JPH0113496B2 - - Google Patents
Info
- Publication number
- JPH0113496B2 JPH0113496B2 JP2293981A JP2293981A JPH0113496B2 JP H0113496 B2 JPH0113496 B2 JP H0113496B2 JP 2293981 A JP2293981 A JP 2293981A JP 2293981 A JP2293981 A JP 2293981A JP H0113496 B2 JPH0113496 B2 JP H0113496B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- brominated
- polyester resin
- polycarbonate
- 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 22
- 229920000515 polycarbonate Polymers 0.000 claims description 20
- 239000004417 polycarbonate Substances 0.000 claims description 20
- -1 Cyclic imino ether compound Chemical class 0.000 claims description 19
- 229920001225 polyester resin Polymers 0.000 claims description 19
- 239000004645 polyester resin Substances 0.000 claims description 19
- 239000004593 Epoxy Substances 0.000 claims description 14
- 239000003063 flame retardant Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 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 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 9
- 229920001283 Polyalkylene terephthalate Polymers 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 10
- 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 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 229910005965 SO 2 Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000002993 cycloalkylene group Chemical group 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- MNJGOAKCQNKYKO-UHFFFAOYSA-N 2-[2-(1,3-oxazol-2-yl)phenyl]-1,3-oxazole Chemical compound C1=COC(C=2C(=CC=CC=2)C=2OC=CN=2)=N1 MNJGOAKCQNKYKO-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- DEZKEVLDRSOMGL-UHFFFAOYSA-N 3,14-dioxabicyclo[14.2.2]icosa-1(18),16,19-triene-2,15-dione Chemical group O=C1OCCCCCCCCCCOC(=O)C2=CC=C1C=C2 DEZKEVLDRSOMGL-UHFFFAOYSA-N 0.000 description 1
- LZFNKJKBRGFWDU-UHFFFAOYSA-N 3,6-dioxabicyclo[6.3.1]dodeca-1(12),8,10-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=CC1=C2 LZFNKJKBRGFWDU-UHFFFAOYSA-N 0.000 description 1
- ZVSXNPBSZYQDKJ-UHFFFAOYSA-N 3,8-dioxabicyclo[8.3.1]tetradeca-1(14),10,12-triene-2,9-dione Chemical group O=C1OCCCCOC(=O)C2=CC=CC1=C2 ZVSXNPBSZYQDKJ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は難燃性ポリエステル樹脂成形品に関す
る。更に詳しくは、本発明は力学的性質殊に伸度
に優れた難燃性のポリエステル樹脂組成物に関す
る。
ポリエチレンテレフタレート、ポリブチレンテ
レフタレート等で代表される熱可塑性のポリエス
テル樹脂は、射出成形等の溶融成形によつて、自
動車部品、電気機器部品等の用途に多量に使用さ
れている。ポリエステル樹脂を自動車部品或いは
電気機器部品用に用いる場合には、高度の力学的
性質と難燃性が要求される。
従来から、熱可塑性ポリエステル樹脂の難燃化
には主としてハロゲン化物の難燃剤が用いられて
いる。しかし、難燃剤を配合した成形品には、当
該難燃剤の影響でその力学的性質を損なつたもの
がしばしば認められる。それ故長期に亘り力学的
耐久性の高い樹脂が強く望まれている。
本発明者は、かかる問題点を克服し、力学的性
質のすぐれた樹脂組成物を得るべく鋭意検討した
結果、熱可塑性ポリエステル樹脂と特定の臭素含
有化合物からなる組成物に特定の環状イミノエー
テル化合物を添加したのち溶融成形した成形品が
上述の特性を有し、所期の目的が達成できること
を見出し、本発明に到達したものである。
すなわち、本発明は、
(A) ポリアルキレンテレフタレートより主として
なるポリエステル樹脂100重量部、
(B) 臭素化ビスフエノール類から得られるポリカ
ーボネート及び/又は臭素化ビスフエノール類
から得られるエポキシ化合物2〜50重量部、並
びに
(C) 下記式〔〕
〔但し式中nは2又は3の数、mは0又は1
数、lは1又は2の数、Dは(l+1)価の有
機基である。〕
で表わされる環状イミノエーテル化合物0.05〜
20重量部
からなる溶融成形用難燃性ポリエステル樹脂組成
物である。
本発明において用いられるポリエステル樹脂(A)
の主たる対象はポリアルキレンテレフタレートで
ある。当該ポリアルキレンテレフタトートは繰り
返し単位の870モル%以上がアルキレンテレフタ
レートよりなる線状ポリエステルであり、アルキ
レンテレフタレート単位を構成するアルキレン基
の炭素数は2〜6であることが好ましい。このア
ルキレン基としてはエチレン、トリメチレン、テ
トラメチレン、ヘキサメチレン等が例示でき、特
にエチレンまたはテトラメチレンが好ましい、ま
たアルキレンテレフタレート単位以外の繰り返し
単位としては例えばエチレンイソフタレート単
位、テトラメチレンイソフタレート単位、エチレ
ン−2,6−ナフタレンジカルボシレート単位、
デカメチレンテレフタレート単位等を挙げること
ができる。全繰り返し単位中、アルキレン(炭素
数2−6)テレフタレート単位の割合が70モル%
未満の場合には得られる成形品の物性が低下し、
又、アルキレンテレフタレート単位中のアルキレ
ン基の炭素数が7以上の場合には組成物の耐熱性
もしくは機械特性が低下する。
ポリエステル樹脂(A)は、前記ポリアルキレンテ
レフタレート以外に、10重量%以下の割合で他の
可燃性熱可塑性樹脂、例えば前記構造以外のポリ
エステル、ポリエーテルエステル、ポリカーボネ
ート、ポリアミド、ポリエーテル等が配合されて
いてもよい。
ポリエステル樹脂(A)は固有粘度が0.4以上、更
には0.5以上のものが好ましく用いられ、また軟
化点又は融点が130−350℃の範囲内にあることが
好ましい。更にまたポリエステル樹脂は末端カル
ボキシル基を有するものが好ましい。
本発明において用いられる難燃剤(B)は臭素化ビ
スフエノール類から得られるポリカーボネート及
び臭素化ビスフエノール類から得られるエポキシ
化合物より成る群から選ばれる。
上記臭素化ビスフエノール類から得られるポリ
カーボネート〔以下臭素化ポリカーボネートと云
う〕としては、下記式〔〕
〔但し式中k、pはそれぞれ1〜4の数、Xは炭
素数1〜6のアルキレン基、炭素数6〜12のシク
ロアルキレン基、−SO2−、−S−又は−O−であ
る。〕
で示される繰り返し単位を含有し、かつ平均繰り
返し単位が2以上のポリカーボネートが例示され
る。このポリカーボネートの平均繰り返し単位は
2〜30、更には2〜25であることが好ましい、ま
た上記式〔〕で示される繰り返し単位は臭素化
ポリカーボネート中にBr原子が10重量%以上含
有される割合であることが好ましい。従つて、臭
素化ポリカーボネートは前記式〔〕で示される
繰り返し単位単独よりなるポリカーボネートであ
つてもよく、また当該繰り返し単位と、非臭素化
ビスフエノール類より導かれる他のカーボネート
繰り返し単位とからなるコポリカーボネートであ
つてもよい。
臭素化ポリカーボネートは、例えば臭素化ビス
フエノール類または当該臭素化ビスフエノール類
と他のビスフエノール類との混合物とポリカーボ
ネート前駆体例えばホスゲンとを反応させる公知
の方法で製造することができる。その際、末端封
鎖剤は使用しなくてもよく、また使用しても良
い。末端封鎖剤を用いるときは得られる臭素化ポ
リカーボネートの融点の大巾な低下を引起さない
ものを用いることが好ましい。特に好ましい末端
封鎖剤としてはハロゲン又は有機基で置換されて
いてもよい芳香族モノヒドロキシ化合物があげら
れる。更に、臭素化ポリカーボネートの具体的製
造例としてテトラブロモビスフエノールA(1モ
ル)及びp−t−ブチルフエノール(0.1モル)
を、10%水酸化ナトリウム水溶液(3Kg)及び塩
化メチレン(2Kg)の混合物に加えて溶解させ、
温度を20〜30℃の範囲に保ちかつPHを約12に保ち
ながらホスゲンガス(2.2〜3.6モル)を吹込み、
ホスゲン吹込み終了後触媒として30%トリエチル
アミン水溶液(2.5ml)を添加して20〜30℃で3
時間反応させ、反応終了後塩化メチレン層を分離
し、充分水洗してからメタノール(10重量倍)中
に投入し、沈澱(白で充分過可能性なものであ
る)させ、沈澱物を過後乾燥させる方法があげ
られる。
臭素化ポリカーボネートのうち臭素化ビスフエ
ノールA、特にテトラビスフエノールAから得ら
れるポリカーボネートが好ましい。また耐熱性が
重要視される場合には平均繰り返し単位が10より
大きいもの特に16以上のものが好ましい。
また、前記臭素化ビスフエノール類から得られ
るエポキシ化合物〔以下臭素化エポキシ化合物と
云う〕としては、下記式〔〕
〔但し、式中k′、k″、p′、p″はそれぞれ0又は1
〜4の数であるが(k′+p′)q+k″+p″は1以上
の数である。Xは炭素数1〜6のアルキレン基、
炭素数6〜12のシクロアルキレン基、−SO2−、−
S−又は−O−である。またqは平均重合度を表
わし、0又は1以上の数である。〕
で示されるジエポキシ化合物が例示される。臭素
化エポキシ化合物はBr原子が10重量%以上含有
されるものであることが好ましい。上記式〔〕
においてqが2以上のとき、k′及びp′は0と1〜
4の数とを同時にとりうる。
このことは上記式〔〕が臭素化ビスフエノー
ル残基を有する(繰り返し)単位と非臭素化ビス
フエノール残基を有する(繰り返し)単位とを同
時に含有する臭素化エポキシ化合物をも包含して
いると理解されるべきである。かかる臭素化エポ
キシ化合物は、例えば臭素化ビスフエノールのジ
グリシジルエーテルと非臭素化ビスフエノールと
の反応、或いは非臭素化ビスフエノールのジグリ
シジルエーテルと臭素化ビスフエノールとの反応
等によつて得られる。前記式〔〕においてqは
臭素化エポキシ化合物の平均重合度を表わすもの
であり、0又は1以上の数を示すが、通常20以
下、好ましくは1〜10の範囲である。qがあまり
に大きすぎると、均一分数が困難となり、樹脂特
性を低下させる原因にもなるので好ましくない。
臭素化エポキシ化合物は、例えばテトラブロモ
ビスフエノールAのジグリシジルエーテルとテト
ラブロモビスフエノールAとをアルカリ金属の水
酸化物あるいはハロゲン化物(例えば塩化リチウ
ム、水酸化ナトリウム等)などを触媒として80〜
250℃で加熱すると容易に得られる。その際平均
重合度qはテトラブロモビスフエノールAのジグ
リシジルエーテルとテトラブロモビスフエノール
Aとの配合割合を変えることによつて容易に変え
ることができる。臭素化エポキシ化合物は通常単
一の化合物でなく、重合度の異なつたものの混合
物である。臭素化エポキシ化合物のうちテトラブ
ロモビスフエノールAから得られるジエポキシ化
合物或いはテトラブロモビスフエノールAとビス
フエノールAから得られるジエポキシ化合物が好
ましい。
臭素化ポリカーボネートと臭素化エポキシ化合
物はそれぞれ単独で用いてもよいが、併用する方
がより好ましい。両者を併用する場合、臭素化ポ
リカーボネートと臭素化エポキシ化合物の割合は
重量比で1:0.01〜1:5であることが好まし
い。
難燃性(B)はポリエステル樹脂(A)100重量部に対
して2〜50重量部、好ましくは5〜40重量部用い
られる。2重量部未満の場合には得られる組成物
の難燃性が劣り、50重量部をこえる場合には成形
品の物性が低下するので好ましくない。
本発明において難燃剤(B)と併用する環状イミノ
エーテル化合物(C)は前記式〔〕で表わされる化
合物である。
式〔〕においてXは(l+1)価の有機基で
あり、例えばエチレン、トリメチレン、テトラメ
チレン、ヘキシレン、オクタメチレン、シクロヘ
キシレン、シクロヘキサン−ジメチレン、ベンゼ
ン環、ビフエニル基、ナフタレン環、キシリレ
ン、式
The present invention relates to flame-retardant polyester resin molded articles. More specifically, the present invention relates to a flame-retardant polyester resin composition with excellent mechanical properties, particularly elongation. Thermoplastic polyester resins represented by polyethylene terephthalate, polybutylene terephthalate, etc. are used in large quantities for applications such as automobile parts and electrical equipment parts by melt molding such as injection molding. When polyester resins are used for automobile parts or electrical equipment parts, high mechanical properties and flame retardance are required. Conventionally, halide flame retardants have been mainly used to make thermoplastic polyester resins flame retardant. However, molded articles containing flame retardants are often found to have impaired mechanical properties due to the influence of the flame retardant. Therefore, resins with high mechanical durability over a long period of time are strongly desired. As a result of intensive studies aimed at overcoming these problems and obtaining a resin composition with excellent mechanical properties, the present inventors discovered that a specific cyclic iminoether compound can be added to a composition consisting of a thermoplastic polyester resin and a specific bromine-containing compound. The inventors have discovered that a molded article obtained by melt-molding after adding the above-described material has the above-mentioned properties and can achieve the intended purpose, and has thus arrived at the present invention. That is, the present invention includes (A) 100 parts by weight of a polyester resin mainly composed of polyalkylene terephthalate, (B) 2 to 50 parts by weight of a polycarbonate obtained from brominated bisphenols and/or an epoxy compound obtained from brominated bisphenols. part, and (C) the following formula [] [However, in the formula, n is the number 2 or 3, m is 0 or 1
number, l is a number of 1 or 2, and D is a (l+1)-valent organic group. ] Cyclic imino ether compound represented by 0.05~
This is a flame-retardant polyester resin composition for melt molding consisting of 20 parts by weight. Polyester resin (A) used in the present invention
The main target is polyalkylene terephthalate. The polyalkylene terephthalate is a linear polyester in which 870 mol% or more of the repeating units are composed of alkylene terephthalate, and the alkylene group constituting the alkylene terephthalate unit preferably has 2 to 6 carbon atoms. Examples of this alkylene group include ethylene, trimethylene, tetramethylene, hexamethylene, etc., with ethylene or tetramethylene being particularly preferred.Repeating units other than alkylene terephthalate units include, for example, ethylene isophthalate units, tetramethylene isophthalate units, ethylene -2,6-naphthalene dicarbosylate units,
Examples include decamethylene terephthalate units. The proportion of alkylene (2-6 carbon atoms) terephthalate units is 70 mol% among all repeating units.
If it is less than that, the physical properties of the obtained molded product will deteriorate,
Furthermore, if the alkylene group in the alkylene terephthalate unit has 7 or more carbon atoms, the heat resistance or mechanical properties of the composition will decrease. In addition to the polyalkylene terephthalate, the polyester resin (A) contains other combustible thermoplastic resins such as polyesters other than the above structure, polyether esters, polycarbonates, polyamides, polyethers, etc. in a proportion of 10% by weight or less. You can leave it there. The polyester resin (A) preferably has an intrinsic viscosity of 0.4 or more, more preferably 0.5 or more, and preferably has a softening point or melting point within the range of 130-350°C. Furthermore, the polyester resin preferably has a terminal carboxyl group. The flame retardant (B) used in the present invention is selected from the group consisting of polycarbonates obtained from brominated bisphenols and epoxy compounds obtained from brominated bisphenols. The polycarbonate obtained from the above-mentioned brominated bisphenols (hereinafter referred to as brominated polycarbonate) has the following formula [] [However, in the formula, k and p are each a number from 1 to 4, and X is an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 6 to 12 carbon atoms, -SO 2 -, -S- or -O- . ] Examples include polycarbonates containing the repeating units shown below and having an average repeating unit of 2 or more. The average repeating unit of this polycarbonate is preferably 2 to 30, more preferably 2 to 25, and the repeating unit represented by the above formula [] is such that the brominated polycarbonate contains 10% by weight or more of Br atoms. It is preferable that there be. Therefore, the brominated polycarbonate may be a polycarbonate consisting of a single repeating unit represented by the above formula [], or a copolycarbonate consisting of the repeating unit and other carbonate repeating units derived from non-brominated bisphenols. It may also be polycarbonate. Brominated polycarbonates can be produced, for example, by a known method of reacting brominated bisphenols or a mixture of the brominated bisphenols and other bisphenols with a polycarbonate precursor such as phosgene. In this case, the terminal blocking agent may not be used or may be used. When using an end-capping agent, it is preferable to use one that does not cause a drastic decrease in the melting point of the resulting brominated polycarbonate. Particularly preferred end-capping agents include aromatic monohydroxy compounds which may be substituted with halogen or organic groups. Furthermore, as a specific production example of brominated polycarbonate, tetrabromobisphenol A (1 mol) and pt-butylphenol (0.1 mol)
was added and dissolved in a mixture of 10% aqueous sodium hydroxide solution (3Kg) and methylene chloride (2Kg),
Blow in phosgene gas (2.2 to 3.6 mol) while keeping the temperature in the range of 20 to 30°C and the pH to about 12.
After the phosgene injection was completed, a 30% triethylamine aqueous solution (2.5 ml) was added as a catalyst and the mixture was heated at 20 to 30°C.
After the reaction was completed, the methylene chloride layer was separated, thoroughly washed with water, poured into methanol (10 times the weight), and precipitated (white and easily permeable). The precipitate was filtered and dried. Here are some ways to do it. Among the brominated polycarbonates, polycarbonates obtained from brominated bisphenol A, particularly tetrabisphenol A, are preferred. Furthermore, when heat resistance is important, those having an average repeating unit of more than 10 are preferred, particularly those with an average repeating unit of 16 or more. In addition, the epoxy compound obtained from the brominated bisphenols (hereinafter referred to as brominated epoxy compound) has the following formula [] [However, in the formula, k′, k″, p′, p″ are each 0 or 1
~4, but (k'+p')q+k''+p'' is a number greater than or equal to 1. X is an alkylene group having 1 to 6 carbon atoms,
Cycloalkylene group having 6 to 12 carbon atoms, -SO 2 -, -
S- or -O-. Moreover, q represents an average degree of polymerization, and is a number of 0 or 1 or more. ] Diepoxy compounds shown by these are exemplified. The brominated epoxy compound preferably contains 10% by weight or more of Br atoms. The above formula []
When q is 2 or more, k' and p' are 0 and 1 ~
It can take on the number 4 at the same time. This means that the above formula [] also includes a brominated epoxy compound that simultaneously contains a (repeat) unit having a brominated bisphenol residue and a (repeat) unit having a non-brominated bisphenol residue. should be understood. Such brominated epoxy compounds can be obtained, for example, by reacting diglycidyl ether of brominated bisphenol with non-brominated bisphenol, or by reacting diglycidyl ether of non-brominated bisphenol with brominated bisphenol. . In the above formula [], q represents the average degree of polymerization of the brominated epoxy compound, and is a number of 0 or 1 or more, but is usually 20 or less, preferably in the range of 1 to 10. If q is too large, it will be difficult to obtain a uniform fraction, which will cause deterioration of resin properties, which is not preferable. The brominated epoxy compound is, for example, prepared by combining diglycidyl ether of tetrabromobisphenol A and tetrabromobisphenol A with an alkali metal hydroxide or halide (e.g. lithium chloride, sodium hydroxide, etc.) as a catalyst.
Easily obtained by heating at 250℃. In this case, the average degree of polymerization q can be easily changed by changing the blending ratio of diglycidyl ether of tetrabromobisphenol A and tetrabromobisphenol A. Brominated epoxy compounds are usually not a single compound but a mixture of compounds with different degrees of polymerization. Among the brominated epoxy compounds, a diepoxy compound obtained from tetrabromobisphenol A or a diepoxy compound obtained from tetrabromobisphenol A and bisphenol A is preferred. Although the brominated polycarbonate and the brominated epoxy compound may be used alone, it is more preferable to use them in combination. When both are used in combination, the ratio of the brominated polycarbonate to the brominated epoxy compound is preferably 1:0.01 to 1:5 by weight. The flame retardant (B) is used in an amount of 2 to 50 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of the polyester resin (A). If it is less than 2 parts by weight, the resulting composition will have poor flame retardancy, and if it exceeds 50 parts by weight, the physical properties of the molded article will deteriorate, which is not preferable. The cyclic iminoether compound (C) used in combination with the flame retardant (B) in the present invention is a compound represented by the above formula []. In the formula [], X is a (l+1)-valent organic group, such as ethylene, trimethylene, tetramethylene, hexylene, octamethylene, cyclohexylene, cyclohexane-dimethylene, benzene ring, biphenyl group, naphthalene ring, xylylene,
【式】(式中Yは
O、S、SO2、CO、COO、CH2基等を表わす)
で表される芳香核等があげられる。
環状イミノエーテル化合物としては更に具体的
にはビス(2−オキサゾリル)、ビス(2−オキ
サジル)、1,2−ビス(2−オキサジル)エタ
ン、1,4−ビス(2−オキサジル)ブタン、
1,8−ビス(2−オキサジル)オクタン、1,
4−ビス(2−オキサジル)シクロヘキサン、ビ
ス(2−オキサゾリル)ベンゼン、2,6−ビス
(2−オキサゾリル)ナフタレン、1,2,4−
トリス(2−オキサゾリル)ベンゼン、3,3,
5−トリス(2−オキサゾリル)ベンゾフエノン
等を例示することができる。かかる環状イミノエ
ーテル化合物は1種又は2種以上を用いることが
でき、その添加量はポリエステル樹脂(A)100重量
部に対して0.05〜20重量部、好ましくは0.1〜10
重量部である。0.05重量部未満では成形品の物性
向上がみられず、20重量部をこえると成形品がも
ろくなり耐熱性が減少するので好ましくない。
本発明のポリエステル樹脂組成物をつくる場合
には、所望により例えばアンチモン化合物(例え
ば三酸化アンチモン等)の如き難燃助剤;タル
ク、カーボンブラツク、シリカ、アルミナ、酸化
チタン等の如き充填材;ガラス繊維、炭素繊維等
の如き補強材;安定剤;着色剤;滑剤;離型剤等
の他の添加物を添加することができる。
本発明において成分(A)、(B)及び(C)を用いての溶
融成形方法は任意の溶融成形法を選ぶことができ
る。例えば、成分(A)と成分(B)を溶融混合して得た
チツプに成分(C)をドライブレンドして溶融成形す
る方法;成分(A)、成分(B)及び成分(C)を溶融混合し
て得たチツプを溶融成形する方法;成分(A)、成分
(B)及び成分(C)をドライブレンドして直接溶融成形
する方法;成分(A)と成分(C)を溶融混合して得たチ
ツプに成分(B)をドライブレンドして溶融成形する
方法等を挙げることができる。
ポリエステル樹脂成形品の形状は、用途に合つ
た所望の形状をとることができ、例えば自動車部
品、電気機器部品、機械部品等として用いるのに
有用な形状をとることができる。
本発明のポリエステル樹脂組成物は、難燃性で
あり、かつポリエステル樹脂本来のすぐれた力学
的特性殊に引張伸度を有する。
以下実施例により本発明を詳述する。尚例中の
ポリエステル樹脂の固有粘度はオルソクロロフエ
ノールを溶媒として35℃で測定したものである。
実施例1〜6及び比較例1〜3
固有粘度1.06のポリブチレンテレフタレート
100重量部当り臭素化物、環状イミノエーテル化
合物及び他の添加剤を表−1に示す割合で混合
し、押出機で230℃で混練させてチツプをつくり、
射出成形機で230℃で成形した。得られた試験片
の物性を表−1に示す。
表−1の結果から明らかなように、本発明のポ
リエステル樹脂組成物から得られる成形品が極め
て高い伸度を有しているのに比較して、ビス(2
−オキサゾリル)を用いないか、ごくわずかしか
用いない場合の成形品は伸度が極めて低いことが
判る。[Formula] (In the formula, Y represents O, S, SO 2 , CO, COO, CH 2 group, etc.)
Examples include aromatic nuclei represented by More specifically, the cyclic imino ether compounds include bis(2-oxazolyl), bis(2-oxazyl), 1,2-bis(2-oxazyl)ethane, 1,4-bis(2-oxazyl)butane,
1,8-bis(2-oxazyl)octane, 1,
4-bis(2-oxazyl)cyclohexane, bis(2-oxazolyl)benzene, 2,6-bis(2-oxazolyl)naphthalene, 1,2,4-
Tris(2-oxazolyl)benzene, 3,3,
Examples include 5-tris(2-oxazolyl)benzophenone. One type or two or more types of such cyclic iminoether compounds can be used, and the amount added is 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the polyester resin (A).
Parts by weight. If it is less than 0.05 parts by weight, no improvement in the physical properties of the molded article will be observed, and if it exceeds 20 parts by weight, the molded article will become brittle and its heat resistance will decrease, which is not preferable. When preparing the polyester resin composition of the present invention, flame retardant additives such as antimony compounds (eg, antimony trioxide, etc.); fillers such as talc, carbon black, silica, alumina, titanium oxide, etc.; glass; Other additives can be added, such as reinforcing materials such as fibers, carbon fibers, etc.; stabilizers; colorants; lubricants; mold release agents. In the present invention, any melt-molding method can be selected as the melt-molding method using components (A), (B), and (C). For example, a method in which component (C) is dry blended into chips obtained by melt-mixing component (A) and component (B) and then melt-molded; Method of melt-molding chips obtained by mixing; Component (A), Component
Method of dry blending (B) and component (C) and direct melt molding; method of dry blending component (B) with chips obtained by melt mixing component (A) and component (C) and melt molding. etc. can be mentioned. The shape of the polyester resin molded product can be any desired shape suitable for the intended use, and can be, for example, a shape useful for use as automobile parts, electrical equipment parts, mechanical parts, etc. The polyester resin composition of the present invention is flame retardant and has excellent mechanical properties, especially tensile elongation, inherent to polyester resins. The present invention will be explained in detail with reference to Examples below. The intrinsic viscosity of the polyester resin in the examples was measured at 35°C using orthochlorophenol as a solvent. Examples 1 to 6 and Comparative Examples 1 to 3 Polybutylene terephthalate with an intrinsic viscosity of 1.06
A bromide, a cyclic imino ether compound and other additives per 100 parts by weight were mixed in the proportions shown in Table 1 and kneaded in an extruder at 230°C to make chips.
Molded at 230℃ using an injection molding machine. Table 1 shows the physical properties of the obtained test piece. As is clear from the results in Table 1, the molded product obtained from the polyester resin composition of the present invention has extremely high elongation, while the bis(2
It can be seen that the elongation of molded products in which no or only a small amount of oxazolyl (-oxazolyl) is used has extremely low elongation.
【表】【table】
【表】
実施例 7
実施例1においてビス(2−オキサゾリル)
0.61重量部の代りにビス(2−オキサジル)0.68
重量部を用いること以外は実施例1と同様にして
得た引張強度は622Kg/cm2、伸度は189%であつ
た。[Table] Example 7 In Example 1, bis(2-oxazolyl)
Bis(2-oxadyl) 0.68 instead of 0.61 parts by weight
The tensile strength obtained was 622 Kg/cm 2 and the elongation was 189% in the same manner as in Example 1 except that parts by weight were used.
Claims (1)
してなるポリエステル樹脂100重量部、 (B) 臭素化ビスフエノール類から得られるポリカ
ーボネート及び/又は臭素化ビスフエノール類
から得られるエポキシ化合物2〜50重量部、並
びに (C) 下記式〔〕 〔但し式中nは2又は3の数、mは0又は1の
数、lは1又は2の数、Dは(l+1)価の有
機基である。〕 で表わされる環状イミノエーテル化合物0.05〜
20重量部からなる溶融成形用難燃性ポリエステ
ル樹脂組成物。[Scope of Claims] 1 (A) 100 parts by weight of a polyester resin mainly composed of polyalkylene terephthalate, (B) 2 to 50 parts by weight of a polycarbonate obtained from a brominated bisphenol and/or an epoxy compound obtained from a brominated bisphenol. Parts by weight, and (C) the following formula [] [However, in the formula, n is a number of 2 or 3, m is a number of 0 or 1, l is a number of 1 or 2, and D is a (l+1)-valent organic group. ] Cyclic imino ether compound represented by 0.05~
A flame-retardant polyester resin composition for melt molding consisting of 20 parts by weight.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2293981A JPS57137348A (en) | 1981-02-20 | 1981-02-20 | Flame-retardant polyester resin molded article |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2293981A JPS57137348A (en) | 1981-02-20 | 1981-02-20 | Flame-retardant polyester resin molded article |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS57137348A JPS57137348A (en) | 1982-08-24 |
JPH0113496B2 true JPH0113496B2 (en) | 1989-03-07 |
Family
ID=12096592
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2293981A Granted JPS57137348A (en) | 1981-02-20 | 1981-02-20 | Flame-retardant polyester resin molded article |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS57137348A (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6172775A (en) * | 1984-09-17 | 1986-04-14 | Matsunaga Kagaku Kogyo Kk | Halogenated epoxy resin |
JPH078944B2 (en) * | 1985-11-12 | 1995-02-01 | ユニチカ株式会社 | Polyester resin composition for sealing |
JP2623558B2 (en) * | 1987-03-23 | 1997-06-25 | 三菱瓦斯化学株式会社 | Polycarbonate resin composition for molding |
JPH0726008B2 (en) * | 1987-03-31 | 1995-03-22 | 住友化学工業株式会社 | Method for producing thermoplastic resin composition |
JP2624974B2 (en) * | 1987-12-09 | 1997-06-25 | ポリプラスチックス株式会社 | Electrical wire |
JP2928266B2 (en) * | 1989-05-08 | 1999-08-03 | ポリプラスチックス株式会社 | Polyester resin composition and molded article |
JP5465506B2 (en) * | 2009-10-14 | 2014-04-09 | 株式会社オートネットワーク技術研究所 | Modified recycled polyester resin and molded product using the same |
-
1981
- 1981-02-20 JP JP2293981A patent/JPS57137348A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS57137348A (en) | 1982-08-24 |
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