JPH05320439A - Flame-retardant polypropylene composition - Google Patents
Flame-retardant polypropylene compositionInfo
- Publication number
- JPH05320439A JPH05320439A JP12615992A JP12615992A JPH05320439A JP H05320439 A JPH05320439 A JP H05320439A JP 12615992 A JP12615992 A JP 12615992A JP 12615992 A JP12615992 A JP 12615992A JP H05320439 A JPH05320439 A JP H05320439A
- Authority
- JP
- Japan
- Prior art keywords
- oligomer
- brominated
- brominated bisphenol
- flame
- ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 35
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 19
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 17
- 239000003063 flame retardant Substances 0.000 title 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 title claims description 27
- 239000000203 mixture Substances 0.000 title claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 24
- YUAPUIKGYCAHGM-UHFFFAOYSA-N 1,2-dibromo-3-(2,3-dibromopropoxy)propane Chemical compound BrCC(Br)COCC(Br)CBr YUAPUIKGYCAHGM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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 claims abstract description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 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 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000000740 bleeding effect Effects 0.000 abstract description 25
- 238000013329 compounding Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 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 5
- 230000007774 longterm Effects 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 2
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002989 phenols Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 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 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 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
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、難燃性ポリプロピレン
組成物に関するものである。更に詳しくは、ブリード性
が少なく且つ高度な難燃効果を発揮する難燃性ポリプロ
ピレン組成物に関するものである。FIELD OF THE INVENTION The present invention relates to a flame-retardant polypropylene composition. More specifically, it relates to a flame-retardant polypropylene composition having a low bleeding property and exhibiting a high flame-retardant effect.
【０００２】[0002]
【従来の技術】従来から、ポリプロピレンの難燃化方法
として、各種ハロゲン化合物の添加が提案されている
が、加熱加工時又は最終成形物の使用時のハロゲン化合
物の揮散性やブリード性が実質的になく、しかも優れた
難燃効果を奏するものは少ない。例えばポリオレフィン
用の難燃剤として臭素化ビスフェノールＳの（２，３−
ジブロムプロピル）エーテルが、ヘキサブロムベンゼ
ン、ポリ臭素化ジフェニル、臭素化ビスフェノールＡエ
チルエーテル等の他の難燃剤に比べて難燃効果が比較的
高く、ブリード性も少ないことが知られている（特公昭
５０−３５１０３号公報）。しかしながら、かかる臭素
化ビスフェノールＳのビス（２，３−ジブロムプロピ
ル）エーテルは短期的なブリード性は優れているが、長
期間の使用においてはブリード性及び揮散性が認めら
れ、成形物の表面不良等の問題が生じるため使用に適さ
ない。2. Description of the Related Art Conventionally, the addition of various halogen compounds has been proposed as a method for making polypropylene flame-retardant. However, the volatility and bleeding properties of halogen compounds during heating or use of the final molded product are substantially reduced. There are few that have excellent flame retardant effects. For example, brominated bisphenol S (2,3-
It is known that dibromopropyl) ether has a relatively high flame retardant effect and a small bleeding property as compared with other flame retardants such as hexabromobenzene, polybrominated diphenyl and brominated bisphenol A ethyl ether ( Japanese Patent Publication No. 50-35103). However, although such bis (2,3-dibromopropyl) ether of brominated bisphenol S is excellent in short-term bleeding property, bleeding property and volatility are observed in long-term use, and the surface of the molded product is recognized. It is not suitable for use because problems such as defects will occur.
【０００３】また、臭素化ビスフェノールＡエチルエー
テルオリゴマーは高度の難燃化を達成するためには多量
の使用を要し、例えばUL規格（UL−９４）に定められて
いる難燃性規準のＶ−０を達成することは不可能であ
る。更に、臭素化ビスフェノールＡ系カーボネートオリ
ゴマーはブリード性は優れているが、高度の難燃化を達
成することは、臭素化ビスフェノールＡエチルエーテル
オリゴマーと同様に不可能である。Further, brominated bisphenol A ethyl ether oligomer requires a large amount of use in order to achieve a high degree of flame retardancy, and for example, V of the flame retardancy standard stipulated in UL standard (UL-94) is required. It is impossible to achieve −0. Further, the brominated bisphenol A-based carbonate oligomer is excellent in bleeding property, but it is impossible to achieve a high degree of flame retardancy, like the brominated bisphenol A ethyl ether oligomer.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、従来
の難燃剤の欠点を解消し、揮散性やブリード性が少なく
且つ難燃性も高いポリプロピレン組成物を提供すること
にある。SUMMARY OF THE INVENTION It is an object of the present invention to solve the drawbacks of conventional flame retardants and to provide a polypropylene composition having low volatility and bleeding properties and high flame retardancy.
【０００５】本発明者は上記目的を達成せんとして鋭意
研究した結果、臭素化ビスフェノールＳのビス（２，３
−ジブロムプロピル）エーテルと、臭素化ビスフェノー
ルＡエチルエーテルオリゴマー及び臭素化ビスフェノー
ルＡ系カーボネートオリゴマーよりなる群から選ばれた
少くとも一種の臭素化オリゴマーを特定割合で併用する
と、これらの相乗効果によってブリードの発生が非常に
少なく且つ優れた難燃効果を発揮し、経済的にも有利な
難燃性ポリプロピレン組成物を得ることができることを
究明し、本発明に到達したものである。As a result of earnest research aimed at achieving the above object, the present inventor has found that bis (2,3
-Dibromopropyl) ether and at least one brominated oligomer selected from the group consisting of brominated bisphenol A ethyl ether oligomer and brominated bisphenol A-based carbonate oligomer in a specific ratio are used to bleed due to their synergistic effect. The present invention has been accomplished by demonstrating that a flame-retardant polypropylene composition exhibiting an extremely low flame retardancy and an excellent flame-retardant effect and being economically advantageous can be obtained.
【０００６】[0006]
【課題を解決するための手段】本発明は、ポリプロピレ
ンに、（Ａ）下記式［１］Means for Solving the Problems The present invention provides a polypropylene (A) represented by the following formula [1]:
【０００７】[0007]
【化４】 [Chemical 4]
【０００８】（式中、ｍは１又は２）で示される臭素化
ビスフェノールＳのビス（２，３−ジブロムプロピル）
エーテルと、（Ｂ）下記式［２］(In the formula, m is 1 or 2) Brominated bisphenol S bis (2,3-dibromopropyl)
Ether and (B) the following formula [2]
【０００９】[0009]
【化５】 [Chemical 5]
【００１０】（式中、ｎは１又は２、ｐは平均重合度を
示す１〜１０の数）で示される臭素化ビスフェノールＡ
エチルエーテルオリゴマー及び下記式［３］Brominated bisphenol A represented by the formula (n is 1 or 2 and p is a number from 1 to 10 showing an average degree of polymerization)
Ethyl ether oligomer and the following formula [3]
【００１１】[0011]
【化６】 [Chemical 6]
【００１２】（式中、ｎは１又は２）で示される繰返単
位を主とする平均重合度が２〜３０の臭素化ビスフェノ
ールＡ系カーボネートオリゴマーよりなる群から選ばれ
た少くとも一種の臭素化オリゴマーを［（Ａ）臭素化ビ
スフェノールＳのビス（２，３−ジブロムプロピル）エ
ーテル］：［（Ｂ）臭素化オリゴマー］の重量比が９．
９：０．１〜５：５の割合で難燃化する量配合してなる
難燃性ポリプロピレン組成物に係るものである。At least one bromine selected from the group consisting of brominated bisphenol A-based carbonate oligomers having an average degree of polymerization of 2 to 30 and mainly composed of repeating units represented by the formula (n is 1 or 2) The weight ratio of [(A) brominated bisphenol S bis (2,3-dibromopropyl) ether]: [(B) brominated oligomer] is 9.
The present invention relates to a flame-retardant polypropylene composition, which is compounded in a flame-retardant amount of 9: 0.1 to 5: 5.
【００１３】本発明で使用する難燃剤（Ａ）である臭素
化ビスフェノールＳの（２，３−ジブロムプロピル）エ
ーテルは前記式［１］で示される化合物であり、なかで
も下記式The (2,3-dibromopropyl) ether of brominated bisphenol S, which is the flame retardant (A) used in the present invention, is a compound represented by the above formula [1].
【００１４】[0014]
【化７】 [Chemical 7]
【００１５】で示されるテトラブロムビスフェノールＳ
のビス（２，３−ジブロムプロピル）エーテルが好まし
い。かかる臭素化ビスフェノールＳのビス（２，３−ジ
ブロムプロピル）エーテルは、臭素化ビスフェノールＳ
にアルカリの存在下にハロゲン化アリルを反応させてビ
スアリルエーテルを製造し、次いでこれに臭素を通常の
方法で付加させれば容易に製造できる。Tetrabromobisphenol S represented by
Bis (2,3-dibromopropyl) ether of is preferred. The bis (2,3-dibromopropyl) ether of brominated bisphenol S is brominated bisphenol S.
It can be easily produced by reacting allyl halide in the presence of alkali to produce a bisallyl ether, and then adding bromine thereto by a usual method.
【００１６】本発明で使用する難燃剤（Ｂ）の一つであ
る臭素化ビスフェノールＡエチルエーテルオリゴマーは
前記式［２］で示される臭素化オリゴマーであリ、その
平均重合度は１〜１０、好ましくは１〜５である。平均
重合度が１０を越えるものを使用するとブリード防止効
果は優れているが、高度の難燃性を達成することはでき
ない。かかる臭素化ビスフェノールＡエチルエーテルオ
リゴマーは、通常重合度の異なるものの混合物として使
用されるが、単一組成のものであってもよい。The brominated bisphenol A ethyl ether oligomer which is one of the flame retardants (B) used in the present invention is a brominated oligomer represented by the above formula [2], and its average degree of polymerization is 1 to 10, It is preferably 1 to 5. If the average degree of polymerization exceeds 10, the effect of preventing bleeding is excellent, but a high degree of flame retardancy cannot be achieved. The brominated bisphenol A ethyl ether oligomer is usually used as a mixture of those having different degrees of polymerization, but may have a single composition.
【００１７】この臭素化オリゴマーの好ましいものは下
記式Preferred of this brominated oligomer is the following formula
【００１８】[0018]
【化８】 [Chemical 8]
【００１９】で示されるテトラブロムビスフェノールＡ
エチルエーテルオリゴマーである。式中、ｐは平均重合
度を示す１〜１０の数であり、特に１〜５の範囲が好ま
しい。かかる臭素化ビスフェノールＡエチルエーテルオ
リゴマーは、例えば臭素化ビスフェノールＡと二臭化エ
チレンをアルカリ及び触媒の存在下水、アルコ−ル又は
キシレン等の溶媒中で加熱反応させることにより製造す
ることができる。この臭素化オリゴマ−の重合度は、臭
素化ビスフェノールＡと二臭化エチレンとのモル比によ
り制御することができる。Tetrabromobisphenol A represented by
It is an ethyl ether oligomer. In the formula, p is a number of 1 to 10 indicating the average degree of polymerization, and a range of 1 to 5 is particularly preferable. The brominated bisphenol A ethyl ether oligomer can be produced, for example, by reacting brominated bisphenol A and ethylene dibromide in the presence of an alkali and a catalyst in a solvent such as water, alcohol or xylene under heating. The degree of polymerization of this brominated oligomer can be controlled by the molar ratio of brominated bisphenol A and ethylene dibromide.
【００２０】難燃剤（Ｂ）の別のひとつは前記式［３］
で示される繰返し単位を主とする平均重合度２〜３０の
臭素化ビスフェノールＡ系カーボネートオリゴマーであ
り、中でも平均重合度が２〜２０で軟化点が３００℃以
下のものが好ましい。平均重合度が２未満のものではブ
リード防止効果が充分でなく、３０を越えると相溶性が
悪くなり、良好な成形品が得られ難くなる。かかる臭素
化ビスフェノールＡ系カーボネートオリゴマーのなかで
も下記式Another one of the flame retardants (B) is the above formula [3].
It is a brominated bisphenol A carbonate oligomer having an average degree of polymerization of 2 to 30 and mainly having a repeating unit represented by, and among them, those having an average degree of polymerization of 2 to 20 and a softening point of 300 ° C. or less are preferable. If the average degree of polymerization is less than 2, the effect of preventing bleeding is not sufficient, and if it exceeds 30, the compatibility becomes poor and it becomes difficult to obtain a good molded product. Among such brominated bisphenol A carbonate oligomers, the following formula
【００２１】[0021]
【化９】 [Chemical 9]
【００２２】で示されるテトラブロムビスフェノールＡ
カーボネートオリゴマーが特に好ましい。かかる臭素化
ビスフェノールＡカーボネートオリゴマーは、種々の方
法で製造できる。例えば末端停止剤として予め選定され
たモル比の単官能フェノールと共に苛性ソーダのような
脱酸剤の存在下に水及びメチレンクロライド中で、ホス
ゲンと反応させることによって容易に製造される。平均
重合度は臭素化ビスフェノールＡと単官能フェノールの
比率を変えることにより容易に調節できる。例えば臭素
化ビスフェノールＡ１０モルに対して、単官能フェノー
ル２モルを用いれば平均重合度が約１０のものが得ら
れ、単官能フェノール４モルを用いれば平均重合度が約
５のものが得られる。また末端停止剤を用いないで、系
のpHを１０〜１１の範囲に保ち、臭素化ビスフェノール
Ａに対するホスゲンのモル比を０．５〜１．１に調節す
る方法によっても平均重合度が２〜１０のオリゴマーを
製造することができる。臭素化ビスフェノールＡカーボ
ネートオリゴマーの末端構造は特に限定されないが、そ
れ自体の安定性を高めるためにフェノール又は低級アル
キル、長鎖アルキル、ハロゲン等で核置換したフェノー
ルで封鎖することが好ましい。Tetrabromobisphenol A represented by
Carbonate oligomers are particularly preferred. The brominated bisphenol A carbonate oligomer can be produced by various methods. For example, it is readily prepared by reacting with phosgene in water and methylene chloride in the presence of a deoxidizing agent such as caustic soda with a preselected molar ratio of monofunctional phenol as the end-capping agent. The average degree of polymerization can be easily adjusted by changing the ratio of brominated bisphenol A and monofunctional phenol. For example, when 10 moles of brominated bisphenol A is used, 2 moles of monofunctional phenol gives an average polymerization degree of about 10, and when 4 moles of monofunctional phenol is used, an average polymerization degree of about 5 is obtained. Further, the average degree of polymerization of 2 is also obtained by a method in which the pH of the system is maintained in the range of 10 to 11 and the molar ratio of phosgene to brominated bisphenol A is adjusted to 0.5 to 1.1 without using a terminal stopper. Ten oligomers can be produced. The terminal structure of the brominated bisphenol A carbonate oligomer is not particularly limited, but in order to increase the stability of itself, it is preferable to block with phenol or phenol substituted with a lower alkyl, a long-chain alkyl, a halogen or the like as a nucleus.
【００２３】更に、臭素化ビスフェノールＡの一部を他
の二価フェノールで置換したオリゴマーも包含する。こ
の場合、臭素化ビスフェノールＡカ−ボネ−トの繰返し
単位が少なくとも５０％を占めるのが好ましい。これら
の二価フェノールの例としては、ビスフェノールＡ、
１，１−ビス（４−ヒドロキシフェニル）シクロヘキサ
ン、ビス（４−ヒドロキシフェニル）スルホン等をあげ
ることができる。Further, an oligomer in which a part of brominated bisphenol A is replaced with another dihydric phenol is also included. In this case, it is preferred that the repeating units of brominated bisphenol A carbonate account for at least 50%. Examples of these dihydric phenols include bisphenol A,
Examples thereof include 1,1-bis (4-hydroxyphenyl) cyclohexane and bis (4-hydroxyphenyl) sulfone.
【００２４】本発明で使用する難燃剤の組成は、
［（Ａ）臭素化ビスフェノールＳの（２，３−ジブロム
プロピル）エーテル］：[(Ｂ）臭素化オリゴマー］の重
量比が９．９：０．１〜５：５であり、好ましくは９．
５：０．５〜６：４である。この割合の範囲よりも、
［（Ｂ）臭素化オリゴマー］が増すに従って耐ブリード
性は優れてくるが、難燃効果が悪くなる。また、この
（Ｂ）臭素化オリゴマーの使用割合が減少するに従って
難燃効果はよくなるが、長期ブリード性が悪くなる。
（Ｂ）臭素化オリゴマーとして臭素化ビスフェノールＡ
エチルエーテルオリゴマーと臭素化ビスフェノールＡ系
カーボネートオリゴマーを併用するときは、その比率は
任意である。The composition of the flame retardant used in the present invention is
The weight ratio of [(A) (2,3-dibromopropyl) ether of brominated bisphenol S]: [(B) brominated oligomer] is 9.9: 0.1 to 5: 5, preferably 9 ．
It is 5: 0.5 to 6: 4. Than the range of this ratio
As the amount of [(B) brominated oligomer] increases, the bleeding resistance becomes excellent, but the flame retardant effect becomes poor. Further, as the proportion of the brominated oligomer (B) used decreases, the flame retardant effect improves, but the long-term bleeding property deteriorates.
(B) Brominated bisphenol A as brominated oligomer
When the ethyl ether oligomer and the brominated bisphenol A carbonate oligomer are used in combination, the ratio is arbitrary.
【００２５】難燃剤（Ａ）と難燃剤（Ｂ）の合計添加量
は、要求される難燃性に応じて調節されるが、全組成物
中の合計ブロム量が１〜３０重量％になる量が好まし
く、１〜１５重量％になる量が特に好ましい。The total amount of flame retardant (A) and flame retardant (B) added is adjusted according to the required flame retardancy, but the total amount of bromine in the total composition is 1 to 30% by weight. Amounts are preferred, with amounts of 1 to 15% by weight being particularly preferred.
【００２６】本発明でいうポリプロピレンは、プロピレ
ンのホモポリマーの他にエチレンその他プロピレンと共
重合可能なモノマーとの共重合体も包含する。The polypropylene referred to in the present invention includes not only a homopolymer of propylene but also a copolymer of ethylene and a monomer copolymerizable with propylene.
【００２７】本発明の難燃性組成物には、難燃助剤とし
て三酸化アンチモンを添加することができ、三酸化アン
チモンを添加することにより、より好ましい難燃効果が
得られる。更に難燃剤の安定剤としてエポキシ化合物、
スズ系安定剤、鉛系安定剤、ホスファイト類等を難燃剤
に対して０．０１〜１０重量％、好ましくは０．１〜５
重量％添加することができる。更に、本発明の組成物に
は、必要に応じてポリプロピレンの改質、着色、増量等
を目的として紫外線吸収剤、酸化安定剤等の添加剤、顔
料、充填剤、その他の物質を添加することができる。To the flame-retardant composition of the present invention, antimony trioxide can be added as a flame retardant auxiliary agent, and by adding antimony trioxide, a more preferable flame retardant effect can be obtained. Furthermore, epoxy compounds as stabilizers for flame retardants,
0.01 to 10% by weight of tin stabilizer, lead stabilizer, phosphite, etc., relative to the flame retardant, preferably 0.1 to 5
% By weight can be added. Further, to the composition of the present invention, an additive such as an ultraviolet absorber, an oxidation stabilizer, a pigment, a filler, and other substances may be added, if necessary, for the purpose of modifying, coloring, and increasing the polypropylene. You can
【００２８】本発明の難燃性組成物を製造するには、必
要な各成分を同時に混合することができるが、（Ａ）臭
素化ビスフェノールＳの（２，３−ジブロムプロピル）
エーテルと、（Ｂ）臭素化オリゴマーとをあらかじめ予
備混合しておくと好結果が得られる。この場合、粉末状
で混合してもよいし、適当なバインダーを用いて高濃度
マスターを一般的な方法で製造する方法をとることも可
能である。To prepare the flame-retardant composition of the present invention, each of the necessary components can be mixed at the same time, but (A) brominated bisphenol S (2,3-dibromopropyl).
Good results are obtained when the ether and (B) brominated oligomer are premixed in advance. In this case, they may be mixed in the form of powder, or a high-concentration master may be produced by a general method using an appropriate binder.
【００２９】本発明の組成物は任意の手段で製造するこ
とができる。例えばロール、バンバリーミキサー、タン
ブラ−型ブレンダ−、押出機等の従来樹脂に添加剤を混
練するに用いられている機械を用いて各成分を配合混和
することにより容易に得られる。また組成物を成形する
に当っても任意の手段が採用される。例えば射出成形
機、押出成形機、プレス成形機等を用いることができ
る。The composition of the present invention can be manufactured by any means. For example, it can be easily obtained by blending and mixing each component using a machine such as a roll, a Banbury mixer, a tumbler type blender, an extruder or the like which is conventionally used for kneading an additive with a resin. Further, any means may be adopted for molding the composition. For example, an injection molding machine, an extrusion molding machine, a press molding machine or the like can be used.
【００３０】[0030]
【実施例】以下に実施例をあげて本発明を更に説明す
る。なお、実施例中での部及び％は重量部及び重量％を
示す。難燃性の測定は、アメリカのUL規格のUL−９４に
定める方法とJIS K-７２０１による酸素指数（OI値）で
行い、ブリード性は下記の短期ブリード性と長期ブリー
ド性の二通りの方法で評価した。EXAMPLES The present invention will be further described with reference to the following examples. In addition, part and% in an Example show a weight part and weight%. The flame retardancy is measured by the method specified in UL-94 of the American UL standard and the oxygen index (OI value) according to JIS K-7201. The bleeding properties are the following two methods: short-term bleeding property and long-term bleeding property. It was evaluated by.
【００３１】短期ブリード性：色見本板（幅４５×長７
０×厚さ２mm）を８０℃のオーブンに５日間放置し、色
見本板上のブリード発生の有無で評価した。評価基準は
ブリードが全く認められないものを○、僅かに認められ
るものを△、多く認められるものを×で示した。Short-term bleeding property: color sample board (width 45 × length 7)
(0 × 2 mm thickness) was left in an oven at 80 ° C. for 5 days and evaluated by the presence or absence of bleeding on the color sample board. The evaluation criteria are indicated by ◯ when no bleeding was observed, Δ when slightly bleeding was observed, and x when many were observed.
【００３２】長期ブリード性：色見本板（幅４５×長７
０×厚さ２mm）を８０℃のオーブンに３０日間放置し、
色見本板上のブリード発生の有無で評価した。評価基準
はブリードが全く認められないものを○、僅かに認めら
れるものを△、多く認められるものを×で示した。Long-term bleeding: Color sample plate (width 45 x length 7
0 x thickness 2 mm), leave it in an oven at 80 ° C for 30 days,
It was evaluated whether or not bleeding occurred on the color sample plate. The evaluation criteria are indicated by ◯ when no bleeding was observed, Δ when slightly bleeding was observed, and x when many were observed.
【００３３】[0033]
【実施例１〜１５，比較例１〜７】ペレット状のプロピ
レン／エチレンコポリマー［ユニオンポリマー（株）製
UPポリプロ K−７０１９］１００部に、下記に示す難燃
剤ａ〜ｆ及び難燃助剤として三酸化アンチモンを表１記
載の量添加し、タンブラー型ブレンダーで混合した後二
軸押出機［池貝鉄工（株）製 PCM−３０］によりシリン
ダ−温度２００℃でペレット化し、次いで射出成形機
［（株）名機製作所製 SJ-２５ B］により成形温度２０
０℃で試験片を成形した。得られた試験片を用いて燃焼
性とブリード性を測定し、その結果を表１に示した。 ａ：テトラブロムビスフェノールＳのビス（２，３−ジ
ブロムプロピル）エーテル ｂ：平均重合度２のテトラブロムビスフェノールＡエチ
ルエーテルオリゴマー ｃ：平均重合度６のテトラブロムビスフェノールＡカー
ボネートオリゴマー ｄ：テトラブロムビスフェノールＡ１モルとビスフェノ
ールＡ０．２モルから得られた平均重合度２．１のテト
ラブロムビスフェノールＡ系カーボネートオリゴマー ｅ：デカブロモジフェニルエーテル［三井東圧ファイン
（株）製プラネロン DE-１００］ ｆ：テトラブロムビスフェノールＡのビス（２，３−ジ
ブロムプロピル）エーテルExamples 1 to 15 and Comparative Examples 1 to 7 Pellet-shaped propylene / ethylene copolymer [Union Polymer Co., Ltd.]
To 100 parts of UP Polypro K-7019], flame retardants a to f shown below and antimony trioxide as a flame retardant aid were added in the amounts shown in Table 1 and mixed in a tumbler type blender, followed by twin-screw extruder [Ikegai Tekko. PCM-30] manufactured by Pellet Co., Ltd., pelletized at a cylinder temperature of 200 ° C., and then molded by an injection molding machine [SJ-25B manufactured by Meiki Co., Ltd.] at a molding temperature of
Test pieces were molded at 0 ° C. The flammability and bleeding property were measured using the obtained test pieces, and the results are shown in Table 1. a: bis (2,3-dibromopropyl) ether of tetrabromobisphenol S b: tetrabromobisphenol A ethyl ether oligomer having an average degree of polymerization of 2 c: tetrabromobisphenol A carbonate oligomer having an average degree of polymerization of 6 d: tetrabromobisphenol Tetrabromobisphenol A-based carbonate oligomer having an average degree of polymerization of 2.1 obtained from 1 mol of A and 0.2 mol of bisphenol A e: Decabromodiphenyl ether [Planeron DE-100 manufactured by Mitsui Toatsu Fine Co., Ltd.] f: Tetrabromobisphenol Bis (2,3-dibromopropyl) ether of A
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【発明の効果】実施例より明らかな通り、本発明の難燃
性ポリプロピレン組成物は、優れた耐ブリード性を有
し、且つ難燃性も極めて高く、その奏する効果は格別な
ものである。As is apparent from the examples, the flame-retardant polypropylene composition of the present invention has excellent bleeding resistance and extremely high flame retardancy, and the effect exhibited by it is remarkable.
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 69/00 ＬＰＰ 9363−4Ｊ 71/10 ＬＱＨ 9167−4Ｊ ＬＱＫ 9167−4Ｊ //(Ｃ０８Ｌ 23/10 69:00） Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI Technical display location C08L 69/00 LPP 9363-4J 71/10 LQH 9167-4J LQK 9167-4J // (C08L 23/10 69: 00)
Claims (2)
ルＳのビス（２，３−ジブロムプロピル）エーテルと、
（Ｂ）下記式［２］ 【化２】 （式中、ｎは１又は２、ｐは平均重合度を示す１〜１０
の数）で示される臭素化ビスフェノールＡエチルエーテ
ルオリゴマー及び下記式［３］ 【化３】 （式中、ｎは１又は２）で示される繰返単位を主とする
平均重合度が２〜３０の臭素化ビスフェノールＡ系カー
ボネートオリゴマーよりなる群から選ばれた少くとも一
種の臭素化オリゴマーを［（Ａ）臭素化ビスフェノール
Ｓのビス（２，３−ジブロムプロピル）エーテル］：
［（Ｂ）臭素化オリゴマー］の重量比が９．９：０．１
〜５：５の割合で難燃化する量配合してなる難燃性ポリ
プロピレン組成物。1. Polypropylene is added with (A) the following formula [1]: (In the formula, m is 1 or 2) and a bis (2,3-dibromopropyl) ether of brominated bisphenol S,
(B) The following formula [2] (In the formula, n is 1 or 2, and p is an average polymerization degree of 1 to 10.
Brominated bisphenol A ethyl ether oligomer represented by the following formula [3] (Wherein n is 1 or 2), at least one brominated oligomer selected from the group consisting of brominated bisphenol A-based carbonate oligomers having an average degree of polymerization of 2 to 30 and mainly composed of repeating units. [(A) Bis (2,3-dibromopropyl) ether of brominated bisphenol S]:
The weight ratio of [(B) brominated oligomer] is 9.9: 0.1.
A flame-retardant polypropylene composition, which is blended in an amount of 5: 5 to make it flame-retardant.
（２，３−ジブロムプロピル）エーテル及び（Ｂ）臭素
化ビスフェノールＡエチルエーテルオリゴマー及び臭素
化ビスフェノールＡ系カーボネートオリゴマーよりなる
群から選ばれた少くとも一種の臭素化オリゴマーを、組
成物中のブロム含量が１〜３０重量％になる量配合して
なる請求項１記載の難燃性ポリプロピレン組成物。2. A compound selected from the group consisting of (A) bis (2,3-dibromopropyl) ether of brominated bisphenol S and (B) brominated bisphenol A ethyl ether oligomer and brominated bisphenol A carbonate oligomer. The flame-retardant polypropylene composition according to claim 1, wherein at least one brominated oligomer is blended in such an amount that the bromine content in the composition is 1 to 30% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12615992A JPH05320439A (en) | 1992-05-19 | 1992-05-19 | Flame-retardant polypropylene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12615992A JPH05320439A (en) | 1992-05-19 | 1992-05-19 | Flame-retardant polypropylene composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05320439A true JPH05320439A (en) | 1993-12-03 |
Family
ID=14928141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12615992A Pending JPH05320439A (en) | 1992-05-19 | 1992-05-19 | Flame-retardant polypropylene composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05320439A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002074853A1 (en) * | 2001-03-19 | 2002-09-26 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Flame-retardant polyolefin resin composition |
| WO2002074852A1 (en) * | 2001-03-19 | 2002-09-26 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Flame-retardant polyolefin resin composition |
| EP1291150A1 (en) | 2001-09-05 | 2003-03-12 | Sumitomo Wiring Systems, Ltd. | Method of producing an electrical cable insulating material |
-
1992
- 1992-05-19 JP JP12615992A patent/JPH05320439A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002074853A1 (en) * | 2001-03-19 | 2002-09-26 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Flame-retardant polyolefin resin composition |
| WO2002074852A1 (en) * | 2001-03-19 | 2002-09-26 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Flame-retardant polyolefin resin composition |
| US6919391B2 (en) | 2001-03-19 | 2005-07-19 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Flame-retardant polyolefin-resin composition |
| US6924331B2 (en) | 2001-03-19 | 2005-08-02 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Flame-retardant polyolefin resin composition |
| EP1291150A1 (en) | 2001-09-05 | 2003-03-12 | Sumitomo Wiring Systems, Ltd. | Method of producing an electrical cable insulating material |
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