JPH02120345A - Flame-retarding polyolefin composition - Google Patents
Flame-retarding polyolefin compositionInfo
- Publication number
- JPH02120345A JPH02120345A JP27314588A JP27314588A JPH02120345A JP H02120345 A JPH02120345 A JP H02120345A JP 27314588 A JP27314588 A JP 27314588A JP 27314588 A JP27314588 A JP 27314588A JP H02120345 A JPH02120345 A JP H02120345A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- flame
- polyolefin
- weight
- magnesium hydroxide
- 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
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 title claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 21
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 21
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 21
- 125000003118 aryl group Chemical group 0.000 claims abstract description 19
- 239000000779 smoke Substances 0.000 claims description 25
- 239000003063 flame retardant Substances 0.000 claims description 9
- 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 8
- 239000004793 Polystyrene Substances 0.000 abstract description 19
- 229920002223 polystyrene Polymers 0.000 abstract description 19
- -1 polyethylene Polymers 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 7
- 229920003023 plastic Polymers 0.000 abstract description 7
- 239000004033 plastic Substances 0.000 abstract description 7
- 239000004698 Polyethylene Substances 0.000 abstract description 6
- 229920000573 polyethylene Polymers 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 235000012254 magnesium hydroxide Nutrition 0.000 abstract 2
- 230000000391 smoking effect Effects 0.000 abstract 2
- 230000000979 retarding effect Effects 0.000 abstract 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 239000000178 monomer Substances 0.000 description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229910052794 bromium Inorganic materials 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- 229920006037 cross link polymer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 4
- 229910052740 iodine Chemical group 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006192 iodination reaction Methods 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 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 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 150000005526 organic bromine compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- RZCJSVRGPHXBSM-UHFFFAOYSA-N 8-chloro-[1,3]dioxolo[4,5-g]quinazoline Chemical compound C1=C2C(Cl)=NC=NC2=CC2=C1OCO2 RZCJSVRGPHXBSM-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229940007424 antimony trisulfide Drugs 0.000 description 1
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000026045 iodination Effects 0.000 description 1
- BIZCJSDBWZTASZ-UHFFFAOYSA-N iodine pentoxide Inorganic materials O=I(=O)OI(=O)=O BIZCJSDBWZTASZ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Organic Insulating Materials (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的］
（産業上の利用分野）
本発明は、電線被覆材料等に使用される難燃性ポリオレ
フィン組成物、とくに発煙性を低減させた難燃性ポリ７
オレフイン組成物に関するものである。Detailed Description of the Invention [Objective of the Invention] (Industrial Application Field) The present invention relates to a flame-retardant polyolefin composition used for electric wire coating materials, etc.
The present invention relates to an olefin composition.
（従来技術）
従来から、電線被覆用等の難燃性プラスチック材料とし
ては、デカブロモビフェニルエーテル、ヘキサブロモベ
ンゼン等の有機臭素化合物や、水酸化マグネシウム、水
酸化アルミニウム等の無機化合物をプラスチックに混線
成形したものが知られている。(Prior art) Conventionally, flame-retardant plastic materials for covering electric wires, etc., have been mixed with organic bromine compounds such as decabromo biphenyl ether and hexabromobenzene, and inorganic compounds such as magnesium hydroxide and aluminum hydroxide. Molded products are known.
（発明が解決しようとする課題）
上記のような有機臭素化合物は高度の燃焼抑制効果を有
し、難燃剤として優れている反面、プラスチック材料か
らの発煙を促進する欠点が認められている。他方、水酸
化マグネシウム等の無機化合物は発煙を促進することは
ないが、難燃性能が劣るため、プラスチック材料に対し
て多量を添加することが必要であり、そのためにプラス
チック材料の成形性が悪化し、また得られた成形品の機
械的強度等の品質が著しく低下するという問題点が指摘
されていた。(Problems to be Solved by the Invention) Although the above-mentioned organic bromine compounds have a high combustion suppressing effect and are excellent as flame retardants, they are recognized to have the drawback of promoting smoke generation from plastic materials. On the other hand, inorganic compounds such as magnesium hydroxide do not promote smoke generation, but their flame retardant performance is poor, so it is necessary to add large amounts to plastic materials, which deteriorates the moldability of plastic materials. However, it has also been pointed out that the quality of the obtained molded product, such as mechanical strength, is significantly reduced.
従って、従来の方法では、プラスチック材料に難燃性と
低発煙性を同時に付与することは不可能であり、このよ
うな特性を有する電線被覆用等のプラスチック材料が強
く要望されていたにもかかわらず、未だ実質的にその技
術手段が確立されていないのが実状である。Therefore, with conventional methods, it is impossible to simultaneously impart flame retardancy and low smoke emission to plastic materials, and although there has been a strong demand for plastic materials for use in covering electric wires, etc., that have these properties. The reality is that the technical means for doing so have not yet been substantially established.
［発明の構成］
（課題を解決するための手段）
本発明者等は、未解決の上記課題を全面的に解決するた
め、ポリオレフィン樹脂に難燃性を付与し、しかも発煙
を効果的に抑制する工業的手段を確立するため鋭意研究
した結果、水酸化マグネシウムとハロゲン化芳香族重合
体の特定量を該ポリオレフィン樹脂に含有させることに
より、この問題点を解決した。[Structure of the Invention] (Means for Solving the Problems) In order to completely solve the above-mentioned unresolved problems, the present inventors have provided a polyolefin resin with flame retardancy and effectively suppressed smoke generation. As a result of extensive research in order to establish an industrial means to do so, this problem was solved by incorporating specific amounts of magnesium hydroxide and a halogenated aromatic polymer into the polyolefin resin.
即ち、本発明は、ポリオレフィン１００重量部に対して
、水酸化マグネシウム６５〜１５０重量部とハロゲン化
芳香族重合体２〜３０重量部を含有する、低発煙性及び
難燃性ポリオレフィン組成物である。That is, the present invention is a low-smoke and flame-retardant polyolefin composition containing 65 to 150 parts by weight of magnesium hydroxide and 2 to 30 parts by weight of a halogenated aromatic polymer based on 100 parts by weight of the polyolefin. .
本発明において、ポリオレフィン樹脂１００重量部に対
して、水酸化マグネシウムが１５０重量部よりも多く含
有する場合には、樹脂成形品の機械強度等の品質低下が
大きくなり、逆に６５重量部未満を含有する場合には、
発煙の抑制効果および難燃効果が不十分となるため、い
ずれの場合も好ましくない、また本発明の目的を更に好
適に達成するためには、水酸化マグネシウムの含有量を
９０−１３０重量部とするとよい、該水酸化マグネシウ
ムの特性については特に制限はないが、衝撃強度、表面
状態等が特に優れた樹脂成形品を得るためには、粒径が
０．１〜５０μ好ましくは０．２〜５ＬＬ、ＢＥＴ法比
法面表面積２０ｒｎ’／グネシウムの分散性、流動性等
を向上させるために、あらかじめステアリン酸ナトリウ
ム、ラウリルスルホン酸ナトリウム等で表面処理するこ
とも可能である。In the present invention, if magnesium hydroxide is contained in an amount greater than 150 parts by weight with respect to 100 parts by weight of the polyolefin resin, quality deterioration such as mechanical strength of the resin molded product will be significant; If it contains,
Either case is undesirable because the smoke suppression effect and flame retardant effect will be insufficient. In order to more preferably achieve the object of the present invention, the content of magnesium hydroxide should be 90 to 130 parts by weight. There are no particular restrictions on the properties of the magnesium hydroxide, but in order to obtain a resin molded product with particularly excellent impact strength, surface condition, etc., the particle size should be 0.1 to 50 μm, preferably 0.2 to 50 μm. 5LL, BET method surface area 20rn'/In order to improve the dispersibility, fluidity, etc. of gnesium, it is also possible to perform a surface treatment with sodium stearate, sodium lauryl sulfonate, etc. in advance.
本発明におけるハロゲン化芳香族重合体とは、臭素また
は沃素原子を結合金有する芳香族重合体であり、該芳香
族重合体としては、スチレン、ビニルトルエン、ビニル
ナフタレン等の芳香族モ／Ｉビニル単量体を重合させた
線状芳香族重合体、並びにこれら芳香族モノビニル単量
体とジビニルベンゼン、トリビニルベンゼン、ジビニル
トルエン、ジビニルジフェニルエーテル、エチレングリ
コールジメタクリレート、トリメチロールプロパントリ
メタクリレート等のポリビニル単量体、さらに必要に応
じて、これらと共重合可能な一種又：よ二種以上の他の
単量体とを、公知の重合方法によって重合させるか、あ
るいは、線状ポリスチレン等の線状芳香族重合体をフリ
ーデルクラフト反応等の公知の方法によって重合体分子
鎖間に交叉結合を形成させて得られる芳香族架橋重合体
を使用することができる。The halogenated aromatic polymer in the present invention refers to an aromatic polymer having a bromine or iodine atom bonded to it. Linear aromatic polymers obtained by polymerizing monomers, and these aromatic monovinyl monomers and polyvinyl monomers such as divinylbenzene, trivinylbenzene, divinyltoluene, divinyl diphenyl ether, ethylene glycol dimethacrylate, and trimethylolpropane trimethacrylate. If necessary, one or more other monomers copolymerizable with these monomers are polymerized by a known polymerization method, or linear aromatic polymers such as linear polystyrene are used. An aromatic crosslinked polymer obtained by forming cross-links between polymer molecular chains by a known method such as Friedel-Crafts reaction can be used.
上記ポリビニル単量体の使用量としては、全ビニル単量
体に対して１〜２０重量％、好ましくは３〜１０重量％
の範囲を用いることができる。ポリビニル単量体の使用
量が２０重量％を超える場合には，架橋度が高くなるた
めに重合体を臭素化又は沃素化する７反応が困難となり
、所望のハロゲン含有率を有するハロゲン化芳香族架橋
重合体を得ることができない。The amount of the polyvinyl monomer used is 1 to 20% by weight, preferably 3 to 10% by weight based on the total vinyl monomer.
A range of can be used. If the amount of the polyvinyl monomer used exceeds 20% by weight, the degree of crosslinking will increase, making it difficult to carry out the bromination or iodination reaction of the polymer, resulting in a halogenated aromatic compound having the desired halogen content. It is not possible to obtain a crosslinked polymer.
該重合体において臭素又は沃素量は可能な限り高含有率
のものが望ましく、少なくとも３０重量％以上、好まし
くは５０重量％以上であることが好ましい．かかる高ハ
ロゲン含有率の重合体を使用することにより、所望の難
燃性を付与するのにその使用量を低減することができ、
従って、樹脂成形品の機械強度等の品質低下を防止する
ことが可能となる。The content of bromine or iodine in the polymer is preferably as high as possible, preferably at least 30% by weight, preferably 50% by weight or more. By using such high halogen content polymers, the amount used can be reduced to impart the desired flame retardancy;
Therefore, it is possible to prevent quality deterioration such as mechanical strength of the resin molded product.
芳香族重合体に臭素又は沃素原子を結合金有させる方法
については特に制限はなく、臭素化及び沃素化反応に関
する公知のいかなる方法も使用することができる０例え
ば、臭素化する方法としては、特公昭６１−３１１４６
号公報に記載されたように、芳香族架橋重合体に分子状
臭素を滴下して臭素化する方法、又は架橋重合体、ジク
ロルエタンのような溶媒及び三塩化アンチモンのような
触媒よりなるスラリーに塩化臭素を作用させる方法．沃
素化する方法としては、架橋重合体を反応溶媒中で塩化
沃素を作用させる方法又は五酸化沃素のような酸化剤の
存在下に沃素を作用させる方法等がある。線状重合体の
場合は、重合体をジクロルエタンに溶解し、三塩化アン
チモン触媒を用いて塩化臭素又は塩化沃素を作用させ、
生成したハロゲン化重合体を再沈殿させて得る。There are no particular restrictions on the method of bonding bromine or iodine atoms to the aromatic polymer, and any known method relating to bromination and iodination reactions may be used. Kosho 61-31146
As described in the publication, a method of brominating an aromatic crosslinked polymer by dropping molecular bromine, or a method of brominating a crosslinked polymer, a slurry consisting of a solvent such as dichloroethane, and a catalyst such as antimony trichloride. How to use bromine. Examples of the iodination method include a method in which the crosslinked polymer is treated with iodine chloride in a reaction solvent, or a method in which the crosslinked polymer is treated with iodine in the presence of an oxidizing agent such as iodine pentoxide. In the case of a linear polymer, the polymer is dissolved in dichloroethane and treated with bromine chloride or iodine chloride using an antimony trichloride catalyst,
The produced halogenated polymer is obtained by reprecipitation.
更に臭素又は／及び沃素原子を結合含有する単量体と、
必要に応じてそれと共重合可能な一種又は二種以上の他
の単量体とを、公知の方法により共重合させたものを使
用することも可能である。Furthermore, a monomer containing bonded bromine or/and iodine atoms,
If necessary, it is also possible to use a product obtained by copolymerizing it with one or more types of other monomers that can be copolymerized by a known method.
本発明において、ポリオレフィン１００重量部に対して
、ハロゲン化芳香族重合体が３０重量部よりも多く含量
する場合は、発煙量が増大すると共に、樹脂成形品の磯
城強度等の品質低下が大きくなり、逆に２重量部未満を
含有する場合には、難燃性が不十分となるため、いずれ
の場合も好ましくない。また本発明の目的を更に好適に
達成するためには、ハロゲン化芳香族重合体の含有量を
３〜２０重量部とするとよい。In the present invention, if the content of the halogenated aromatic polymer is more than 30 parts by weight with respect to 100 parts by weight of the polyolefin, the amount of smoke generated will increase and the quality of the resin molded product, such as its strength, will be significantly reduced. On the other hand, if the content is less than 2 parts by weight, the flame retardance will be insufficient, so either case is not preferable. Further, in order to more preferably achieve the object of the present invention, the content of the halogenated aromatic polymer is preferably 3 to 20 parts by weight.
本発明におけるポリオレフィンとしては、エチレン、プ
ロピレン、■−ブテン等の単独重合体又はそれ等の共重
合体、あるいはそれ等と共重合可能なジエン化合物等と
の三元重合体等をあげることができる。Examples of the polyolefin in the present invention include homopolymers of ethylene, propylene, and -butene, copolymers thereof, and terpolymers of these and diene compounds copolymerizable with them. .
本発明においては、他の難燃助剤として三酸化アンチモ
ン、五酸化アンチモン、三塩化アンチモン、三硫化アン
チモン等を併用することも可能である。更に、酸化防止
剤、熱安定剤、紫外線吸収剤、可塑剤、離型剤、着色剤
等の樹脂添加剤を使用することも何ら差し支えない。In the present invention, it is also possible to use antimony trioxide, antimony pentoxide, antimony trichloride, antimony trisulfide, etc. as other flame retardant aids. Furthermore, there is no problem in using resin additives such as antioxidants, heat stabilizers, ultraviolet absorbers, plasticizers, mold release agents, and colorants.
本発明の組成物を製造する方法は特に限定されるもので
はないが、ポリオレフィン、水酸化マグネシウム、ハロ
ゲン化芳香族重合体及び必要に応じて前記の各種成分を
所定の配合比率に調整し、これをロールニーダ−等で混
練した後、必要に応じてベレット化したものを射出、押
出し、圧縮等公知の方法によって成形することができる
。Although the method for producing the composition of the present invention is not particularly limited, the polyolefin, magnesium hydroxide, halogenated aromatic polymer, and, if necessary, the various components described above are adjusted to a predetermined blending ratio, and After kneading with a roll kneader or the like, if necessary, the pelletized product can be molded by known methods such as injection, extrusion, and compression.
（発明の効果）
本発明においては、ポリオレフィンに対して特定含有率
の水酸化マグネシウム及びハロゲン化芳香族重合体が複
合的に作用することにより、ポリオレフィンの難燃化と
発煙抑制を同時に達成することが可能である。(Effects of the Invention) In the present invention, flame retardance of polyolefin and suppression of smoke generation can be achieved at the same time by the composite action of magnesium hydroxide and halogenated aromatic polymer at a specific content on polyolefin. is possible.
（実施例）
本発明の内容を更番こ具体的に説明するため、以下に実
施例を記載するが、本発明の要旨はこれ等実施例の記載
によって何ら限定されるものではない。なお実施例にお
いて示される部は、特に断りのない限り全て重量基準に
よるものである。(Examples) In order to specifically explain the content of the present invention, Examples are described below, but the gist of the present invention is not limited in any way by the description of these Examples. Note that all parts shown in the examples are based on weight unless otherwise specified.
実施例１
ハロゲン化芳香族重合体である臭素化架橋ポリスチレン
は下記の方法で調製した。即ち、水５００−とポリビニ
ルアルコール１ｇを反応容器にとり、撹拌下８０〜９０
°Ｃで、これにスチレンＬｏｇ、ジビニルベンゼン１ｇ
、トルエン５ｇ、ドデカン５ｇ及び過酸化ベンゾイル０
２ｇの混合溶液を添加した後、激しく撹拌して２４時間
重合を継続した。ついで濾過、熱水洗処理をした後乾燥
した。このようにして得た架橋ポリスチレンをジクロル
エタン１ｏｏｋ及び三塩化アンチモン１．２５ｇよりな
る溶液中に懸濁させ、攪拌下ｌＯ〜２０″Ｃで塩化臭素
６０ｇを３時間かけて添加し、その後１時間の熟成を経
た後、水２０Ｊ、続いて４８％水酸化ナトリウム水溶液
４３ｇを加えて中和し、濾過、ジクロルエタンで洗浄、
乾燥、粉砕処理を経て、臭素含有率６５．７％の臭素化
架橋ポリスチレン２５ｇを得た。Example 1 Brominated crosslinked polystyrene, which is a halogenated aromatic polymer, was prepared by the following method. That is, 500 g of water and 1 g of polyvinyl alcohol were placed in a reaction vessel, and 80 to 90 g of water was added under stirring.
At °C, add styrene Log, divinylbenzene 1g
, toluene 5g, dodecane 5g and benzoyl peroxide 0
After adding 2 g of the mixed solution, the polymerization was continued for 24 hours with vigorous stirring. It was then filtered, washed with hot water, and then dried. The cross-linked polystyrene thus obtained was suspended in a solution consisting of 1 ook of dichloroethane and 1.25 g of antimony trichloride, and 60 g of bromine chloride was added over a period of 3 hours at 10 to 20"C with stirring, followed by the addition of 60 g of bromine chloride for 1 hour. After aging, neutralize by adding 20 J of water and then 43 g of 48% sodium hydroxide aqueous solution, filter, wash with dichloroethane,
After drying and pulverization, 25 g of brominated crosslinked polystyrene with a bromine content of 65.7% was obtained.
次に、以下の方法で本発明のポリエチレン樹脂組成物を
製造した。即ち、低密度ポリエチレン（ＪＩＳ Ｋ
７２１０、試験温度１９０℃、試験荷重５．ＯＯｋｇ
ｆで測定したＭＦＲが４．６）１００部に水酸化マグネ
シウム（平均粒子径０．６〜０．７μ、ＢＥＴ法比法面
表面積４ｒｒ？／ｇ＞ １２５部、前記の臭素化架橋
ポリスチレン６．６部及び三酸化アンチモン１．６部を
ロール温度１４０〜Ｌ ５０ ’Ｃで混練したシートを
、所定厚みの金枠に仕込み、１７０’Ｃ（３０〜５０ｋ
ｇ／ｃｍ２）でプレス成形した。加圧下（３０〜６０
ｋｇ／ｃｍ” ）に冷却した後、プレス機から取り出し
、試験片の形状に打ち抜いた。Next, a polyethylene resin composition of the present invention was produced by the following method. That is, low density polyethylene (JIS K
7210, test temperature 190°C, test load 5. OOkg
MFR measured by f is 4.6), 100 parts of magnesium hydroxide (average particle size 0.6 to 0.7μ, BET specific slope surface area 4rr?/g> 125 parts, brominated crosslinked polystyrene 6. A sheet prepared by kneading 6 parts of antimony trioxide and 1.6 parts of antimony trioxide at a roll temperature of 140 to 50'C is placed in a metal frame of a predetermined thickness, and heated to 170'C (30 to 50k
g/cm2). Under pressure (30-60
kg/cm"), it was taken out from the press and punched into the shape of a test piece.
このようにして製造した所定形状、厚みの試験片を用い
て難燃性、発煙性を評価した結果を第１表に示す、ここ
において、難燃性の評価は米国難燃性試験法ＵＬ−９４
に基づき、表中ｖ−０は着火後１０秒以内で自己消火し
、溶融落下物による綿着火がないことを示す。また、発
煙性の評価はＪＩＳ Ｄ １２０１により、表中の
数値は減光係数を示し、減光係数が０．２に満たない場
合を発煙１級、０．２以上１．０に満たない場合を発煙
２級、１．０以上２．４に満たない場合を発煙３級とし
た。Table 1 shows the results of evaluating flame retardancy and smoke generation using the test pieces of the predetermined shape and thickness manufactured in this way. 94
Based on this, v-0 in the table indicates that the fire self-extinguished within 10 seconds after ignition, and there was no cotton ignition due to molten falling matter. In addition, the smoke generation evaluation is based on JIS D 1201, and the numbers in the table indicate the light attenuation coefficient.If the light attenuation coefficient is less than 0.2, it is grade 1 smoke generation, and if it is 0.2 or more but less than 1.0. The smoke generation was classified as 2nd grade, and the smoke generation was classified as 3rd grade when it was 1.0 or more but less than 2.4.
第１表から、本発明のポリエチレン樹脂組成物は難燃性
、低発煙性共に優れていることがわかる。From Table 1, it can be seen that the polyethylene resin composition of the present invention has excellent flame retardancy and low smoke generation properties.
実施例２〜５
実施例１のポリエチレン、水酸化マグネシウム、臭素化
架橋ポリスチレン及び三酸化アンチモンを使用し、実施
例１と同様の方法により各種配合比率の樹脂組成物を製
造して、その難燃性、発煙性を評価した（第１表）。本
発明の組成範囲に属する樹脂は、いずれも優れた難燃性
、低発煙性を示すことがわかる。Examples 2 to 5 Using the polyethylene, magnesium hydroxide, brominated crosslinked polystyrene, and antimony trioxide of Example 1, resin compositions with various blending ratios were manufactured in the same manner as in Example 1, and their flame retardant properties were evaluated. The properties and smoke generation properties were evaluated (Table 1). It can be seen that all the resins falling within the composition range of the present invention exhibit excellent flame retardancy and low smoke generation.
比較例１〜３
ポリエチレン１００部に水酸化マグネシウム／臭素化架
橋ポリスチレンの配合比率が６０部／１８．７部、６０
部１５，２部、０部／３４．３部と本発明の範囲外であ
る樹脂を実施例１と同様の方法で製造し、難燃性、発煙
性を評価した（第１表）。このような組成範囲である場
合は、難燃性と発煙性を共に改善することはできないこ
とがわかる。Comparative Examples 1 to 3 The blending ratio of magnesium hydroxide/brominated crosslinked polystyrene to 100 parts of polyethylene was 60 parts/18.7 parts, 60 parts
Resins of 15.2 parts, 0 parts/34.3 parts, which are outside the scope of the present invention, were produced in the same manner as in Example 1, and their flame retardance and smoke-emitting properties were evaluated (Table 1). It can be seen that in the case of such a composition range, it is not possible to improve both flame retardancy and smoke-emitting property.
実施例６
実施例１のポリエチレンに代えてポリプロピレン（ＪＩ
Ｓ Ｋ ７２１０、試験温度２３０℃、試験荷重２
．１６ｋｇｆで測定したＭＦＲが８．０）に所定量の水
酸化マグネシウム、臭素化架橋ポリスチレン及び三酸化
アンチモンを配合し、実施例１と同様の方法で樹脂組成
物を製造し、難燃性と発煙性を評価した（第１表）１本
発明の組成物が優れた難燃性と低発煙性を示すことがわ
かる。Example 6 Polypropylene (JI
S K 7210, test temperature 230℃, test load 2
．． A resin composition was prepared in the same manner as in Example 1 by blending predetermined amounts of magnesium hydroxide, brominated cross-linked polystyrene, and antimony trioxide with MFR of 8.0 measured at 16 kgf. (Table 1) It can be seen that the composition of the present invention exhibits excellent flame retardancy and low smoke generation.
実施例７〜８
ハロゲン化芳香族重合体として、実施例１の臭素化架橋
ポリスチレンに代えて、臭素化ポリスチレン（非架橋）
又は沃素化架橋ポリスチレンを使用した。該臭素化ボリ
スチ１ノン（非架橋）は次の方法により調製した。即ち
、ポリスチレン（ＧＰＣ法分子量５８０００）をジクロ
ルエタンに溶解し、実施例１の臭素化架橋ポリスチレン
と同様の処方により臭素化した後、中和、再沈殿、γ濾
過、洗浄、乾燥した（臭素含有率６８．５％）、また、
該沃素化架橋ポリスチレンは実施例１で得た架橋ポリス
チレンをジクロルエタンに懸濁させ、塩化沃素で沃素化
した後、中和、水洗、濾過、乾燥して調製した（沃素含
有量３５．０％）。Examples 7-8 Brominated polystyrene (non-crosslinked) was used instead of the brominated crosslinked polystyrene of Example 1 as the halogenated aromatic polymer.
Alternatively, iodinated crosslinked polystyrene was used. The brominated boristinone (non-crosslinked) was prepared by the following method. That is, polystyrene (molecular weight by GPC method: 58,000) was dissolved in dichloroethane, brominated using the same recipe as the brominated crosslinked polystyrene of Example 1, and then neutralized, reprecipitated, gamma-filtered, washed, and dried (bromine content 68.5%), and
The iodinated cross-linked polystyrene was prepared by suspending the cross-linked polystyrene obtained in Example 1 in dichloroethane, iodizing with iodine chloride, neutralizing, washing with water, filtering, and drying (iodine content 35.0%). .
実施例１のポリエチレン１００部、水酸化マグネシウム
１１２部に対して、前記の臭素化ポリスチレン８．０部
及び三酸化アンチモン２．０部、又は沃素化架橋ポリス
チレン１７．４部及び三酸化アンチモン２．３部の配合
比率で、実施例１と同様の方法で本発明の樹脂組成物を
製造し、難燃性と発煙１生を評価した（第１表）６本発
明により、難燃性と低発煙性が共に優れた樹脂組成物が
得られることがわかる。To 100 parts of the polyethylene of Example 1 and 112 parts of magnesium hydroxide, 8.0 parts of the above-mentioned brominated polystyrene and 2.0 parts of antimony trioxide, or 17.4 parts of iodinated crosslinked polystyrene and 2.0 parts of antimony trioxide were added. A resin composition of the present invention was produced in the same manner as in Example 1 using a blending ratio of 3 parts, and the flame retardance and smoke generation were evaluated (Table 1)6. It can be seen that a resin composition with excellent smoke generation properties can be obtained.
比較例４
実施例１のポリエチレン１００部に対して、水酸化マグ
ネシウム１００部、ハロゲン化芳香族重合体に代えてデ
カブロモジフェニルエーテル１０．０部及び三酸化アン
チモン３．１部を配合し、実施例１と同様に樹脂組成物
を製造し、難燃性と発煙性を評価した（第１表）。この
場合は、難燃性は優れているが発煙性は劣ることがわか
る。Comparative Example 4 To 100 parts of the polyethylene of Example 1, 100 parts of magnesium hydroxide, 10.0 parts of decabromodiphenyl ether and 3.1 parts of antimony trioxide were added in place of the halogenated aromatic polymer, and the Example A resin composition was produced in the same manner as in Example 1, and its flame retardancy and smoke generation properties were evaluated (Table 1). In this case, it can be seen that the flame retardance is excellent, but the smoke generation property is poor.
実施例９、比較例５、参考例
実施例１のポリエチレン１００部に対して、水酸化マグ
ネシウム９０部、臭素化架橋ポリスチレン５．５部及び
三酸化アンチモン１．４部を配合したもの（実施例８）
、水酸化マグネシウムのみを１７０部配白したもの（比
較例５）。更に、なにも配合しない低密度ポリエチレン
（参考例）３種類の試験片を、実施例１と同様の方法で
成形し、それ等の難燃性、発煙性及び衝撃強度（ＪＩＳ
Ｋ ７１１０のアイゾツト衝撃値ｋｇｆ −ｃｍ
／ ｃｍ” ）を評価した（第２表）、第２表から明ら
かなように、水酸化マグネシウム単独添加（比較例５）
で難燃性と低発煙性を達成するためには本発明より多量
の配合が必要であり、そのために衝撃強度が著しく低下
することがわかる。これと比べて本発明の場合、樹脂性
能の低下が少なく、しかも難燃性、低発煙性が優れた樹
脂成形品を得ることができる。Example 9, Comparative Example 5, Reference Example 100 parts of the polyethylene of Example 1 was blended with 90 parts of magnesium hydroxide, 5.5 parts of brominated crosslinked polystyrene, and 1.4 parts of antimony trioxide (Example 8)
, 170 parts of magnesium hydroxide alone (Comparative Example 5). Furthermore, three types of test pieces of low-density polyethylene (reference example) containing no additive were molded in the same manner as in Example 1, and their flame retardance, smoke emitting property, and impact strength (JIS
K 7110 Izot impact value kgf -cm
/ cm”) (Table 2). As is clear from Table 2, magnesium hydroxide was added alone (Comparative Example 5)
It can be seen that in order to achieve flame retardancy and low smoke generation properties, a larger amount is required than in the present invention, and as a result, the impact strength is significantly reduced. In contrast, in the case of the present invention, a resin molded article with less deterioration in resin performance and excellent flame retardancy and low smoke emission can be obtained.
Claims (1)
ウム６５〜１５０重量部とハロゲン化芳香族重合体２〜
３０重量部を含有する、低発煙性及び難燃性ポリオレフ
ィン組成物。For 100 parts by weight of polyolefin, 65 to 150 parts by weight of magnesium hydroxide and 2 to 2 parts by weight of halogenated aromatic polymer
A low smoke and flame retardant polyolefin composition containing 30 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27314588A JPH02120345A (en) | 1988-10-31 | 1988-10-31 | Flame-retarding polyolefin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27314588A JPH02120345A (en) | 1988-10-31 | 1988-10-31 | Flame-retarding polyolefin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02120345A true JPH02120345A (en) | 1990-05-08 |
Family
ID=17523745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27314588A Pending JPH02120345A (en) | 1988-10-31 | 1988-10-31 | Flame-retarding polyolefin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02120345A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014106928A1 (en) * | 2013-01-07 | 2014-07-10 | 矢崎総業株式会社 | Thermally resistant crosslinked wire |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS575734A (en) * | 1980-06-16 | 1982-01-12 | Tokuyama Soda Co Ltd | Polyolefin composition |
-
1988
- 1988-10-31 JP JP27314588A patent/JPH02120345A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS575734A (en) * | 1980-06-16 | 1982-01-12 | Tokuyama Soda Co Ltd | Polyolefin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014106928A1 (en) * | 2013-01-07 | 2014-07-10 | 矢崎総業株式会社 | Thermally resistant crosslinked wire |
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