JPH0320514B2 - - Google Patents
Info
- Publication number
- JPH0320514B2 JPH0320514B2 JP6580984A JP6580984A JPH0320514B2 JP H0320514 B2 JPH0320514 B2 JP H0320514B2 JP 6580984 A JP6580984 A JP 6580984A JP 6580984 A JP6580984 A JP 6580984A JP H0320514 B2 JPH0320514 B2 JP H0320514B2
- Authority
- JP
- Japan
- Prior art keywords
- flame
- water
- artificial leather
- compounds
- retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000001875 compounds Chemical class 0.000 claims description 34
- 239000003063 flame retardant Substances 0.000 claims description 33
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 21
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052794 bromium Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- -1 halogenated phosphate ester Chemical class 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 5
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 239000007983 Tris buffer Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 6
- UJSSNDKVUQJEGE-UHFFFAOYSA-N dichloro propyl phosphate Chemical compound CCCOP(=O)(OCl)OCl UJSSNDKVUQJEGE-UHFFFAOYSA-N 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 230000033228 biological regulation Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000002649 leather substitute Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- 239000012209 synthetic fiber Substances 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 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 3
- 239000004114 Ammonium polyphosphate Substances 0.000 description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000000986 disperse dye Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- OZHJEQVYCBTHJT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-methylbenzene Chemical compound CC1=C(Br)C(Br)=C(Br)C(Br)=C1Br OZHJEQVYCBTHJT-UHFFFAOYSA-N 0.000 description 1
- AHBGXHAWSHTPOM-UHFFFAOYSA-N 1,3,2$l^{4},4$l^{4}-dioxadistibetane 2,4-dioxide Chemical compound O=[Sb]O[Sb](=O)=O AHBGXHAWSHTPOM-UHFFFAOYSA-N 0.000 description 1
- SUIOPXSLPPMBJN-UHFFFAOYSA-N 1,3-dichloropropyl dihydrogen phosphate Chemical compound OP(O)(=O)OC(Cl)CCCl SUIOPXSLPPMBJN-UHFFFAOYSA-N 0.000 description 1
- GMAAWZONVLTAMA-UHFFFAOYSA-N 2,3-dibromopropyl dihydrogen phosphate Chemical compound OP(O)(=O)OCC(Br)CBr GMAAWZONVLTAMA-UHFFFAOYSA-N 0.000 description 1
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-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
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- NMDGMYNXRRCPGM-UHFFFAOYSA-N dibromo propyl phosphate Chemical compound P(=O)(OBr)(OBr)OCCC NMDGMYNXRRCPGM-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- MTZWHHIREPJPTG-UHFFFAOYSA-N phorone Chemical compound CC(C)=CC(=O)C=C(C)C MTZWHHIREPJPTG-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- XHTMGDWCCPGGET-UHFFFAOYSA-N tris(3,3-dichloropropyl) phosphate Chemical compound ClC(Cl)CCOP(=O)(OCCC(Cl)Cl)OCCC(Cl)Cl XHTMGDWCCPGGET-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Description
(発明の技術分野)
本発明は耐水性を有し、かつ柔軟で優れた難燃
性人工皮革状構造物に関する。
(従来技術とその問題点)
近年、衣料やインテリア材料、産業資材などに
人工皮革などの合成繊維と樹脂からなる複合材料
が多用され、たてえば衣料としてはコート、ジヤ
ンバー、スーツなどにまたインテリア材料として
は航空機、船舶、鉄道、自動車などの乗物あるい
はホテル、病院などの座席シートやカーテン、壁
装材などに適用されている。靴やカバンなどにも
人工皮革の特徴が生かされている。しかし、イン
テリア材料を中心に衣料、産業資材などに適用し
た場合、火災による人的被害が大きいために、法
的規制が厳しく、これに合格するもの以外は実資
的に実用できない。たとえば自動車用内装材には
FMVSS−302またはJIS・D−1201、壁装材には
JIS・A−1321、航空機内装材にはFAAなどの法
規則があり、その規制に合格しなければならな
い。さらに自動車メーカーで法規制よりも厳しい
規格を独自に定めている場合が多い。
通常、繊維の難燃性製品は各種のものが知られ
ているが、合成繊維と樹脂からなる複合材料の難
燃性製品は次のような問題を有するために、高級
品としての価値を損わずに難燃性を付与すること
は容易にできなかつた。
(1) 合成繊維と樹脂と燃焼機構が異なり、両方の
難燃化を満足に達成するものがなかつた。
(2) 難燃性を満足させるためには多量の難燃剤を
含有させる必要があり、その結果風合の粗硬
化、染色堅牢度の低下、更にはベタツキ感を惹
起するなどの欠点があつた。
(3) 難燃剤は移行しやすく、ベタツキ感と併せて
染料のしみ出しを惹起し、表面品位を損う欠点
があつた。
(4) 水に浸漬した場合や汗や濡れた衣服が接触し
た場合など難燃剤が溶出し難燃性の低下および
品位不良などの問題が発生した。
人工皮革状構造物の難燃化に関する公知例とし
ては特開昭54−127002、特開昭56−85478、特開
昭58−13786があるが、いずれも耐水性がなく、
その用途にはかなりの制限を受けざるを得なかつ
た。
(発明の目的)
本発明はJIS・D−1201、FMVSS−302、
FAAなど更にはJIS・L−1091、DOC−FF−5
−74で規定される難燃規格をクリアする優れた難
燃性を発揮すると共に、従来みられなかつた耐水
性ならびに柔軟性を達成し得る難燃性人工皮革状
構造物を提供し得たものである。
(発明の構成)
ポリウレタンと繊維からなる人工皮革状構造物
において、該構造の厚さの主として裏面の部分
に、下記A、B、C、D4群から少なくとも1種
ずつ選ばれた化合物の混合組成物を、該構造物に
対して10〜100重量%付与されてなる難燃性人工
皮革状構造物。
A:40℃以下の温度で流動性があり、同温度以下
での水への溶解度が1%以下であるハロゲン化
リン酸エステル。
B:0℃から40℃の範囲で水への溶解度が1%以
下であり、融点が110℃以上であり、かつ臭素
含有量が30%以上である臭素含有化合物。
C:酸化アンチモン
D:JIS・K−5400に基づく鉛筆引つかき試験に
よる硬度が2H以下である非水溶性有機樹脂。
(構成の説明)
本発明でいう人工皮革状構造物とは、ポリエス
テル、ナイロンまたはポリアクリロニトリル系繊
維からなる極細繊維(主として1デニール以下)
の不織布に高分子弾性体として主にポリウレタン
が含浸されものである。ポリウレタン以外に天然
ゴム、クロロプレンゴム、SBR、アクリル系ゴ
ム、シリコーン系ゴム状物などの各種ゴム状物が
併用されてもよい。これら高分子弾性重合体には
艶消剤、顔料、安定剤などの添加物が適宜用いら
れる。人工皮革状構造物には表面に立毛を有する
スエード調人工皮革および表面を弾性ポリマで被
覆された靴、カバン、ジヤンバー用人工皮革があ
るが、いずれの形態に対しても本発明は適用され
る。人工皮革状構造物はその形態保持または物理
的補強のため、裏面に織物または編物を接着され
たものであつてもよい。
混合組成物は人工皮革状構造物の裏面にコーテ
イング、プリント、含浸などの方法で付与され
る。混合組成物は人工皮革状構造物の厚さの裏面
から2/3まで、特に1/2以下の範囲までに分布をと
どめるのが、表面品位、染色堅牢度、染料のしみ
出し、ベタツキなどの点から好ましい。
本発明の混合組成物すなわち難燃剤は前記A、
B、C、Dの4群の化合物で、各群から少なくと
も1種類選ばれてなる組成物である。A群は40℃
以下の温度で流動性があり、同温度以下での水へ
の溶解度が1%以下であるハロゲン化リン酸エス
テル、たとえばトリスジブロモプロピルホスフエ
ート、トリスジクロロプロピルホスフエート、ト
リスクロロエチルホスフエート、モノ2、3ジク
ロロプロピルビス2、3ジブロモブロピルホスフ
エート、トリスクロロエチルホスフアイドなどの
常温で液体である水不溶性の化合物である。好ま
しくは0℃以下でも流動性を有する液状物であ
り、180℃以下で気化しないハロゲン化リン酸エ
ステルである。
A群からなる化合物は、人工皮革状構造物を構
成する高分子弾性体の可塑効果を有し、さらには
D群からなる樹脂の柔軟剤としても作用する。通
常、該ハロゲン化リン酸エステルはエマルジヨン
として調整されたものが他の化合物と配合され均
一な混合組成物を形成する。とりわけ、1、3ジ
クロロプロピルホスフエートが柔軟効果の作用が
大きく好ましく用いられる。
本発明のB群からなる化合物は40℃以下の温度
で水への溶解度が1%以下であり、融点が110℃
以上であり、かつ臭素含有量が30%以上である臭
素含有化合物である。このB群からなる化合物が
本発明の混合組成物の主成分となるものであり、
臭素含有量の高いものが好ましく用いられる。臭
素含有量が30%未満の化合物は難燃性が十分に発
現しない。とりわけ臭素含有量が高いデカブロモ
ジフエニルエーテル、ヘキサブロモシクロドデカ
ンが好ましい。融点は110℃以上であることが好
ましく、110℃未満では染色堅牢度低下、ブリー
ドなどを誘発し品位を低下させる。B群の化合物
としては次のようなものが例示される。
デカブロモジフエニルエーテル(融点;290℃、
臭素顔料;82%)、テトラブロモビスフエノール
A(融点;178℃、臭素含量;58%)およびその誘
導体、テトラブロモビスフエノールS(融点;280
℃、臭素含量;56%)およびその誘導体、テトラ
ブロモフタリツクアンハイドライド(融点;269
℃、臭素含量;67%)、ヘキサブロモベンゼン
(融点;325℃、臭素含量;86%)、ヘキサブロモ
シクロドデカン(融点;172℃、臭素含量;72
%)、ペンタブロモトルエン(融点;280℃、臭素
含量;81%)、ペンタブロモフエニルアクリルエ
ーテル(融点;165℃、臭素含有量;74%)など
水不溶性粉体。
本発明のC群は酸化アンチモンであり、この化
合物は上記B群の臭素化合物と併用することによ
り、高い相乗効果を有する難燃性が得られる。酸
化アンチモンは三酸化アンチモン、四酸化アンチ
モン、五酸化アンチモンなどが例示されるが、特
に三酸化アンチモンは臭素化合物と燃焼時に結合
し高い難燃性を発揮するために好ましく用いられ
る。酸化アンチモンは臭素化合物に対し20〜80%
配合される。好ましくは30〜50%配合される。
D群は、JIS・K5400の6・14による鉛筆引つ
かき試験法測定した樹脂皮膜単独の硬度が2H以
下の非水溶性有機樹脂である。D群からなる樹脂
はA〜C群の難燃性化合物、特にB、C群の化合
物を皮膜形成時に包含することの可能な柔軟な皮
膜形成樹脂であり、好ましくは硬度2B〜6Bの樹
脂が好ましい。さらには80〜120℃の温度範囲で
皮膜形成する樹脂が好ましく用いられる。たとえ
ばポリ塩化ビニル、ポリウレタン、ポリアクリ酸
エステル、ポリエステルなどの樹脂である。特
に、エチルアクリレート、ブチルアクリレート、
2エチルヘキシルアリレートの3共重合体からな
る均一性、相溶性および柔軟性の点で好ましく用
いられる。
本発明の混合組成物は分散剤、増粘剤、着色
剤、含リン化合物など適宜添加配合しても何ら差
しつかえない。
本発明のA〜Dの4群の化合物を主成分とする
混合組成物は水素分散体または溶剤系液状物とし
て、通常有効成分30〜70重量%に調整される。人
工皮革状構造物の裏面に混合組成物がコーテイン
グ法などにより付与され、乾燥後の重量で10〜
100%付与し、所望の難燃性を得る。自動車内装
材に対しては10〜30%、壁装材、航空機内装材に
対しては30〜70%付与されたとき好ましい難燃性
を発揮し、かつ十分な耐水性が得られた。
本発明の混合組成物はA〜D群の化合物の組合
せにより、その性能をより最適化することが可能
である。すなわち各群の特徴を活用することが重
要であり、A群からなる化合物は柔軟化、B群か
らなる化合物は主難燃化剤、C群からなる化合物
は難燃助剤として臭素化合物との相乗効果および
D群の化合物は柔軟性を有するバインダーとして
の役割を最大限に発揮させる。好ましい混合割合
は次のとおりである。
A群の化合物 10〜30部
B 〃 20〜60〃
C 〃 10〜30〃
D 〃 5〜30部
さらに好ましくはA、B、C群の化合物の総重量
に対するD群の化合物の混合比が30%以下で5%
以上の混合組成物である。
(発明の作用機構)
本発明による難燃剤は上記A〜Dの4群からな
る化合物を分散化したものであり、その各々の化
合物は人工皮革状構造物の難燃化に対して必須で
ある。A群の化合物は難燃性化合物の中で唯一の
液体であり、この化合物は人工皮革状構造物およ
びD群から選ばれた有機樹脂の難燃性可塑剤とし
ての作用を発揮し、柔軟性を付与する。B、C群
の化合物は両方の化合物が燃焼時に結合し、臭素
とアンチモンによる相乗効果を発揮して高い難燃
性が得られる。特に臭素含有量が高い化合物は難
燃化に有効に作用するため低付着量での難燃化が
可能になつた。さらにD群からなる非水系有機樹
脂はA〜C群の難燃性化合物を人工皮革状構造物
に固着させる作用がある。各々、特性の異なる化
合物の混合組成物を分散化した難燃剤はその分散
体に粘性、湿潤性、透湿性を付与することによ
り、人工皮革状構造物への難燃性化合物の透湿性
や付着分布状態の調整が可能にされる。
(発明の効果)
本発明は、特定な水不溶性の難燃性化合物と樹
脂の組合せにより、柔軟剤と耐水性を有する高い
難燃性人工皮革状構造物を実現した。
各々、特定な性能を有する化合物の特徴を生か
し、相乗効果による難燃性の向上を達成し、低付
着量での難燃性付与が可能になつた。
以下、本発明を実施例を挙げて、さらに説明す
る。
実施例 1
厚さ1.1mmのポリウレタン含浸熱可塑性合成繊
維からなる人工スエード(東レ製“エクセーヌ”)
の裏面に、低融点ポリアミド系樹脂接着剤を用い
て、目付80g/m2のポリエステル織物を裏張布と
して加熱融着せしめた。次に下記の水不溶性難燃
化合物とアクリル樹脂からなる水分散難燃剤を調
整した。粘度は3000CPS(25℃)であつた。
トリス−ジクロロプロピルホスフエート 10部
デカブロモジフエニルエーテル 20〃
三酸化アンチモン 10〃
アクリル樹脂 4〃
(日本ライヒホールド製、ボンコートWP−210)
分散剤 2部
(アルキルフエノールのエチレンオキサイド付加
物)
増粘剤(CMC) 1〃
水 53〃
合計 100部
難燃剤の調整に際しては、トリスジクロロプロ
ピルホスフエートを乳化したものをデカブロモジ
フエニルエーテルと三酸化アンチモンの分散体に
混合した。次にアクリル樹脂と増粘剤を撹拌しな
がら添加混合した。
この混合組成物を上記人工スエードの裏張布に
丸刃ナイフコータにより塗布した後、110℃、15
分間熱処理した。該組成物の付着量は24重量%で
あつた。
比較として、上記実施例と同じく、織物を裏張
りした人工スエードに難燃性化合物トリスジクロ
ロプロピルホスフエートの代替としてポリリン酸
アンモニウムを配合したもの(比較例1)、トリ
スジクロロプロピルホスフエートを含まないもの
(比較例2)さらにはデカブロモジフエニルホキ
サイド(比較例3)または三酸化アンチモン(比
較例4)を含有しない混合組成物からなる難燃剤
をコーテイングし、23〜25%付着させたものを作
製した。
これらについて、FMVSS−302規格により難
燃性(燃焼速度)を、JIS−L1079規格により柔
軟性をそれぞれ測定した。耐水性は常温の水中に
24時間浸漬(浴比1:300)後、家庭用洗濯機で
2分間脱水後乾燥した。耐水性は重量変化により
減量率で算出した。
本発明の人工スエードは高い難燃性を有し、耐
水性にも優れていた。一方、比較例で、トリスジ
クロロプロピルホスフエートの代替としてポリリ
ン酸アンモニウムを配合したものは耐水性がな
く、含有しないものは柔軟性に欠けていた。デカ
ブロモジフエニルエーテルまたは三酸化アンチモ
ンを含有しないものは難燃性不良であつた。結果
は第1表に示す。データーはすべて測定数5個の
平均値である。
(Technical Field of the Invention) The present invention relates to a flame-retardant artificial leather-like structure that is water resistant and flexible. (Prior art and its problems) In recent years, composite materials made of synthetic fibers such as artificial leather and resin have been widely used for clothing, interior materials, industrial materials, etc. As a material, it is applied to seats, curtains, wall coverings, etc. in vehicles such as aircraft, ships, trains, and automobiles, as well as in hotels and hospitals. The characteristics of artificial leather are also utilized in things such as shoes and bags. However, when applied to interior materials, clothing, industrial materials, etc., there are strict legal regulations due to the large amount of human damage caused by fire, and only those that pass these regulations cannot be put to practical use. For example, for automobile interior materials,
FMVSS-302 or JIS・D-1201, for wall covering materials
JIS A-1321, aircraft interior materials have laws and regulations such as the FAA, and must pass these regulations. Additionally, automakers often set their own standards that are stricter than legal regulations. Generally, various kinds of flame-retardant fiber products are known, but flame-retardant products made of composite materials made of synthetic fibers and resins have the following problems, so they lose their value as luxury products. It has not been possible to easily impart flame retardancy without adding flame retardance. (1) Synthetic fibers and resins have different combustion mechanisms, and there was no material that could satisfactorily achieve flame retardancy for both. (2) In order to satisfy flame retardancy, it is necessary to contain a large amount of flame retardant, which results in disadvantages such as rough hardening of the texture, decrease in color fastness, and even a sticky feeling. . (3) The flame retardant easily migrates, causing a sticky feeling and oozing of the dye, which has the disadvantage of impairing the surface quality. (4) When immersed in water or when sweat or wet clothing comes into contact with the product, the flame retardant elutes, causing problems such as decreased flame retardancy and poor quality. Known examples of flame-retardant artificial leather-like structures include JP-A-54-127002, JP-A-56-85478, and JP-A-58-13786, but none of them have water resistance.
Its use was subject to considerable restrictions. (Object of the invention) The present invention is based on JIS D-1201, FMVSS-302,
FAA, etc. as well as JIS/L-1091, DOC-FF-5
A flame-retardant artificial leather-like structure can be provided that exhibits excellent flame retardancy that meets the flame retardant standards stipulated in ``-74'' and can achieve unprecedented water resistance and flexibility. It is. (Structure of the Invention) In an artificial leather-like structure made of polyurethane and fibers, a mixed composition of at least one compound selected from the following groups A, B, C, and D4 mainly on the back surface of the structure. 1. A flame-retardant artificial leather-like structure, in which 10 to 100% by weight of the compound is added to the structure. A: A halogenated phosphate ester that has fluidity at a temperature of 40°C or lower and has a solubility in water of 1% or lower at the same temperature or lower. B: A bromine-containing compound having a solubility in water of 1% or less in the range of 0°C to 40°C, a melting point of 110°C or more, and a bromine content of 30% or more. C: Antimony oxide D: Water-insoluble organic resin having a hardness of 2H or less in a pencil scratch test based on JIS K-5400. (Description of structure) The artificial leather-like structure as used in the present invention refers to ultrafine fibers (mainly 1 denier or less) made of polyester, nylon, or polyacrylonitrile fibers.
The nonwoven fabric is impregnated with mainly polyurethane as a polymeric elastic material. In addition to polyurethane, various rubber materials such as natural rubber, chloroprene rubber, SBR, acrylic rubber, and silicone rubber materials may be used in combination. Additives such as matting agents, pigments, and stabilizers are appropriately used in these elastic polymers. Artificial leather-like structures include suede-like artificial leather with a raised surface and artificial leather for shoes, bags, and jackets whose surface is coated with an elastic polymer, and the present invention is applicable to both forms. . The artificial leather-like structure may have a woven or knitted fabric adhered to the back side for shape retention or physical reinforcement. The mixed composition is applied to the back side of the artificial leather-like structure by coating, printing, impregnation, or other methods. It is important to keep the distribution of the mixed composition within 2/3 of the thickness of the artificial leather-like structure, especially within 1/2 or less, in order to maintain surface quality, color fastness, dye oozing, stickiness, etc. Preferable from this point of view. The mixed composition of the present invention, that is, the flame retardant has the above-mentioned A,
This is a composition consisting of compounds of four groups B, C, and D, and at least one compound selected from each group. Group A is 40℃
Halogenated phosphate esters that are fluid at the following temperatures and have a solubility in water of 1% or less at the same temperature or below, such as tris dibromopropyl phosphate, tris dichloropropyl phosphate, tris chloroethyl phosphate, mono It is a water-insoluble compound that is liquid at room temperature, such as 2,3 dichloropropyl bis 2,3 dibromopropyl phosphate and trischloroethyl phosphide. Preferably, it is a halogenated phosphate ester that is a liquid material that has fluidity even at 0°C or lower and does not vaporize at 180°C or lower. The compounds of group A have a plasticizing effect on the polymeric elastomer constituting the artificial leather-like structure, and further act as softeners for the resins of group D. Usually, the halogenated phosphate ester is prepared as an emulsion and then mixed with other compounds to form a uniform mixed composition. In particular, 1,3 dichloropropyl phosphate is preferably used because it has a great softening effect. The compound of Group B of the present invention has a solubility in water of 1% or less at a temperature of 40°C or lower, and a melting point of 110°C.
It is a bromine-containing compound which is above and has a bromine content of 30% or more. The compound consisting of this group B is the main component of the mixed composition of the present invention,
Those with a high bromine content are preferably used. Compounds with a bromine content of less than 30% do not exhibit sufficient flame retardancy. Particularly preferred are decabromodiphenyl ether and hexabromocyclododecane, which have a high bromine content. It is preferable that the melting point is 110°C or higher; if it is lower than 110°C, color fastness decreases, bleeding occurs, and the quality deteriorates. Examples of Group B compounds include the following. Decabromodiphenyl ether (melting point: 290℃,
Bromine pigment; 82%), tetrabromobisphenol A (melting point: 178°C, bromine content: 58%) and its derivatives, tetrabromobisphenol S (melting point: 280
°C, bromine content; 56%) and its derivatives, tetrabromophthalic anhydride (melting point; 269
°C, bromine content: 67%), hexabromobenzene (melting point: 325 °C, bromine content: 86%), hexabromocyclododecane (melting point: 172 °C, bromine content: 72
%), pentabromotoluene (melting point: 280°C, bromine content: 81%), pentabromophenyl acrylic ether (melting point: 165°C, bromine content: 74%), and other water-insoluble powders. Group C of the present invention is antimony oxide, and when this compound is used in combination with the bromine compound of Group B, flame retardancy with a high synergistic effect can be obtained. Examples of antimony oxide include antimony trioxide, antimony tetroxide, and antimony pentoxide, and antimony trioxide is particularly preferably used because it combines with bromine compounds during combustion and exhibits high flame retardancy. Antimony oxide is 20-80% compared to bromine compounds
It is blended. Preferably, it is blended in an amount of 30 to 50%. Group D is a water-insoluble organic resin whose resin film alone has a hardness of 2H or less as measured by the pencil scratch test method according to JIS K5400 6.14. The resin consisting of group D is a flexible film-forming resin that can contain flame-retardant compounds of groups A to C, especially compounds of groups B and C during film formation, and preferably has a hardness of 2B to 6B. preferable. Furthermore, resins that form a film in the temperature range of 80 to 120°C are preferably used. Examples include resins such as polyvinyl chloride, polyurethane, polyacrylate, and polyester. In particular, ethyl acrylate, butyl acrylate,
It is preferably used in terms of uniformity, compatibility, and flexibility, consisting of a 3-copolymer of 2-ethylhexyl arylate. The mixed composition of the present invention may be mixed with dispersants, thickeners, colorants, phosphorus-containing compounds, etc. as appropriate. The mixed composition containing the compounds of the four groups A to D of the present invention as main components is prepared as a hydrogen dispersion or a solvent-based liquid and is usually adjusted to contain 30 to 70% by weight of the active ingredients. The mixed composition is applied to the back side of the artificial leather-like structure by a coating method, etc., and the weight after drying is 10 ~
100% and obtain the desired flame retardancy. Preferred flame retardancy was exhibited and sufficient water resistance was obtained when it was applied at 10 to 30% for automobile interior materials and at 30 to 70% for wall covering materials and aircraft interior materials. The performance of the mixed composition of the present invention can be further optimized by combining the compounds of groups A to D. In other words, it is important to utilize the characteristics of each group. Compounds from group A are used as softening agents, compounds from group B are used as main flame retardants, and compounds from group C are used as flame retardant aids in combination with bromine compounds. The synergistic effect and group D compounds maximize their role as flexible binders. The preferred mixing ratio is as follows. Compound of group A 10 to 30 parts B 20 to 60 C 10 to 30 D 5 to 30 parts More preferably, the mixing ratio of the compound of group D to the total weight of the compounds of groups A, B, and C is 30 % or less 5%
This is the above mixed composition. (Mechanism of action of the invention) The flame retardant according to the invention is a dispersion of compounds consisting of the above four groups A to D, each of which is essential for flame retardation of artificial leather-like structures. . The compound of group A is the only liquid among flame-retardant compounds, and this compound acts as a flame-retardant plasticizer for artificial leather-like structures and organic resins selected from group D, and improves flexibility. Grant. Both compounds of Groups B and C combine during combustion, exhibiting a synergistic effect of bromine and antimony, and achieving high flame retardancy. In particular, compounds with a high bromine content have an effective effect on flame retardation, making it possible to achieve flame retardancy with a low amount of adhesion. Furthermore, the non-aqueous organic resin of group D has the effect of fixing the flame-retardant compounds of groups A to C to the artificial leather-like structure. The flame retardant, which is a dispersion of a mixed composition of compounds with different properties, imparts viscosity, wettability, and moisture permeability to the dispersion, thereby improving the moisture permeability and adhesion of the flame retardant compound to artificial leather-like structures. Adjustment of the distribution state is enabled. (Effects of the Invention) The present invention has realized a highly flame-retardant artificial leather-like structure that has a softener and water resistance by combining a specific water-insoluble flame-retardant compound and a resin. By taking advantage of the characteristics of each compound that has a specific performance, we have achieved an improvement in flame retardancy due to a synergistic effect, making it possible to impart flame retardancy with a low amount of adhesion. Hereinafter, the present invention will be further explained with reference to Examples. Example 1 Artificial suede made of polyurethane-impregnated thermoplastic synthetic fiber with a thickness of 1.1 mm (“Ecsaine” manufactured by Toray Industries)
A polyester fabric having a basis weight of 80 g/m 2 was heat-sealed to the back side of the fabric as a backing fabric using a low melting point polyamide resin adhesive. Next, a water-dispersed flame retardant consisting of the following water-insoluble flame retardant compound and acrylic resin was prepared. The viscosity was 3000 CPS (25°C). Tris-dichloropropyl phosphate 10 parts Decabromodiphenyl ether 20 Antimony trioxide 10 Acrylic resin 4 (Nippon Reichhold, Boncourt WP-210) Dispersant 2 parts (ethylene oxide adduct of alkylphenol) Thickening Agent (CMC) 1 Water 53 Total 100 parts To prepare a flame retardant, an emulsified version of tris dichloropropyl phosphate was mixed with a dispersion of decabromodiphenyl ether and antimony trioxide. Next, the acrylic resin and the thickener were added and mixed while stirring. This mixed composition was applied to the artificial suede lining fabric using a round blade knife coater, and then heated at 110°C for 15 minutes.
Heat treated for minutes. The amount of the composition deposited was 24% by weight. As a comparison, as in the above example, ammonium polyphosphate was added as a substitute for the flame-retardant compound tris dichloropropyl phosphate to the artificial suede lined with the fabric (Comparative Example 1), and one that did not contain tris dichloropropyl phosphate. (Comparative Example 2) Furthermore, a flame retardant consisting of a mixed composition not containing decabromodiphenyl oxide (Comparative Example 3) or antimony trioxide (Comparative Example 4) was coated, and 23 to 25% of the flame retardant was adhered. was created. Regarding these, flame retardancy (burning rate) was measured according to the FMVSS-302 standard, and flexibility was measured according to the JIS-L1079 standard. Water resistant in water at room temperature
After immersion for 24 hours (bath ratio 1:300), it was dehydrated for 2 minutes in a domestic washing machine and then dried. Water resistance was calculated by weight loss rate based on weight change. The artificial suede of the present invention had high flame retardancy and excellent water resistance. On the other hand, in comparative examples, those containing ammonium polyphosphate as a substitute for tris dichloropropyl phosphate lacked water resistance, and those containing no ammonium polyphosphate lacked flexibility. Those containing no decabromodiphenyl ether or antimony trioxide had poor flame retardancy. The results are shown in Table 1. All data are average values of 5 measurements.
【表】
** 数値の大きいほど硬い
実施例 2
厚さ0.8mmの人工スエード(東レ製“エクセー
ヌ”)の裏面にドクターナイフを用いて、難燃剤
をコーテイングし、120℃で10分間熱処理した。
得られた難燃人工スエードの難燃性をJIS・L−
1091(A−4法)での垂直法での燃焼試験を行い
炭化長を測定した。耐水性は家庭用洗濯機で50℃
×10分間湯洗いしたものの重量変化および燃焼性
で評価した。一方難燃剤の含浸分布状態は分散染
料の着色により、裏面からの含浸深さ(mm)を断
面で観察した。
トリスジクロロプロピルホスフエート 8部
ヘキサブロモシクロドデカン 24〃
三酸化アンチモン 8〃
アクリル樹脂 6〃
(ウルトラゾール2635;武田薬品製)
分散剤 2〃
(ダウフアクス−2A;ダウケミカル製)
増粘剤(CMC) 1.2〃
分散染料(Foron Red FB) 1〃
水 49.8〃
合計 100部
比較例としては市販の難燃剤を実施例2と同様
にコーテイングし、120℃で10分間熱処理したも
のを用いた。
第2表に示す結果から明らかなように、実施例
2の難燃剤で処理された人工スエードは優れた耐
水性と難燃性が付与された。一方、比較例におけ
る難燃剤を処理したものは耐水性に欠け、洗濯機
で洗浄後は難燃性が著しく低下した。市販の難燃
際はいずれも高付着量にもかかわらず十分な難燃
性が得られず、本発明のごとく特定な組成物のみ
良好であつた。[Table] ** The larger the number, the harder it is Example 2 A flame retardant was coated on the back side of 0.8 mm thick artificial suede (Toray's "Ecsaine") using a doctor knife, and heat treated at 120°C for 10 minutes.
The flame retardancy of the obtained flame retardant artificial suede was determined by JIS L-
A vertical combustion test using 1091 (A-4 method) was conducted to measure the carbonization length. Water resistance is 50℃ in a home washing machine.
After washing in hot water for 10 minutes, the weight change and flammability were evaluated. On the other hand, the impregnated distribution state of the flame retardant was determined by coloring with a disperse dye, and the impregnation depth (mm) from the back surface was observed in a cross section. Tris dichloropropyl phosphate 8 parts Hexabromocyclododecane 24〃 Antimony trioxide 8〃 Acrylic resin 6〃 (Ultrasol 2635; manufactured by Takeda Pharmaceutical) Dispersant 2〃 (Daufu Ax-2A; manufactured by Dow Chemical) Thickener (CMC) 1.2〃 Disperse dye (Foron Red FB) 1〃 Water 49.8〃 Total 100 parts As a comparative example, one coated with a commercially available flame retardant in the same manner as in Example 2 and heat-treated at 120°C for 10 minutes was used. As is clear from the results shown in Table 2, the artificial suede treated with the flame retardant of Example 2 was provided with excellent water resistance and flame retardancy. On the other hand, those treated with a flame retardant in Comparative Examples lacked water resistance, and the flame retardancy significantly decreased after washing in a washing machine. All commercially available flame retardant compositions failed to provide sufficient flame retardancy despite the high coating weight, and only a specific composition such as the one of the present invention was good.
Claims (1)
物において、該構造物の厚さの主として裏面の部
分に、下記A、B、C、D4群から少なくとも1
種ずつ選ばれた化合物の混合組成物を、該構造物
に対して10〜100重量%付与されてなる難燃性人
工皮革状構造物。 A:40℃以下の温度で流動性があり、同温度以下
での水への溶解度が1%以下であるハロゲン化
リン酸エステル。 B:0℃から40℃の温度範囲での水への溶解度が
1%以下であり、融点が110℃以上であり、か
つ臭素含有量が30%以上である臭素含有化合
物。 C:酸化アンチモン D:JIS・K−5400に基づく鉛筆引つかき試験に
よる硬度が2H以下である非水溶性有機樹脂。[Claims] 1. In an artificial leather-like structure made of polyurethane and fibers, at least one of the following groups A, B, C, and D4 is applied mainly to the back surface of the structure.
1. A flame-retardant artificial leather-like structure obtained by adding 10 to 100% by weight of a mixed composition of selected compounds to the structure. A: A halogenated phosphate ester that has fluidity at a temperature of 40°C or lower and has a solubility in water of 1% or lower at the same temperature or lower. B: A bromine-containing compound having a solubility in water of 1% or less in a temperature range of 0°C to 40°C, a melting point of 110°C or more, and a bromine content of 30% or more. C: Antimony oxide D: Water-insoluble organic resin having a hardness of 2H or less in a pencil scratch test based on JIS K-5400.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6580984A JPS60215878A (en) | 1984-04-04 | 1984-04-04 | Flame-retardant artificial leather structure |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6580984A JPS60215878A (en) | 1984-04-04 | 1984-04-04 | Flame-retardant artificial leather structure |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60215878A JPS60215878A (en) | 1985-10-29 |
JPH0320514B2 true JPH0320514B2 (en) | 1991-03-19 |
Family
ID=13297721
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6580984A Granted JPS60215878A (en) | 1984-04-04 | 1984-04-04 | Flame-retardant artificial leather structure |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60215878A (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0745588B2 (en) * | 1986-03-27 | 1995-05-17 | 出光石油化学株式会社 | Method for manufacturing leather-like sheet material |
JP4664135B2 (en) | 2005-07-08 | 2011-04-06 | 大京化学株式会社 | Suede-like artificial leather with excellent flame retardancy and method for producing the same |
KR101030313B1 (en) | 2007-12-10 | 2011-04-20 | 코오롱인더스트리 주식회사 | Artificial leather and method of manufacturing the same |
JPWO2022071049A1 (en) * | 2020-09-29 | 2022-04-07 |
-
1984
- 1984-04-04 JP JP6580984A patent/JPS60215878A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS60215878A (en) | 1985-10-29 |
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