッキング加工、浸漬加工、浴中吸尽加工、スプレー加工、サーモゾル加工、グラビア加工等のいずれも適用することができる。 The method of treatment with the flame retardant treatment agent of the present invention is not particularly limited, and can be carried out using known processing methods and processing equipment. For example, any of padding processing, backing processing, immersion processing, bath exhaustion processing, spray processing, thermosol processing, gravure processing, etc. can be applied.
より具体的には、１）ポリエステル系繊維に本発明難燃処理剤を接触させる工程（接触工程）及び２）加熱下でキュアリングする工程（キュアリング工程）を含む方法を好適に採用することができる。 More specifically, a method including 1) a step of contacting the polyester fiber with the flame retardant treatment agent of the present invention (contact step) and 2) a step of curing under heat (curing step) can be preferably adopted.
接触工程では、ポリエステル系繊維に本発明難燃処理剤を接触させることができれば良く、例えばスプレー、浸漬加工等のいずれの方法も採用することができる。繊維に対して均一に処理を行い易いという観点から、浸漬加工がより好ましい。ポリエステル系繊維に対する本発明難燃処理剤の付与量は、所望の難燃性等に応じて適宜設定することができるが、通常はポリエステル系繊維１００質量部に対してホスホン酸化合物の量として１～１０質量部程度とすることができる。 In the contact step, it is sufficient to bring the flame retardant treatment agent of the present invention into contact with the polyester fiber, and any method such as spraying or immersion processing can be used. From the viewpoint of ease of uniform treatment on the fiber, immersion processing is more preferable. The amount of the flame retardant treatment agent of the present invention applied to the polyester fiber can be appropriately set according to the desired flame retardancy, etc., but the amount of the phosphonic acid compound is usually about 1 to 10 parts by mass per 100 parts by mass of the polyester fiber.
なお、接触工程では、キュアリング工程に先立って、例えば５０～１２０℃程度で乾燥工程を実施することができる。 In addition, in the contact process, a drying process can be carried out, for example, at about 50 to 120°C prior to the curing process.
キュアリング工程では、本発明難燃処理剤を含むポリエステル系繊維を熱処理すれば良い。例えば大気中１５０～２００℃程度で熱処理することができる。このようにして本発明難燃処理剤の難燃成分（ホスホン酸化合物のほか、上記ホスホン酸化合物及び上記窒素含有化合物との塩等）を含む難燃性ポリエステル繊維を得ることができる。すなわち、前記ホスホン酸化合物の少なくとも１種及び前記窒素含有化合物の少なくとも１種がポリエステル系繊維に付着してなる難燃性ポリエステル系繊維を提供することができる。ホスホン酸化合物及び窒素含有化合物は、それぞれ単独でポリエステル系繊維に付着していても良いし、両者の塩の形態でポリエステル系繊維に付着していても良い。 In the curing process, the polyester fiber containing the flame retardant treatment agent of the present invention may be heat-treated. For example, the heat treatment may be performed at about 150 to 200°C in air. In this way, a flame-retardant polyester fiber containing the flame-retardant components of the flame retardant treatment agent of the present invention (phosphonic acid compounds, salts of the above-mentioned phosphonic acid compounds and nitrogen-containing compounds, etc.) can be obtained. That is, a flame-retardant polyester fiber can be provided in which at least one of the above-mentioned phosphonic acid compounds and at least one of the above-mentioned nitrogen-containing compounds are attached to the polyester fiber. The phosphonic acid compound and the nitrogen-containing compound may be attached to the polyester fiber alone, or may be attached to the polyester fiber in the form of a salt of both.
以下において、実施例及び比較例を示し、本発明の内容より具体的に説明する。ただし、本発明の範囲は、実施例に限定されない。なお、以下の「％」表示（含有量）は「質量％」を示す。 The following examples and comparative examples are presented to more specifically explain the present invention. However, the scope of the present invention is not limited to the examples. The "%" indications (contents) below indicate "mass %."
実施例１
攪拌機を付帯した２００ｍＬガラス製フラスコに６０％濃度の１－ヒドロキシエタン－１，１－ジホスホン酸水溶液５６．４０ｇを測り取り、攪拌しつつ水１８．９６ｇ加えた。その後、フラスコをアイスバスにて冷却し、これに２５％濃度のアンモニア水２４．６４ｇを内温２５℃を超えないように冷却しながらゆっくり添加することにより中和し、ｐＨを５．７とした。得られた無色透明の水溶液を薬剤Ａ（得量１００．０ｇ、ホスホン酸化合物として３３．８％含有)とした。
Example 1
56.40 g of 60% 1-hydroxyethane-1,1-diphosphonic acid aqueous solution was weighed into a 200 mL glass flask equipped with a stirrer, and 18.96 g of water was added while stirring. The flask was then cooled in an ice bath, and 24.64 g of 25% ammonia water was slowly added to the flask while cooling so that the internal temperature did not exceed 25° C., to neutralize the solution and adjust the pH to 5.7. The resulting colorless and transparent aqueous solution was designated as Drug A (yield: 100.0 g, 33.8% content as phosphonic acid compound).
実施例２
攪拌機を付帯した２００ｍＬガラス製フラスコに６０％濃度の１－ヒドロキシエタン－１，１－ジホスホン酸水溶液４２．６０ｇを測り取り、攪拌しつつ水１６．９３ｇを加えた。その後、フラスコをアイスバスにて冷却し、これに８５％濃度のジイソプロパノールアミン水溶液４０．４７ｇを内温２５℃を超えないように冷却しながらゆっくり添加することにより中和し、ｐＨを５．６とした。得られた無色透明の水溶液を薬剤Ｂ（得量１００．０ｇ、ホスホン酸化合物として２５．６％含有)とした。
Example 2
42.60 g of 60% concentration 1-hydroxyethane-1,1-diphosphonic acid aqueous solution was weighed into a 200 mL glass flask equipped with a stirrer, and 16.93 g of water was added while stirring. The flask was then cooled in an ice bath, and 40.47 g of 85% concentration diisopropanolamine aqueous solution was slowly added thereto while cooling so that the internal temperature did not exceed 25°C, thereby neutralizing the solution to a pH of 5.6. The resulting colorless and transparent aqueous solution was designated as Drug B (amount obtained: 100.0 g, containing 25.6% as phosphonic acid compound).
実施例３
攪拌機を付帯した２００ｍＬガラス製フラスコに６０％濃度の１－ヒドロキシエタン－１，１－ジホスホン酸水溶液５４．１５ｇを測り取り、攪拌しつつ水２７．５０ｇ加えた。その後、フラスコをアイスバスにて冷却し、これにモルホリン１８．３５ｇを内温２５℃を超えないように冷却しながらゆっくり添加することにより中和し、ｐＨを５．５とした。得られた無色透明の水溶液を薬剤Ｃ（得量１００．０ｇ、ホスホン酸成分３２．５％含有)とした。
Example 3
54.15 g of 60% concentration 1-hydroxyethane-1,1-diphosphonic acid aqueous solution was weighed out into a 200 mL glass flask equipped with a stirrer, and 27.50 g of water was added while stirring. The flask was then cooled in an ice bath, and 18.35 g of morpholine was slowly added thereto while cooling so that the internal temperature did not exceed 25°C, thereby neutralizing the solution to a pH of 5.5. The resulting colorless and transparent aqueous solution was designated as Chemical C (yield amount 100.0 g, containing 32.5% phosphonic acid component).
実施例４
攪拌機を付帯した２００ｍＬガラス製フラスコにｎ－ブチルホスホン酸４４．２６ｇを測り取り、攪拌しつつ水３２．８１ｇ加えた。その後、フラスコをアイスバスにて冷却し、これに２５％濃度のアンモニア水２２．９３ｇを内温２５℃を超えないように冷却しながらゆっくり添加することにより中和し、ｐＨを６．４とした。得られた無色透明の水溶液を薬剤Ｄ（得量１００．０ｇ、ホスホン酸化合物として４４．３％含有)とした。
Example 4
44.26 g of n-butylphosphonic acid was weighed into a 200 mL glass flask equipped with a stirrer, and 32.81 g of water was added while stirring. The flask was then cooled in an ice bath, and 22.93 g of 25% aqueous ammonia was slowly added to the flask while cooling so that the internal temperature did not exceed 25°C, to neutralize the mixture and adjust the pH to 6.4. The resulting colorless and transparent aqueous solution was designated as Drug D (amount obtained: 100.0 g, 44.3% content as phosphonic acid compound).
実施例５
攪拌機を付帯した２００ｍＬガラス製フラスコにｎ－ブチルホスホン酸３０．６６ｇを測り取り、攪拌しつつ水３４．８２ｇ加えた。その後、フラスコをアイスバスにて冷却し、これに８５％濃度のジイソプロパノールアミン３４．５２ｇを内温２５℃を超えないように冷却しながらゆっくり添加することにより中和し、ｐＨを４．６とした。得られた無色透明の水溶液を薬剤Ｅ（得量１００．０ｇ、ホスホン酸化合物として３０．７％含有)とした。
Example 5
30.66 g of n-butylphosphonic acid was weighed into a 200 mL glass flask equipped with a stirrer, and 34.82 g of water was added while stirring. The flask was then cooled in an ice bath, and 34.52 g of 85% diisopropanolamine was slowly added to the flask while cooling so that the internal temperature did not exceed 25°C, to neutralize the mixture and adjust the pH to 4.6. The resulting colorless and transparent aqueous solution was designated as Drug E (amount obtained: 100.0 g, 30.7% content as phosphonic acid compound).
比較例１
６０％濃度の１－ヒドロキシエタン－１，１－ジホスホン酸水溶液（キレスト株式会社製「キレストＰＨ－２１０」）を薬剤Ｆとした（ホスホン酸化合物として６０．０％含有)。
Comparative Example 1
A 60% aqueous solution of 1-hydroxyethane-1,1-diphosphonic acid (Chilest PH-210, manufactured by Chelest Co., Ltd.) was used as drug F (containing 60.0% of the phosphonic acid compound).
比較例２
攪拌機を付帯した２００ｍＬガラス製フラスコに６０％濃度の１－ヒドロキシエタン－１，１－ジホスホン酸水溶液５７．１４ｇを測り取り、攪拌しつつ水１７．１４ｇ加えた。その後、フラスコをアイスバスにて冷却し、これに炭酸グアニジン２５．７２ｇを内温２５℃を超えないように冷却しながらゆっくり添加することにより中和し、ｐＨを４．６とした。得られた無色透明の水溶液を薬剤Ｇ（得量９０．２ｇ、ホスホン酸化合物として３７．６％含有)とした。なお、中和時には、激しい炭酸ガスの発生が確認された。
Comparative Example 2
57.14 g of 60% aqueous 1-hydroxyethane-1,1-diphosphonic acid solution was weighed out into a 200 mL glass flask equipped with a stirrer, and 17.14 g of water was added while stirring. The flask was then cooled in an ice bath, and 25.72 g of guanidine carbonate was slowly added while cooling so that the internal temperature did not exceed 25°C, to neutralize the solution and adjust the pH to 4.6. The resulting colorless and transparent aqueous solution was designated as Drug G (yield: 90.2 g, 37.6% content as phosphonic acid compound). During neutralization, vigorous generation of carbon dioxide gas was confirmed.
比較例３
リン酸グアニジンの６０％水溶液（丸菱油化工業株式会社製「ノンネン９８４」）を薬剤Ｈとした。
Comparative Example 3
Drug H was a 60% aqueous solution of guanidine phosphate ("Nonnen 984" manufactured by Marubishi Yuka Kogyo Co., Ltd.).
比較例４
攪拌機を付帯した２００ｍＬガラス製フラスコにメチルホスホン酸１０．００ｇを測り取り、攪拌しつつ水８２．１４ｇ加えた。その後、フラスコをアイスバスにて冷却し、これにグアニル尿素７．８６ｇを内温２５℃を超えないように冷却しながらゆっくり添加することにより中和し、ｐＨを４．９とした。得られた無色透明の水溶液を薬剤Ｉ（得量１００．０ｇ、ホスホン酸化合物として１０．０％含有)とした。なお、用いたグアニル尿素は、米国特許2,277,823号に記載の製造法に従って製造したものを用いた。
Comparative Example 4
10.00g of methylphosphonic acid was weighed into a 200mL glass flask equipped with a stirrer, and 82.14g of water was added while stirring. The flask was then cooled in an ice bath, and 7.86g of guanylurea was slowly added to the flask while cooling so that the internal temperature did not exceed 25°C, to neutralize the mixture and adjust the pH to 4.9. The resulting colorless and transparent aqueous solution was designated as Drug I (amount obtained: 100.0g, containing 10.0% as phosphonic acid compound). The guanylurea used was prepared according to the method described in U.S. Patent No. 2,277,823.
試験例１
（１）加工布（試験片）の調製
薬剤Ａ～薬剤Ｈをホスホン酸化合物ベースで１．５％（比較例３のみ、リン酸ベースで１．５％）になるように、シリコン系可縫製向上剤「ＰＯＬＯＮ ＭＦ２９（信越化学工業株式会社製）」の０．１％水溶液で希釈し、加工液とした。絞り率８０％にてポリエステル布（目付３００ｇ／ｍ２のカーシート用黒色ポリエステル布）をパディング処理した。さらに、８０℃で１０分間予備乾燥した後、１８０℃で１分間キュアリングを行い、加工布を得た。各薬剤の有効成分（ホスホン酸化合物）の付与量は、いずれも約３．６ｇ／ｍ２とした。
Test Example 1
(1) Preparation of processed fabric (test piece) Agents A to H were diluted with a 0.1% aqueous solution of a silicon-based sewability improver "POLON MF29 (manufactured by Shin-Etsu Chemical Co., Ltd.)" to a concentration of 1.5% based on phosphonic acid compound (only Comparative Example 3, 1.5% based on phosphoric acid) to prepare a processing solution. A polyester fabric (black polyester fabric for car seats with a basis weight of 300 g/ m2 ) was padded at a squeezing rate of 80%. Further, the fabric was pre-dried at 80°C for 10 minutes and then cured at 180°C for 1 minute to obtain a processed fabric. The amount of the active ingredient (phosphonic acid compound) of each agent was about 3.6 g/ m2 .
（２）試験・評価
各薬剤で処理された加工布を用いて以下の試験を行った。その結果を表１に示す。
（２－１） 難燃性
米国規格ＦＭＶＳＳ３０２法(自動車内装用品の安全基準)に従い、車両用内装材の燃焼距離、燃焼時間及び燃焼速度を測定した。評価基準は、以下の通りとした。
不燃性：Ａ標線を超えて燃焼しない。（Ａ標線前自消）
難燃性：Ａ標線を超えて燃焼するが、燃焼距離が５０ｍｍ未満、かつ、燃焼速度が８０ｍｍ／分未満である。
遅燃性：燃焼速度が１００ｍｍ／分未満である。
不合格：燃焼速度が１００ｍｍ／分以上である。
（２－２）キワツキ（際付き）
温度８０℃の蒸留水３ｍＬを水平にした加工布の表面に滴下し、室温にて風乾した。乾燥後の加工布表面を目視で観察し、キワツキの程度を確認した。キワツキの評価は、以下のように「◎」～「×」の４段階で評価した。
◎：際がわからず、濡れた部分の色調変化がない
〇：際および濡れた部分の色調変化が微かに確認できる
△：際および濡れた部分の色調変化が確認できる
×：際が明確に確認でき、濡れた部分の色調が明らかに異なっている
（２－３）風合い
加工布の風合いを触感で確認した。風合いの評価は、以下のように「◎」～「×」の４段階で評価した。
◎：未処理布と同等の柔軟性（触感）を維持している
〇：未処理布に比べ、微かに触感が硬い
△：未処理布に比べ、ごわつきを感じる
×：未処理布に比べ、強いごわつきを感じる
（２－４）耐湿熱性
温度７０℃×湿度９５％ＲＨの環境下に加工布を４週間にわたって静置し、その後に温度２３℃×湿度５０％ＲＨの環境下で２４時間の順化を行った。難燃処理の前後で引き裂き試験を行い、加工布の物性低下の度合いを調べた。初期の引き裂き強度（Ｎ）を１００％としたときの試験後の強度を％で示した。また、試験はｎ＝５で行い、その平均値で評価した。
(2) Tests and Evaluation The following tests were carried out using the treated fabrics with each agent. The results are shown in Table 1.
(2-1) Flame Retardancy According to the US standard FMVSS302 (safety standard for automotive interior products), the burning distance, burning time and burning speed of the vehicle interior materials were measured. The evaluation criteria were as follows:
Non-flammable: Does not burn beyond the A mark. (Self-extinguishing before the A mark)
Flame retardant: Burns beyond the A-marked line, but the burning distance is less than 50 mm and the burning rate is less than 80 mm/min.
Slow burning: Burning rate is less than 100 mm/min.
Fail: The burning rate is 100 mm/min or more.
(2-2) Kiwatsuki (Edge)
3 mL of distilled water at 80°C was dropped onto the surface of the horizontally placed processed fabric and air-dried at room temperature. The surface of the processed fabric after drying was visually observed to confirm the degree of roughness. The roughness was evaluated on a four-level scale from "◎" to "×" as follows.
◎: Edges are not visible, and there is no color change in the wet area. ◯: Color changes in the edges and wet area are slightly visible. △: Color changes in the edges and wet area are visible. ×: Edges are clearly visible, and the color of the wet area is clearly different. (2-3) Texture The texture of the processed fabric was checked by touch. Texture was evaluated on a four-level scale from "◎" to "×" as follows.
◎: Maintains the same flexibility (touch) as untreated fabric. ◯: Slightly harder to the touch than untreated fabric. △: Feels stiffer than untreated fabric. ×: Feels very stiffer than untreated fabric. (2-4) Moisture and heat resistance The treated fabric was left in an environment of 70°C temperature and 95% RH for 4 weeks, and then acclimatized for 24 hours in an environment of 23°C temperature and 50% RH. A tear test was performed before and after the flame retardant treatment to examine the degree of deterioration in the physical properties of the treated fabric. The strength after the test was expressed in %, with the initial tear strength (N) being 100%. The test was performed with n=5, and the average value was used for evaluation.
表１の結果からも明らかなように、ホスホン酸化合物のみを含む難燃処理剤である比較例１では、高温高湿下で繊維が脆化していることがわかる。
また、ホスホン酸化合物とグアニジン化合物との塩を用いた比較例２では、ある程度の難燃性は認められるものの、キワツキが顕著で風合いも低く、ポリエステル系繊維本来の物性が損なわれていた。
グアニジン化合物単体を用いた比較例３～４では、ポリエステル系繊維に対して十分な難燃性を付与することができなかった。
これら比較例に対し、実施例１～５のように、所定のホスホン酸化合物と窒素含有化合物を含む本発明難燃処理剤をポリエステル系繊維に付与することにより、「不燃」という高い難燃性能が発現し、なおかつ、キワツキ又は風合いを損ねない生地を提供できることがわかる。しかも、これらの実施例では、耐湿熱性試験を行っても、耐湿熱性が６８～７５％であり、繊維の強度の低下は少ないこともわかる。
As is clear from the results in Table 1, in Comparative Example 1, which is a flame retardant treatment agent containing only a phosphonic acid compound, the fibers become embrittled under high temperature and high humidity conditions.
In addition, in Comparative Example 2 using a salt of a phosphonic acid compound and a guanidine compound, although a certain degree of flame retardancy was observed, there was significant edgeiness and poor feel, and the inherent physical properties of polyester-based fibers were impaired.
In Comparative Examples 3 and 4, in which the guanidine compound was used alone, sufficient flame retardancy could not be imparted to the polyester fiber.
In contrast to these comparative examples, it is clear that by applying the flame retardant treatment agent of the present invention containing a specific phosphonic acid compound and a nitrogen-containing compound to polyester fibers as in Examples 1 to 5, a fabric with high flame retardant performance of "non-flammable" can be provided without roughness or loss of texture. Moreover, in these examples, even when a moist heat resistance test was performed, the moist heat resistance was 68 to 75%, and it is also clear that there was little decrease in the strength of the fiber.
Claims (4)
（１）（ａ）下記式１－１
（ｂ）下記式２－１及び式２－２
で示される窒素含有化合物の少なくとも１種
が水に溶解してなる水溶液であって、
（２）前記水溶液のｐＨが４～８である
ことを特徴とするポリエステル系繊維用難燃処理剤。 A composition for imparting flame retardancy to polyester-based fibers, comprising:
(a) Formula 1-1 below
(b) Formula 2-1 and Formula 2-2 below
An aqueous solution in which at least one nitrogen-containing compound represented by the formula:
(2) A flame retardant treatment agent for polyester fibers, characterized in that the pH of the aqueous solution is 4 to 8.
（ｂ）下記式２－１及び式２－２
で示される窒素含有化合物の少なくとも１種
がポリエステル系繊維に付着してなる難燃性ポリエステル系繊維。 (a) the following formula 1-1
(b) Formula 2-1 and Formula 2-2 below
The flame-retardant polyester fiber is obtained by adhering to the polyester fiber at least one nitrogen-containing compound represented by the following formula:
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020116034A JP7549863B2 (en) | 2020-07-04 | 2020-07-04 | Flame retardant treatment for polyester fibers |
| JP2024141096A JP7793230B2 (en) | 2020-07-04 | 2024-08-22 | Flame retardant treatment for polyester fibers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020116034A JP7549863B2 (en) | 2020-07-04 | 2020-07-04 | Flame retardant treatment for polyester fibers |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2024141096A Division JP7793230B2 (en) | 2020-07-04 | 2024-08-22 | Flame retardant treatment for polyester fibers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2022013456A JP2022013456A (en) | 2022-01-18 |
| JP7549863B2 true JP7549863B2 (en) | 2024-09-12 |
Family
ID=80169665
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020116034A Active JP7549863B2 (en) | 2020-07-04 | 2020-07-04 | Flame retardant treatment for polyester fibers |
| JP2024141096A Active JP7793230B2 (en) | 2020-07-04 | 2024-08-22 | Flame retardant treatment for polyester fibers |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2024141096A Active JP7793230B2 (en) | 2020-07-04 | 2024-08-22 | Flame retardant treatment for polyester fibers |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JP7549863B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000160036A (en) | 1998-09-24 | 2000-06-13 | Toray Ind Inc | Flame-retardant resin composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6032747B2 (en) * | 1980-08-27 | 1985-07-30 | 株式会社クラレ | Flame retardant treatment method for fabric |
| US4452849A (en) * | 1981-02-03 | 1984-06-05 | Ciba-Geigy Corporation | Phosphonic acid salts, their preparation and their use for fireproofing organic fibre material |
| GB8401003D0 (en) * | 1984-01-14 | 1984-02-15 | Ciba Geigy Ag | Phosphonic acid salts |
| IT1244440B (en) * | 1990-09-13 | 1994-07-15 | Ministero Dall Uni E Della Ric | SELF-EXTINGUISHING POLYMERIC COMPOSITIONS |
-
2020
- 2020-07-04 JP JP2020116034A patent/JP7549863B2/en active Active
-
2024
- 2024-08-22 JP JP2024141096A patent/JP7793230B2/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000160036A (en) | 1998-09-24 | 2000-06-13 | Toray Ind Inc | Flame-retardant resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2022013456A (en) | 2022-01-18 |
| JP2024161056A (en) | 2024-11-15 |
| JP7793230B2 (en) | 2026-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6097017B2 (en) | Flame retardant artificial leather, method for producing the same, and flame retardant processing agent for artificial leather | |
| WO2016059882A1 (en) | Flame-retardant polyurethane resin and flame-retardant synthetic leather | |
| Drake et al. | Industrial uses of phosphonates | |
| JPWO2013187492A1 (en) | Flame retardant synthetic leather | |
| EP2832924B1 (en) | Process for manufacturing a flameproof fiber product | |
| US3671304A (en) | Process for flameproofing and resultant product | |
| CA1039458A (en) | Flameproofing of fabrics | |
| JP7549863B2 (en) | Flame retardant treatment for polyester fibers | |
| WO2007032277A1 (en) | Phosphorus compound, use thereof and flame-retardant polyester fiber | |
| EP0000024A1 (en) | Polyadducts containing phosphorus and their application in the flameproofing of textile materials | |
| EP0525081A4 (en) | Flame-proofing compositions | |
| WO2021204571A1 (en) | Flame-retardant finishing of textile fabrics with polycondensation products | |
| JP4720492B2 (en) | Polyester fiber structure | |
| EP2710184A1 (en) | Method for fireproofing textiles | |
| EP2209863A2 (en) | Water-compatible sols for coating various substrates | |
| JP2014224336A (en) | Method for producing flame retardant fiber, flame retardant-processing agent, and flame-retardant processing aid | |
| GB2306477A (en) | Flame retardant compositions containing a non-salt ammonia neutralisate of a nitrilotris(alkylenephosphonic acid) | |
| DE2458510A1 (en) | PROCESS FOR MAKING NITROGENIC ORGANIC POLYMERS FLAME RESISTANT | |
| JP5215221B2 (en) | Flame-retardant processing agent for fibers, flame-retardant processing method using the same, and flame-retardant processed fiber products | |
| JP6271424B2 (en) | Flame retardant processing chemical, flame retardant fiber production method and flame retardant fiber | |
| US10640646B2 (en) | Flame retardant polyurethane artificial leather and method for manufacturing the same | |
| CN102057102B (en) | Composition for treating fibrous materials, especially by exhaust dyeing methods | |
| NO173790B (en) | PROCEDURE FOR AA GIVE A SUBSTANCE OF POLYESTER / COTTON ELLERNYLON / COTTON WASH RESISTANT FLAME RESISTANCE | |
| JPS6215387A (en) | Method for flame-proof processing of fiber product excellentin feeling | |
| JP6363832B2 (en) | Method for producing flame retardant polyester fiber fabric for vehicle interior material, and flame retardant polyester fiber fabric for vehicle interior material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230701 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20240319 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240402 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20240523 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240715 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20240806 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20240826 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7549863 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |