JPS6234253B2 - - Google Patents
Info
- Publication number
- JPS6234253B2 JPS6234253B2 JP56041702A JP4170281A JPS6234253B2 JP S6234253 B2 JPS6234253 B2 JP S6234253B2 JP 56041702 A JP56041702 A JP 56041702A JP 4170281 A JP4170281 A JP 4170281A JP S6234253 B2 JPS6234253 B2 JP S6234253B2
- Authority
- JP
- Japan
- Prior art keywords
- flame retardant
- bis
- bisphenol
- ether
- flame
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003063 flame retardant Substances 0.000 claims description 42
- 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 38
- 229920000098 polyolefin Polymers 0.000 claims description 27
- 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 20
- 239000000203 mixture Substances 0.000 claims description 15
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001246 bromo group Chemical group Br* 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 2
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 claims description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 125000001931 aliphatic group Chemical group 0.000 description 14
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 11
- 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
- 239000007983 Tris buffer Substances 0.000 description 10
- -1 ethylene, propylene Chemical group 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 229910000410 antimony oxide Inorganic materials 0.000 description 8
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 8
- 238000000465 moulding Methods 0.000 description 7
- 229930185605 Bisphenol Natural products 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 4
- NKBJAXQSZYUMIM-UHFFFAOYSA-N 1,1-dibromo-4-(4,4-dibromobutoxy)butane Chemical compound BrC(CCCOCCCC(Br)Br)Br NKBJAXQSZYUMIM-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- PWYPGMLLXRAVEN-UHFFFAOYSA-N 1,1,1-tribromo-3-(3,3,3-tribromopropoxy)propane Chemical compound BrC(CCOCCC(Br)(Br)Br)(Br)Br PWYPGMLLXRAVEN-UHFFFAOYSA-N 0.000 description 2
- VOPCVXBZWVMCEI-UHFFFAOYSA-N 1,1,1-tribromo-4-(4,4,4-tribromobutoxy)butane Chemical compound BrC(CCCOCCCC(Br)(Br)Br)(Br)Br VOPCVXBZWVMCEI-UHFFFAOYSA-N 0.000 description 2
- VPVMCHYSPWAZFD-UHFFFAOYSA-N 1,1-dibromo-2-(2,2-dibromoethoxy)ethane Chemical compound BrC(Br)COCC(Br)Br VPVMCHYSPWAZFD-UHFFFAOYSA-N 0.000 description 2
- XQKQZOLAVMIQHZ-UHFFFAOYSA-N 1,1-dibromo-3-(3,3-dibromopropoxy)propane Chemical compound BrC(Br)CCOCCC(Br)Br XQKQZOLAVMIQHZ-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical class C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- NLJYVSRAICBDSH-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,15,15-triacontachlorocyclopentadecane Chemical compound ClC1(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C1(Cl)Cl NLJYVSRAICBDSH-UHFFFAOYSA-N 0.000 description 1
- AQPHBYQUCKHJLT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4,5,6-pentabromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br AQPHBYQUCKHJLT-UHFFFAOYSA-N 0.000 description 1
- 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
- ZHMURHNGRUXDMO-UHFFFAOYSA-N 1,2,3,4-tetrabromo-5-methylbenzene Chemical compound CC1=CC(Br)=C(Br)C(Br)=C1Br ZHMURHNGRUXDMO-UHFFFAOYSA-N 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004698 Polyethylene 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
- 230000002411 adverse Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl 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
- 239000004566 building material Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- UGQQAJOWXNCOPY-UHFFFAOYSA-N dechlorane plus Chemical compound C12CCC3C(C4(Cl)Cl)(Cl)C(Cl)=C(Cl)C4(Cl)C3CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl UGQQAJOWXNCOPY-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- GVYLCNUFSHDAAW-UHFFFAOYSA-N mirex Chemical compound ClC12C(Cl)(Cl)C3(Cl)C4(Cl)C1(Cl)C1(Cl)C2(Cl)C3(Cl)C4(Cl)C1(Cl)Cl GVYLCNUFSHDAAW-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003381 stabilizer Substances 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
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は難燃性と成形時のヒケ防止性を併せ有
するポリオレフイン組成物に関する。
ポリオレフインは着火しやすい、燃えやすいと
いう欠点を有するために、難燃化について種々の
提案がなされている。また、ポリオレフインはそ
の使用分野も電気製品、自動車部品などの機械部
品、建材等と多くなつている。そのため外観上や
寸法性の観点から、成形時のヒケが問題になる。
一般にポリオレフインのヒケを防止するために
は無機物の添加が考えられるが、同時に難燃性を
附与せしめるには種々の問題がある。すなわち、
無機系の難燃剤である水酸化アルミニウムや水酸
化マグネシウムを添加することによつて、ヒケの
無いかつ難燃性のある組成物は得られるが、水酸
化アルミニウムや水酸化マグネシウムの添加量を
非常に多くしなければ難燃効果が出ない。また、
水酸化アルミニウムや水酸化マグネシウムを多量
に添加したポリオレフイン組成物は造粒などの作
業性ばかりか衝撃性の低下をきたしたり比重が大
きくなるなど使用分野が制限される。
他方、ポリオレフインの成形温度より融点の高
い有機系難燃剤を使用することによつてヒケを防
止することも考えられるが、これらも無機系の難
燃剤と同様に難燃効果が低いため多量の添加が必
要である。また、臭素化脂肪族炭化水素基を有す
る難燃剤は、ポリオレフインの成形温度より低い
融点を有し、少量の添加でポリオレフインに難燃
性を附与せしめることが出来るが、該ポリオレフ
イン組成物は成形時のヒケ防止効果が無く使用分
野が制限される。
また前記脂肪族臭素化物を有する難燃剤と、無
機物を併用したポリオレフイン組成物は、ヒケ防
止効果を発揮するが、難燃性が減少し可燃性とな
る欠点がある。従つて、少量の添加で難燃性を有
し、かつヒケ防止効果も有する難燃剤の開発が望
まれる。
本発明者らは、造粒作業の困難性を伴わず、ま
た衝撃強度の低下が少なく、かつ比重も低く、さ
らに難燃性の良好なポリオレフイン組成物を開発
するべく種々検討した結果、臭素化脂肪族炭化水
素基を有する難燃剤と高融点（融点が240℃以
上）の難燃剤、及び酸化アンチモンを併用するこ
とによつて、所望のポリオレフイン組成物が得ら
れることを見出し、本発明を完成させるに至つ
た。
本発明は、ポリオレフインに臭素化脂肪族炭化
水素基を有する難燃剤、融点が240℃以上の難燃
剤、および酸化アンチモンを含有してなる難燃性
ポリオレフイン組成物である。
本発明で用いられるポリオレフインとしてはエ
チレン、プロピレン、ブチレン等のα−オレフイ
ンの単独重合体、該α−オレフインと他のα−オ
レフインとの共重合体、ブロツク共重合体あるい
はこれらの混合物等が挙げられ、特にポリプロピ
レンを主成分とするポリオレフインが好ましく用
いられる。
また、臭素化脂肪族炭化水素基を有する難燃剤
としては、少くとも２個以上の臭素原子を結合す
る炭素数２〜18のアルキル基を有する公知の難燃
剤が好適である。例えば一般式
（但し、R1及びR2は同種又は異種の少くとも２個
の臭素原子を結合する炭素数２〜18のアルキル
基）で示されるエーテル化四臭化ビスフエノール
Ａ、一般式
（但し、R3、及びR4は同種又は異種の少くとも２
個の臭素原子を結合する炭素数２〜18のアルキル
基）で示されるエーテル化四臭化ビスフエノール
Ｓ、一般式
The present invention relates to a polyolefin composition that has both flame retardancy and sink mark prevention properties during molding. Since polyolefins have the disadvantage of being easily ignited and combustible, various proposals have been made to make them flame retardant. Furthermore, polyolefins are being used in many fields such as electrical products, mechanical parts such as automobile parts, and building materials. Therefore, from the viewpoint of appearance and dimensional properties, sink marks during molding become a problem. Generally, adding inorganic substances is considered to prevent sink marks in polyolefins, but there are various problems in simultaneously imparting flame retardancy. That is,
By adding aluminum hydroxide and magnesium hydroxide, which are inorganic flame retardants, a composition with no sink marks and flame retardancy can be obtained, but the amount of aluminum hydroxide or magnesium hydroxide added must be extremely small. The flame retardant effect will not be achieved unless the amount is increased. Also,
Polyolefin compositions containing a large amount of aluminum hydroxide or magnesium hydroxide are limited in the field of use because they not only have workability such as granulation, but also have reduced impact resistance and increased specific gravity. On the other hand, it is possible to prevent sink marks by using an organic flame retardant whose melting point is higher than the molding temperature of the polyolefin, but these also have a low flame retardant effect like inorganic flame retardants, so they must be added in large amounts. is necessary. Furthermore, a flame retardant having a brominated aliphatic hydrocarbon group has a melting point lower than the molding temperature of polyolefin, and can impart flame retardancy to polyolefin when added in a small amount. It has no effect on preventing sink marks, and its field of use is limited. Further, a polyolefin composition using a flame retardant having an aliphatic brominated compound in combination with an inorganic substance exhibits an effect of preventing sink marks, but has the drawback of decreased flame retardancy and becoming combustible. Therefore, it is desired to develop a flame retardant that exhibits flame retardancy when added in a small amount and also has a sink mark prevention effect. The present inventors have conducted various studies to develop a polyolefin composition that does not cause difficulty in granulation work, has little decrease in impact strength, has a low specific gravity, and has good flame retardancy. It was discovered that a desired polyolefin composition could be obtained by using a flame retardant having an aliphatic hydrocarbon group, a flame retardant with a high melting point (melting point of 240°C or higher), and antimony oxide, and the present invention was completed. I ended up letting it happen. The present invention is a flame-retardant polyolefin composition comprising a polyolefin containing a flame retardant having a brominated aliphatic hydrocarbon group, a flame retardant having a melting point of 240° C. or higher, and antimony oxide. Examples of the polyolefin used in the present invention include homopolymers of α-olefins such as ethylene, propylene, and butylene, copolymers of the α-olefins with other α-olefins, block copolymers, and mixtures thereof. In particular, polyolefin containing polypropylene as a main component is preferably used. Further, as the flame retardant having a brominated aliphatic hydrocarbon group, a known flame retardant having an alkyl group having 2 to 18 carbon atoms bonding at least two or more bromine atoms is suitable. For example, general formula (However, R 1 and R 2 are alkyl groups having 2 to 18 carbon atoms bonding at least two bromine atoms of the same or different types) Etherified tetrabromide bisphenol A represented by the general formula (However, R 3 and R 4 are at least two of the same or different types.
Etherified tetrabrominated bisphenol S represented by an alkyl group having 2 to 18 carbon atoms bonding bromine atoms, general formula
【式】
（但しR5、R6及びR7は同種又は異種の少くとも２
個の臭素原子を結合する炭素数２〜18のアルキル
基）で示されるイソシアヌル酸と臭素化脂肪族ア
ルコールのエステル化物などが用いられる。具体
的には、エーテル化ビスフエノールＡとしては、
一般に四臭化ビスフエノールＡビス（ジブロモエ
チルエーテル）、四臭化ビスフエノールＡビス
（ジブロモプロピルエーテル）、四臭化ビスフエノ
ールＡビス（ジブロモブチルエーテル）、四臭化
ビスフエノールＡビス（トリブロモプロピエーテ
ル）、四臭化ビスフエノールＡビス（テトラブロ
モプロピルエーテル）、四臭化ビスフエノールＡ
ビス（トリブロモブチルエーテル）、四臭化ビス
フエノールＡビス（テトラブロモブチルエーテ
ル）等の四臭化ビスフエノールＡビス（ポリブロ
モアルキルエーテル）が好適に使用される。
またエーテル化ビスフエノールＳとしては、一
般に四臭化ビスフエノールＳビス（ジブロモエチ
ルエーテル）、四臭化ビスフエノールＳビス（ジ
ブロモプロピルエーテル）、四臭化ビスフエノー
ルＳビス（ジブロモブチルエーテル）、四臭化ビ
スフエノールＳビス（トリブロモプロピルエーテ
ル）、四臭化ビスフエノールＳビス（テトラブロ
モプロピルエーテル）、四臭化ビスフエノールＳ
ビス（トリブロモブチルエーテル）、四臭化ビス
フエノールＳビス（テトラブロモブチルエーテ
ル）、等の四臭化ビスフエノールＳビス（ポリプ
ロモアルキルエーテル）が好適に使用される。
またイソシアヌル酸と臭素化脂肪族アルコール
のエステルとしては、一般にトリス（ジブロモエ
チル）イソシアヌレート、ビス（ジブロモエチ
ル）イソシアヌレート、トリス（ジブロモプロピ
ル）イソシアヌレート、ビス（ジブロモプロピ
ル）イソシアヌレート、トリス（ジブロモブチ
ル）イソシアヌレート、ビス（ジブロモブチル）
イソシアヌレート、トリス（トリブロモプロピ
ル）イソシアヌレート、ビス（トリブロモプロピ
ル）イソシアヌレート、トリス（テトラブロモプ
ロピル）イソシアヌレート、ビス（テトラブロモ
プロピル）イソシアヌレート、トリス（トリブロ
モブチル）イソシアヌレート、ビス（トリブロモ
ブチル）イソシアヌレート、トリス（テトラブロ
モブチル）イソシアヌレート、ビス（テトラブロ
モブチル）イソシアヌレート等の臭素化アルキル
イソシアヌレートが好適に使用される。
臭素化脂肪族炭化水素基を有する難燃剤の配合
量はポリオレフイン100重量部に対して0.5〜50重
量部、好ましくは１〜40重量部である。かかる臭
素化脂肪族炭化水素基を有する難燃剤の配合量
が、上記範囲より少ない場合は充分な難燃効果が
発揮できず、また上記上限値より多い場合は難燃
効果の増大が無く不経済であるばかりでなく、押
出機内での熱分解が激しくなり、ポリオレフイン
の分解が起るため好ましくない。
また本発明においては臭素化脂肪族炭化水素基
を有する難燃剤と共に、融点が240℃以上の難燃
剤を用いることが、特に難燃性と成形時のヒケ防
止性を発揮するために極めて重要である。即ち、
臭素化脂肪族炭化水素基を有する難燃剤に融点が
240℃以下の難燃剤を併用しても、難燃性は得ら
れるが、成形時のヒケ防止性を有するポリオレフ
イン組成物が得られない。融点が240℃以上の難
燃剤としては臭素系、塩素系、リン系等を問わず
公知の難燃剤から選択され、併用する臭素化脂肪
族炭化水素基を有する難燃剤の難燃効果を阻害す
るものでなければ特に制限されず使用される。
例えばデカブロムジフエニルエーテル、デカブ
ロムジフエニル、ヘキサブロムベンゼン、ペンタ
ブロムトルエン、テトラブロム無水フタル酸など
の芳香族臭素化合物；デクロラン、デクロランプ
ラス（いずれも商品名）などパークロロシクロペ
ンタデカン系の塩素系有機化合物；そのほかエチ
レンビス〔トリス（２−シアノアルキル）ホスホ
ニウムブロマイド〕などのリン系有機化合物など
があげられる。
上記した融点が240℃以上の難燃剤の配合量は
ポリオレフイン100重量部に対して１〜70重量
部、好ましくは３〜50重量部である。融点が240
℃以上の難燃剤の添加量が前記下限量より低い場
合は、ポリオレフイン組成物の成形時におけるヒ
ケ防止効果が充分でなく、また逆に上限量より高
い場合はポリオレフイン組成物が高比重となつた
り、衝撃性が低下するため好ましくない。
さらに酸化アンチモンの添加は難燃剤の効果を
十分に向上するために添加される。酸化アンチモ
ンとしては市販の一般的な酸化アンチモンが使用
され、その配合量は臭素化脂肪族炭化水素基を有
する難燃剤と融点が240℃以上の難燃剤の合計量
に対して、一般に10〜250重量％である。酸化ア
ンチモンの配合量が前記下限値より低い場合は難
燃性の向上が充分でなく、また前記上限値よりも
高い場合も、難燃性は低下するため好ましくな
い。
本発明においてポリオレフインに対して臭素化
脂肪族炭化水素基を有する難燃剤、融点が240℃
以上の難燃剤、および酸化アンチモンの混合順序
は特に限定されず、各成分を同時に混合しても良
く、数種を予じめ混合し残りを後から混合しても
良い。
また混合方法も特に限定されず、一般にタンブ
ラー式ブレンダー、Ｖ型ブレンダー、ヘンシエル
ミキサー、リボンミキサー等を用いて行なわれ
る。更に、予め数種をヘンシエルミキサーで混合
し、次いで残りを加えてタンボラー式ブレンダー
で混合するといつた、混合順序、装置を変える方
法も採用できる。
本発明に於けるポリオレフイン組成物は基本的
に前記ポリオレフイン、臭素化脂肪族炭化水素基
を有する難燃剤、融点が240℃以上の難燃剤、お
よび酸化アンチモンよりなるものであるが、これ
らの成分とともに従来公知の安定剤、着色剤、帯
電防止剤、滑剤、核剤、また難燃性に悪影響をお
よぼさない程度の量の無機物などを添加してもよ
い。
本発明のポリオレフイン組成物は、臭素化脂肪
族炭化水素基を有する難燃剤の非常に高い難燃性
と、240℃以上の融点を有する難燃剤が有するヒ
ケ防止性と難燃性をうまく組み合わせることによ
り、それぞれ難燃剤の少量添加にもかかわらず、
難燃性とヒケ防止性の効果を同時に発揮されるも
のである。
本発明を更に具体的に説明するために、以下に
実施例及び比較例を挙げて説明するが、本発明は
これら実施例に限定されるものではない。なお実
施例及び比較例で示した難燃性試験結果はUL94
規格の垂直法に準拠して行ない、平均自己消火時
間として10本の燃焼試験片において各２回の着
炎、すなわち合計20回の着炎後の自己消火時間の
平均を示した。また最大自己消火時間は前記20回
の着炎後の自己消火時間中の最大値を示した。ま
た綿花着火率は試験片下の綿花が試験片からの
“火だれ”により着火する程度として試験片10本
中何本が着火させるかで表示した。例えば10本中
に３本が着火させたとすると3/10と表示した。
尚、試験片の形状は５インチ×0.5インチ×1/8
で行なつた。
また、ヒケ防止性を検討するため、ある程度ヒ
ケが発生する金型Ｋ−と、非常にヒケが発生し
やすい金型Ｋ−の二つの金型を用いて成形物を
作成し、目視でヒケの発生程度を観察した。この
時の判断基準として、ほとんどヒケの発生が観察
されないものを◎とし、わずかにヒケが発生して
いるものを〇とし、ある程度ヒケが発生している
ものを△とし、大きくヒケが発生しているものを
×とした。
実施例１および比較例１
ポリプロピレン（徳山曹達社製ME140、MI9の
ホモポリマー）100重量部に対して、第１表に示
す割合の四臭化ビスフエノールＡビス（二臭化プ
ロピルエーテル）、デカブロムジフエニルエー
ル、三酸化アンチモンおよび熱安定剤をスーパー
ミキサーで混合した。
次いで、押出機を用いて熔融混練し、ペレツト
化した。このペレツトを射出成形機を用いて成形
し、燃焼性試験片を得た。
この試験片を用い、燃焼試験（UL規格Sb94垂
直法）を行ない、自己消火時間の平均値及び最大
値と綿花着火率を測定し、この値を第１表に併記
した。
また該ペレツトを射出成形機を用いて、ヒケ観
察用試験片を作成し、これを観察した。この結果
を第１表に併記した。[Formula] (However, R 5 , R 6 and R 7 are at least two of the same or different types.
An esterified product of isocyanuric acid and a brominated aliphatic alcohol represented by an alkyl group having 2 to 18 carbon atoms bonding bromine atoms is used. Specifically, as etherified bisphenol A,
Generally, bisphenol tetrabromide A bis (dibromoethyl ether), bisphenol tetrabromide A bis (dibromopropyl ether), bisphenol tetrabromide A bis (dibromobutyl ether), bisphenol tetrabromide A bis (tribromopropylether), ether), tetrabromide bisphenol A bis(tetrabromopropyl ether), tetrabromide bisphenol A
Bisphenol A bis(polybromoalkyl ether) such as bis(tribromobutyl ether) and bisphenol A bis(tetrabromobutyl ether) are preferably used. Etherified bisphenol S generally includes tetrabromide bisphenol S bis(dibromoethyl ether), tetrabromide bisphenol S bis(dibromopropyl ether), tetrabromide bisphenol S bis(dibromobutyl ether), and tetrabromide bisphenol S bis(dibromobutyl ether). bisphenol S bis(tribromopropyl ether), bisphenol tetrabromide S bis(tetrabromopropyl ether), bisphenol S tetrabromide
Bisphenol S bis(polypromoalkyl ether) such as bis(tribromobutyl ether), bisphenol S bis(tetrabromobutyl ether), and bis(polypromoalkyl ether) are preferably used. Esters of isocyanuric acid and brominated aliphatic alcohols generally include tris(dibromoethyl)isocyanurate, bis(dibromoethyl)isocyanurate, tris(dibromopropyl)isocyanurate, bis(dibromopropyl)isocyanurate, tris(dibromoethyl)isocyanurate, and tris(dibromoethyl)isocyanurate. butyl) isocyanurate, bis(dibromobutyl)
Isocyanurate, Tris(tribromopropyl)isocyanurate, Bis(tribromopropyl)isocyanurate, Tris(tetrabromopropyl)isocyanurate, Bis(tetrabromopropyl)isocyanurate, Tris(tribromobutyl)isocyanurate, Bis( Brominated alkyl isocyanurates such as tribromobutyl) isocyanurate, tris(tetrabromobutyl) isocyanurate, and bis(tetrabromobutyl) isocyanurate are preferably used. The amount of the flame retardant having a brominated aliphatic hydrocarbon group is 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight, based on 100 parts by weight of the polyolefin. If the blending amount of the flame retardant having a brominated aliphatic hydrocarbon group is less than the above range, a sufficient flame retardant effect cannot be exhibited, and if it is more than the above upper limit, the flame retardant effect will not increase and it will be uneconomical. Not only this, but also the thermal decomposition in the extruder becomes intense, causing decomposition of the polyolefin, which is not preferable. In addition, in the present invention, it is extremely important to use a flame retardant with a melting point of 240°C or higher in addition to a flame retardant having a brominated aliphatic hydrocarbon group, especially in order to achieve flame retardancy and prevent sink marks during molding. be. That is,
Flame retardants with brominated aliphatic hydrocarbon groups have melting points.
Even if a flame retardant having a temperature of 240° C. or lower is used in combination, flame retardancy can be obtained, but a polyolefin composition that does not prevent sink marks during molding cannot be obtained. Flame retardants with a melting point of 240°C or higher are selected from known flame retardants, regardless of whether they are bromine-based, chlorine-based, phosphorus-based, etc., and inhibit the flame retardant effect of the flame retardant with a brominated aliphatic hydrocarbon group used in combination. Unless otherwise specified, it can be used without any particular restrictions. For example, aromatic bromine compounds such as decabrom diphenyl ether, decabrom diphenyl, hexabromobenzene, pentabromotoluene, and tetrabromophthalic anhydride; perchlorocyclopentadecane-based chlorine such as dechlorane and dechlorane plus (all trade names) Other examples include phosphorus-based organic compounds such as ethylene bis[tris(2-cyanoalkyl)phosphonium bromide]. The blending amount of the flame retardant having a melting point of 240° C. or higher is 1 to 70 parts by weight, preferably 3 to 50 parts by weight, per 100 parts by weight of the polyolefin. Melting point is 240
If the amount of the flame retardant added is lower than the above-mentioned lower limit amount, the effect of preventing sink marks during molding of the polyolefin composition will not be sufficient, and if it is higher than the upper limit amount, the polyolefin composition may have a high specific gravity. , which is not preferable because impact resistance decreases. Furthermore, antimony oxide is added to sufficiently improve the effect of the flame retardant. Commercially available general antimony oxide is used as the antimony oxide, and its blending amount is generally 10 to 250% of the total amount of the flame retardant having a brominated aliphatic hydrocarbon group and the flame retardant with a melting point of 240°C or higher. Weight%. If the blending amount of antimony oxide is lower than the lower limit value, the flame retardance will not be improved sufficiently, and if it is higher than the upper limit value, the flame retardance will decrease, which is not preferable. In the present invention, a flame retardant having a brominated aliphatic hydrocarbon group for polyolefin and a melting point of 240°C
The mixing order of the above flame retardants and antimony oxide is not particularly limited, and each component may be mixed at the same time, or several types may be mixed in advance and the remaining components may be mixed later. Further, the mixing method is not particularly limited, and is generally carried out using a tumbler type blender, a V-type blender, a Henschel mixer, a ribbon mixer, or the like. Furthermore, it is also possible to adopt a method of changing the mixing order and equipment, such as mixing several types in advance in a Henschel mixer, then adding the rest and mixing in a tumbler blender. The polyolefin composition of the present invention basically consists of the polyolefin described above, a flame retardant having a brominated aliphatic hydrocarbon group, a flame retardant with a melting point of 240°C or higher, and antimony oxide. Conventionally known stabilizers, colorants, antistatic agents, lubricants, nucleating agents, and inorganic substances in amounts that do not adversely affect flame retardancy may be added. The polyolefin composition of the present invention successfully combines the very high flame retardancy of a flame retardant having a brominated aliphatic hydrocarbon group with the anti-sink and flame retardant properties of a flame retardant having a melting point of 240°C or higher. Despite the addition of a small amount of flame retardant,
It exhibits flame retardant and sink mark prevention effects at the same time. EXAMPLES In order to explain the present invention more specifically, Examples and Comparative Examples will be given below, but the present invention is not limited to these Examples. The flame retardant test results shown in the examples and comparative examples are UL94.
The test was carried out in accordance with the vertical method of the standard, and the average self-extinguishing time was the average self-extinguishing time after ignition of fire twice for each of the 10 combustion test pieces, that is, 20 times in total. Moreover, the maximum self-extinguishing time was the maximum value among the self-extinguishing times after the 20 ignitions. The cotton ignition rate was expressed as the extent to which the cotton under the test piece ignited due to "flame" from the test piece, and was expressed as how many out of 10 test pieces were ignited. For example, if 3 out of 10 lights were ignited, it would be displayed as 3/10. The shape of the test piece is 5 inches x 0.5 inches x 1/8
I did it at In addition, in order to examine sink prevention properties, we created molded products using two molds: mold K-, which causes sink marks to some extent, and mold K-, which tends to cause sink marks very easily. The degree of occurrence was observed. The criteria for judgment at this time is ◎ if almost no sink marks are observed, ○ if there are only a few sink marks, △ if some sink marks are observed, and △ if there are large sink marks. The ones that are present are marked as ×. Example 1 and Comparative Example 1 To 100 parts by weight of polypropylene (ME140, MI9 homopolymer manufactured by Tokuyama Soda Co., Ltd.), tetrabromide bisphenol A bis (dibromide propyl ether) and deca Bromodiphenyl ale, antimony trioxide and heat stabilizer were mixed in a super mixer. Next, the mixture was melt-kneaded using an extruder to form pellets. This pellet was molded using an injection molding machine to obtain a combustibility test piece. Using this test piece, a combustion test (UL standard Sb94 vertical method) was conducted, and the average and maximum values of self-extinguishing time and cotton ignition rate were measured, and these values are also listed in Table 1. Further, test pieces for sink mark observation were prepared from the pellets using an injection molding machine, and the test pieces were observed. The results are also listed in Table 1.
【表】【table】
【表】
実施例２および比較例２
ポリプロピレン（徳山曹達社製MS640、MI6.5
のポリエチレンとのブロツクコポリマー）100重
量部に対して、第２表に示す割合の四臭化ビスフ
エノールＳビス（二臭化プロピルエーテル）、ヘ
キサブロムベンゼン、三酸化アンチモンおよび熱
安定剤をスーパーミキサーで混合した。
以下、実施例１と同様にしてペンタイズ後、燃
焼試験及びヒケの観察を行なつた。この結果を第
２表に併記した。[Table] Example 2 and Comparative Example 2 Polypropylene (MS640 manufactured by Tokuyama Soda Co., Ltd., MI6.5
To 100 parts by weight of a block copolymer (block copolymer with polyethylene of mixed with. After pentizing, a combustion test and sink mark observation were conducted in the same manner as in Example 1. The results are also listed in Table 2.
【表】
実施例３および比較例３
ポリプロピレン（徳山曹達社製ME440、MI9の
ポリエチレンとのランダムコポリマー）100重量
部に対して第３表に示す割合のトリス（２・３−
ジブロムプロピル）イソシアヌレート、テトラブ
ロムトルエン、三酸化アンチモンおよび熱安定剤
をスーパーミキサーで混合した。
以下、実施例１と同様にしてペレタイズ後、燃
焼試験及びヒケの観察を行なつた。この結果を第
３表に併記した。[Table] Example 3 and Comparative Example 3 Tris (2.3-
Dibromopropyl) isocyanurate, tetrabromotoluene, antimony trioxide and heat stabilizer were mixed in a super mixer. After pelletizing, a combustion test and sink marks were observed in the same manner as in Example 1. The results are also listed in Table 3.
Claims (1)
くとも２個の臭素原子を結合する炭素数２〜18
のアルキル基） で示されるエーテル化四臭化ビスフエノールＡ
または 一般式 （式中、R3およびR4は、同種または異種の少な
くとも２個の臭素原子を結合する炭素数２〜18
のアルキル基） で示されるエーテル化四臭化ビスフエノールＳ (B) デカブロムジフエニルエーテルまたはヘキサ
ブロムベンゼン および (C) 三酸化アンチモン を含有して成り、該ポリオレフイン100重量部に
対して、上記の(A)成分が0.5〜50重量部、(B)成分
が１〜70重量部、および(A)成分と(B)成分との合計
重量に対して(C)成分が10〜250重量％である難燃
性ポリオレフイン組成物。[Claims] 1 Polyolefin (A) General formula (In the formula, R 1 and R 2 have 2 to 18 carbon atoms bonding at least two bromine atoms of the same or different types.
etherified tetrabrominated bisphenol A represented by
or general formula (In the formula, R 3 and R 4 have 2 to 18 carbon atoms bonding at least two bromine atoms of the same or different types.
(B) decabrom diphenyl ether or hexabromobenzene and (C) antimony trioxide. Component (A) is 0.5 to 50 parts by weight, component (B) is 1 to 70 parts by weight, and component (C) is 10 to 250 parts by weight based on the total weight of components (A) and (B). A flame retardant polyolefin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4170281A JPS57158247A (en) | 1981-03-24 | 1981-03-24 | Flame retardant polyolefin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4170281A JPS57158247A (en) | 1981-03-24 | 1981-03-24 | Flame retardant polyolefin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57158247A JPS57158247A (en) | 1982-09-30 |
| JPS6234253B2 true JPS6234253B2 (en) | 1987-07-25 |
Family
ID=12615750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4170281A Granted JPS57158247A (en) | 1981-03-24 | 1981-03-24 | Flame retardant polyolefin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57158247A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5935650A (en) * | 1982-08-23 | 1984-02-27 | Kubota Ltd | Composite cylinder liner |
| JP2811987B2 (en) * | 1991-03-28 | 1998-10-15 | 大日本インキ化学工業株式会社 | Flame retardant polyethylene resin composition and material for extrusion coating |
| US5216059A (en) * | 1992-04-13 | 1993-06-01 | Great Lakes Chemical Corp. | Flame retardant additive composition useful with polyolefins |
| KR100644978B1 (en) | 2002-09-30 | 2006-11-14 | 산요덴키가부시키가이샤 | Network telephone and voice decording device |
| KR100964436B1 (en) | 2004-08-30 | 2010-06-16 | 퀄컴 인코포레이티드 | Adaptive de-jitter buffer for voice over ip |
| US7783482B2 (en) * | 2004-09-24 | 2010-08-24 | Alcatel-Lucent Usa Inc. | Method and apparatus for enhancing voice intelligibility in voice-over-IP network applications with late arriving packets |
| US8085678B2 (en) | 2004-10-13 | 2011-12-27 | Qualcomm Incorporated | Media (voice) playback (de-jitter) buffer adjustments based on air interface |
| US8155965B2 (en) | 2005-03-11 | 2012-04-10 | Qualcomm Incorporated | Time warping frames inside the vocoder by modifying the residual |
| US8355907B2 (en) | 2005-03-11 | 2013-01-15 | Qualcomm Incorporated | Method and apparatus for phase matching frames in vocoders |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5096640A (en) * | 1973-12-27 | 1975-07-31 | ||
| JPS5423653A (en) * | 1977-07-25 | 1979-02-22 | Sumitomo Electric Ind Ltd | Polyolefin composition |
| JPS5425485A (en) * | 1977-07-27 | 1979-02-26 | Sumitomo Electric Ind Ltd | Bridged polyolefin insulated wire |
| JPS54120654A (en) * | 1978-03-14 | 1979-09-19 | Furukawa Electric Co Ltd:The | Flame-retardant ethylene-vinyl acetate copolymer composition |
| JPS54120653A (en) * | 1978-03-14 | 1979-09-19 | Furukawa Electric Co Ltd:The | Flame retardant ethylene-propylene copolymer composition |
| JPS5550037A (en) * | 1978-10-02 | 1980-04-11 | Monsanto Co | Flame retardant polymer |
| JPS5618635A (en) * | 1979-07-25 | 1981-02-21 | Tatsuta Electric Wire & Cable Co Ltd | Flame-retarding polyolefin resin composition |
| JPS5773032A (en) * | 1980-10-24 | 1982-05-07 | Teijin Chem Ltd | Flame-retardant polypropylene composition |
-
1981
- 1981-03-24 JP JP4170281A patent/JPS57158247A/en active Granted
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5096640A (en) * | 1973-12-27 | 1975-07-31 | ||
| JPS5423653A (en) * | 1977-07-25 | 1979-02-22 | Sumitomo Electric Ind Ltd | Polyolefin composition |
| JPS5425485A (en) * | 1977-07-27 | 1979-02-26 | Sumitomo Electric Ind Ltd | Bridged polyolefin insulated wire |
| JPS54120654A (en) * | 1978-03-14 | 1979-09-19 | Furukawa Electric Co Ltd:The | Flame-retardant ethylene-vinyl acetate copolymer composition |
| JPS54120653A (en) * | 1978-03-14 | 1979-09-19 | Furukawa Electric Co Ltd:The | Flame retardant ethylene-propylene copolymer composition |
| JPS5550037A (en) * | 1978-10-02 | 1980-04-11 | Monsanto Co | Flame retardant polymer |
| JPS5618635A (en) * | 1979-07-25 | 1981-02-21 | Tatsuta Electric Wire & Cable Co Ltd | Flame-retarding polyolefin resin composition |
| JPS5773032A (en) * | 1980-10-24 | 1982-05-07 | Teijin Chem Ltd | Flame-retardant polypropylene composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57158247A (en) | 1982-09-30 |
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