JPH03134049A - Flame-retardant resin composition - Google Patents
Flame-retardant resin compositionInfo
- Publication number
- JPH03134049A JPH03134049A JP27400289A JP27400289A JPH03134049A JP H03134049 A JPH03134049 A JP H03134049A JP 27400289 A JP27400289 A JP 27400289A JP 27400289 A JP27400289 A JP 27400289A JP H03134049 A JPH03134049 A JP H03134049A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- flame
- parts
- weight
- halogen
- 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
- 239000003063 flame retardant Substances 0.000 title claims abstract description 29
- 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 abstract description 26
- 239000011342 resin composition Substances 0.000 title claims description 11
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 10
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 10
- 229920001971 elastomer Polymers 0.000 claims abstract description 8
- 239000005060 rubber Substances 0.000 claims abstract description 7
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- 125000002947 alkylene group Chemical group 0.000 claims abstract 2
- 125000001118 alkylidene group Chemical group 0.000 claims abstract 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract 2
- 239000004593 Epoxy Substances 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 18
- 239000011347 resin Substances 0.000 abstract description 18
- 239000003822 epoxy resin Substances 0.000 abstract description 5
- 229920000647 polyepoxide Polymers 0.000 abstract description 5
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- -1 2-hydroxy-3-phenoxypropyl Chemical group 0.000 abstract description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- 125000002348 vinylic group Chemical group 0.000 abstract 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 abstract 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 abstract 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 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 description 8
- 238000000034 method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 229920006942 ABS/PC Polymers 0.000 description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical class C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- ZTHJQCDAHYOPIK-UHFFFAOYSA-N 3-methylbut-2-en-2-ylbenzene Chemical compound CC(C)=C(C)C1=CC=CC=C1 ZTHJQCDAHYOPIK-UHFFFAOYSA-N 0.000 description 1
- 229910001339 C alloy Inorganic materials 0.000 description 1
- 241000218645 Cedrus Species 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、難燃性に優れ、耐熱性、熱安定性、機械特性
の良好な難燃性樹脂組成物に間するものである。さらに
詳しくは、ビニル系単量体あるいはその重合体の共重合
物で、その一部もしくは全部をゴム成分存在下で共重合
した樹脂（Ａ）及びポリカーボネート樹脂（Ｂ）から成
る熱可塑性樹脂組成物（Ｃ）にハロゲン含有エポキシ変
性物を配合してなる難燃性樹脂組成物に間するものであ
る。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides a flame-retardant resin composition that has excellent flame retardancy, heat resistance, thermal stability, and mechanical properties. More specifically, a thermoplastic resin composition consisting of a resin (A) which is a copolymer of a vinyl monomer or its polymer, part or all of which is copolymerized in the presence of a rubber component, and a polycarbonate resin (B). This is a flame-retardant resin composition obtained by blending (C) with a halogen-containing epoxy modified product.
（従来の技術）
ポリカーボネート樹脂とＡＢＳｖＡ脂を混合したＡＢＳ
／ＰＣ７０イ樹脂等の熱可塑性ポリマーアロイ樹脂は、
耐熱性、機械特性などの優れた諸特性を利用して目勤軍
部品、電気部品、ＯＡ機器等の分野で近年徐々に用いら
れるようになってきている。一方これらの工業材料の中
でも特に電気及び電子部品の分野では火災に対する安全
性の要求が高まり、米国ＵＬ規格に代表される難燃化に
関する各種規制が強化されるに伴い、この樹脂も他の樹
脂と同様に、多くの使用上の制限を受けるようになって
きた。(Prior technology) ABS made by mixing polycarbonate resin and ABSvA fat
/PC70 resin and other thermoplastic polymer alloy resins are
In recent years, it has gradually come to be used in fields such as military parts, electrical parts, and OA equipment, taking advantage of its excellent properties such as heat resistance and mechanical properties. On the other hand, among these industrial materials, demands for fire safety are increasing, especially in the field of electrical and electronic components, and various regulations regarding flame retardation, such as the U.S. UL standards, are being tightened. Similarly, it has come to be subject to many restrictions on its use.
すでに、ＡＢＳ／ＰＣアロイ樹脂用の難燃剤としては、
臭素化ポリカーボネートなとのハロゲン系難燃剤と、二
酸化アンチモンとを併用して使用することが提案されて
いる。しかしながら、このような難燃剤は、ＡＢＳ／Ｐ
Ｃアロイ樹脂本来の優れた耐衝撃性を始めとする機械特
性や耐熱性、高温での熱安定性を著しく低下させてしま
うという欠点があった。Already, flame retardants for ABS/PC alloy resins include:
It has been proposed to use a halogenated flame retardant such as brominated polycarbonate in combination with antimony dioxide. However, such flame retardants
This has the disadvantage that the mechanical properties including the excellent impact resistance inherent to C alloy resin, heat resistance, and thermal stability at high temperatures are significantly reduced.
（問題点を解決するための手段）
本発明者らは、この欠点に間し、ＡＢＳ／ＰＣアロイ樹
脂本来の優れた耐衝撃性を始めとする機械特性や耐熱性
、高温での熱安定性を低下させずに、難燃性を付与する
難燃剤を開発するため、鋭意検討を重ねた結果、ビニル
系単量体あるいはその重合体の共重合物で、その一部も
しくは全部をゴム成分存在下で共重合した樹脂（Ａ）及
びポリカーボネート樹脂（Ｂ）から成る熱可塑性樹脂組
成物（Ｃ）１００重量部に対し、
一般式
（式中Ｒ２及びＲ３は炭素数１〜４のアルキリデン基又
はアルキレン基、−８０２−基、Ｒ１及びＲ４Ｘ及びＹ
、 Ｚはハロゲン原子、ｐ及びｑ、 ｒ、 ｓは
Ｏ〜４の整数、 ｔはＯ〜５の整数、ｋ、 ｌ、
ｍは整数であり、 （ｋ＋ ｌ）Ｘｍ＝ｎが平均重合度
で１１以上の整数を示す、）で表されハロゲン含有率が
２０重量％であるハロゲン含有エポキシ変性物３〜５０
３１量部、難燃助剤０．１〜２０重量部を配合してなる
難燃性樹脂組成物は、樹脂本来の特性を著しく低下させ
ることなく、優れた難燃性が付与されることを見いだし
本発明に至った。(Means for Solving the Problem) The present inventors have solved this drawback by improving the mechanical properties, heat resistance, and thermal stability at high temperatures, including the excellent impact resistance inherent to ABS/PC alloy resin. In order to develop a flame retardant that imparts flame retardant properties without reducing the For 100 parts by weight of the thermoplastic resin composition (C) consisting of the resin (A) and polycarbonate resin (B) copolymerized below, group, -802- group, R1 and R4X and Y
, Z is a halogen atom, p, q, r, s is an integer from O to 4, t is an integer from O to 5, k, l,
m is an integer, (k + l)
A flame retardant resin composition containing 31 parts by weight and 0.1 to 20 parts by weight of a flame retardant aid has excellent flame retardancy without significantly deteriorating the inherent properties of the resin. This discovery led to the present invention.
本発明で用いられる樹脂（Ａ）は、不飽和カルボン酸エ
ステル単量体、芳香族ビニル単量体、シアン化ビニル単
量体等からなるビニル化合物の１種又は２種以上の共重
合可能な単量体又は重合体の１部または全部をブタジェ
ン系ゴム成分、アクリル系ゴム成分、エチレン−プロピ
レンゴム成分などからなる１１又は２ｆ！以上が複合化
されたゴム成分の存在下で共重合して得られる共重合樹
脂である。この樹脂（Ａ）は、塊状重合、溶液重合、懸
濁重合、乳化重合又はそれらの組合せ重合のいずれの方
法ででも製造することができるが、特にゴム成分含有量
が多い樹脂を製造する場合には乳化グラフト重合によっ
て製造するのが好ましい。The resin (A) used in the present invention is a copolymerizable one or more vinyl compounds consisting of unsaturated carboxylic acid ester monomers, aromatic vinyl monomers, vinyl cyanide monomers, etc. 11 or 2f where part or all of the monomer or polymer is composed of a butadiene rubber component, an acrylic rubber component, an ethylene-propylene rubber component, etc. The above is a copolymer resin obtained by copolymerizing in the presence of a composite rubber component. This resin (A) can be produced by any method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, or a combination thereof, but especially when producing a resin with a high rubber component content. is preferably produced by emulsion graft polymerization.
不飽和カルボン酸エステル単量体としては、例えば、ア
クリル酸メチル、アクリル酸エチル、アクリル酸プロピ
ル、アクリル酸イソプロピル、アクリル酸ブチル、メタ
クリル酸メチル、メタクリル酸エチル、メタクリル酸プ
ロピル、メタクリル酸イソプロピル、メタクリル酸ブチ
ル等が挙げられ、特にアクリル酸メチル、アクリル酸エ
チル、メタクリル酸メチル、メタクリル酸エチル等が好
ましい。Examples of unsaturated carboxylic acid ester monomers include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, and methacrylate. Among them, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and the like are particularly preferred.
芳香族ビニル単量体としては、スチレン、α−メチルス
チレン、ビニルトルエン、ビニルキシレン、 トリメチ
ルスチレン、ハロゲン化スチレン等が挙げられ、特にス
チレン、α−メチルスチレンが好ましい。Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene, vinylxylene, trimethylstyrene, and halogenated styrene, with styrene and α-methylstyrene being particularly preferred.
シアン化ビニル単量体としては、アクリルニドノル、メ
タクリルニトリル等が挙げられる。Examples of vinyl cyanide monomers include acrylnidonol, methacrylnitrile, and the like.
ブタジェンゴム成分としては、ポリブタジェン、ブタジ
ェン−スチレン共重合体、ブタジェン−アクリロニトリ
ル共重合体等が挙げられる。又、アクリル系ゴム成分と
しては、アクリル酸エチル、アクリル酸ブチル、アクリ
ル酸２エチルヘキシル等のアクリル酸エステル単量体を
主成分として得られるゴム状重合体である。Examples of the butadiene rubber component include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and the like. The acrylic rubber component is a rubbery polymer obtained mainly from an acrylic ester monomer such as ethyl acrylate, butyl acrylate, or 2-ethylhexyl acrylate.
本発明における樹脂（Ａ）の使用量は、熱可望性樹脂（
Ｃ）中５〜９５！ＩＩ％である。好ましくは、３５〜６
５＠量・％である。The amount of resin (A) used in the present invention is the thermoplastic resin (
C) Middle school 5-95! II%. Preferably 35-6
5@Amount/%.
本発明でいうポリカーボネート樹脂（Ｂ）は、４゜４′
−ジオキシジアリルアルカン系ポリカーボネート樹脂で
あり、特に２． ２’ −（４，４’ジヒドロキシジフ
エニル）プロパンを成分として用い、エステル交換法あ
るいはホスゲン法により得られたポリカーボネート樹脂
が好ましい、またその使用量は、熱可塑性樹脂（Ｃ）中
５〜９５１ｉ１％であり、好ましくは、 ３５〜６５重
量％である。The polycarbonate resin (B) in the present invention is 4°4'
-dioxydiallylalkane-based polycarbonate resin, especially 2. A polycarbonate resin obtained by a transesterification method or a phosgene method using 2'-(4,4'dihydroxydiphenyl)propane as a component is preferable, and the amount used is 5 to 951i1% in the thermoplastic resin (C). and preferably 35 to 65% by weight.
本発明の難燃剤製造方法としては、ハロゲン化ビスフェ
ノールＡ等とハロゲン化ビスフェノールＡジグリシジル
エーテル等を触媒存在化で加熱して得ることができるが
これのみに限定されるものではない。The flame retardant of the present invention can be produced by heating halogenated bisphenol A and the like and halogenated bisphenol A diglycidyl ether in the presence of a catalyst, but is not limited thereto.
特に、本発明に使用する難燃剤を得る理想的な製造方法
としては、本発明者が特願昭６３−９１０４号及び特願
昭６３−６４９３５号で示した製造方法である。In particular, the ideal manufacturing method for obtaining the flame retardant used in the present invention is the manufacturing method disclosed by the present inventor in Japanese Patent Application No. 63-9104 and Japanese Patent Application No. 63-64935.
すなわち、ハロゲン化ビスフェノールＡ等とハロゲン化
ビスフェノールＡジグリシジルエーテル等を触媒存在化
、溶媒中で加熱反応を行ない、反応終了後、反応液を生
成物がほとんど溶解しない大量の溶媒中に投入し生成物
を析出させた後、乾燥させることにより高分子型の難燃
剤を得る方法、もしくは、ハロゲン化ビスフェノールＡ
等とハロゲン化ビスフェノールＡジグリシジルエーテル
等を触媒存在化、溶媒中で加熱反応を行ない、反応終了
後、反応液をイオン交換樹脂で処理し、触媒を除いた後
、溶媒を除去乾燥することにより高分子量型の難燃剤を
得る方法である。That is, halogenated bisphenol A, etc. and halogenated bisphenol A diglycidyl ether, etc. are placed in the presence of a catalyst, a heating reaction is carried out in a solvent, and after the reaction is completed, the reaction solution is poured into a large amount of solvent in which the product is hardly dissolved. A method of obtaining a polymer type flame retardant by precipitating a substance and then drying it, or a method of obtaining a polymer type flame retardant by precipitating a substance and then drying it, or halogenated bisphenol A
etc. and halogenated bisphenol A diglycidyl ether etc. in the presence of a catalyst, heat the reaction in a solvent, and after the reaction is completed, treat the reaction solution with an ion exchange resin to remove the catalyst, then remove the solvent and dry. This is a method for obtaining high molecular weight flame retardants.
本発明による一般式（１）で表されるハロゲン含有エポ
キシ変性物を難燃剤として使用するにあたっては、単独
使用でも良く、耐熱性、耐候性、耐衝撃性を著しく損わ
ない範囲で、他の公知の難燃剤（窒素系化合物、リン化
合物、ハロゲン系化合物なと）や難燃助剤く酸化アンチ
モン、酸化モリブデン、酸化スズなど）を配合しても良
く、更に、他の各種の添加剤、例えば、紫外線吸収剤、
可塑剤、着色剤、充填剤、滑剤、安定剤などを添加して
もよい。When using the halogen-containing epoxy modified product represented by the general formula (1) according to the present invention as a flame retardant, it may be used alone, or other materials may be used as long as the heat resistance, weather resistance, and impact resistance are not significantly impaired. Known flame retardants (nitrogen compounds, phosphorus compounds, halogen compounds, etc.) and flame retardant aids (antimony oxide, molybdenum oxide, tin oxide, etc.) may be added, and various other additives, For example, ultraviolet absorbers,
Plasticizers, colorants, fillers, lubricants, stabilizers, etc. may be added.
この様にして配合された難燃性樹脂組成物は、難燃効果
が高く、耐熱性、熱安定性、耐候性、成形性に優れ、各
種機械特性のバランスの良い、特に耐衝撃性に優れたも
のとなる。The flame-retardant resin composition formulated in this way has a high flame-retardant effect, excellent heat resistance, thermal stability, weather resistance, and moldability, and has a good balance of various mechanical properties, especially excellent impact resistance. It becomes something.
本発明における難燃性樹脂組成物を調整する方法として
は、加熱ロール、単軸または多軸押し出し機などの任意
の方法が適用でき、溶融、混練することによって得るこ
とができる。As a method for preparing the flame-retardant resin composition in the present invention, any method such as a heating roll, a single-screw extruder, or a multi-screw extruder can be applied, and it can be obtained by melting and kneading.
以下に合成例及び実施例を挙げて本発明を具体的に説明
するが、本発明は、その要旨をこえないかぎり、以下に
示す合成例及び実施例に制約されるものではない。The present invention will be specifically explained below with reference to synthesis examples and examples; however, the present invention is not limited to the synthesis examples and examples shown below unless it exceeds the gist thereof.
合成例１
臭素化ビスフェノールＡ型エポキシ樹脂（ＳＲ−Ｔ Ｂ
Ａ ４００． エポキシ当量３９５（版本薬品工業
） ） ７１１ ｇ’（０，９モル）とビスフェノール
Ａ型エポキシ樹脂（エビコー１−８２８、エポキシ当１
１１８８ （油化シェルエポキシ））３７．６ｇ（０，
１モル）とテトラブロモビスフェノールＡ（以下ＴＢＡ
と略す）５２８ｇ （０，９６７モル）とジオキサン６
００ｇをフラスコにとり、トリブチルアミン５ｇを添加
したのち、窒素気流下、還流温度（約１００℃）にて、
２４時間反応した。反応終了後、ジオキサン２０００
ｇ−陽イオン交換樹脂（アンバーリスト１５（オルガハ
１）６０糟１、陰イオン交換樹脂（ダイヤイオンＷＡ−
２０（三菱化成工業製））９０１を加え、５０〜６０℃
で１時間攪拌した。この溶液を濾過し、イオン交換樹脂
を除去した後、炉液中の溶媒を真空乾燥装置で除去し、
白色粉末の生成物を得た。この生成物は、酸価０．３（
ｓ（にＯＨ／ｇ）、エポキシ当量１９．８００、軟化点
２００℃以上、平均重合度＋１＝６５、臭素含有量５１
．２＠量％であった。Synthesis Example 1 Brominated bisphenol A epoxy resin (SR-T B
A 400. Epoxy equivalent 395 (Hanhon Yakuhin Kogyo)) 711 g' (0.9 mol) and bisphenol A epoxy resin (Ebicor 1-828, epoxy equivalent 1
1188 (oiled shell epoxy)) 37.6g (0,
1 mol) and tetrabromobisphenol A (hereinafter referred to as TBA)
) 528g (0,967mol) and dioxane 6
After adding 00g of 00g to a flask and adding 5g of tributylamine, at reflux temperature (approximately 100°C) under a nitrogen stream,
The reaction was carried out for 24 hours. After the reaction is completed, dioxane 2000
g-Cation exchange resin (Amberlyst 15 (Orgaha 1) 60 1, anion exchange resin (Diaion WA-
20 (manufactured by Mitsubishi Chemical Industries)) 901 and heated to 50-60°C.
The mixture was stirred for 1 hour. After filtering this solution and removing the ion exchange resin, the solvent in the furnace solution was removed using a vacuum dryer.
A white powder product was obtained. This product has an acid value of 0.3 (
s (OH/g), epoxy equivalent 19.800, softening point 200°C or higher, average degree of polymerization +1 = 65, bromine content 51
．． It was 2@% by weight.
合成例２
臭素化ビスフェノールＡ型エポキシ樹脂（ＳＲ−ＴＢＡ
４００、エポキシ当＠３９５（版本薬品工業））７９０
ｇ （］モル）とＴＢＡ５０９ｇ （０，９３５モル）
とジオキサン６００ｇをフラスコにとり、 トリブチル
アミン５ｇを添加したのち、窒素気流下、還流温度（約
１００℃）にて、２４時間反応した０反応終了後、合成
例１と同様にし、白色粉末の生成物を得た。この生成物
は、酸価０．３（＋ＩＩｇＫｏＨｚｇ）、エポキシ当量
９．４４０、軟化点２００℃以上、平均重合度ｎ＝３２
、臭素含有ｆｆ１５２．４重量％であった。Synthesis Example 2 Brominated bisphenol A type epoxy resin (SR-TBA
400, epoxy @ 395 (Hanhon Yakuhin Kogyo)) 790
g (] mol) and TBA509g (0,935 mol)
and 600 g of dioxane were placed in a flask, 5 g of tributylamine was added, and the mixture was reacted for 24 hours at reflux temperature (approximately 100°C) under a nitrogen atmosphere. I got it. This product has an acid value of 0.3 (+IIgKoHzg), an epoxy equivalent of 9.440, a softening point of 200°C or more, and an average degree of polymerization n = 32.
, bromine-containing ff was 152.4% by weight.
合成例３
臭素化ビスフェノールＡ型エポキシ樹脂（ＳＲ−・ＴＢ
Ａ４００、エポキシ当！１３９５（版本薬品工業））７
９０ｇ （１モル）とＴＢＡ４５８ｇ （０，８３８モ
ル）とトリブロモフェノール５３．６ｇ（０，１６２モ
ル）をセパラブル四つロフラスコにとり、 トリブチル
アミン０．６ ｇを添加した後、窒素気流下１４０〜１
７０℃で８時間反応した。Synthesis Example 3 Brominated bisphenol A type epoxy resin (SR-・TB
A400, epoxy! 1395 (Hanhon Yakuhin Kogyo)) 7
90 g (1 mol), 458 g (0,838 mol) of TBA, and 53.6 g (0,162 mol) of tribromophenol were placed in a separable four-bottle flask, and after adding 0.6 g of tributylamine, the mixture was heated for 140 to 1 mol under a nitrogen stream.
The reaction was carried out at 70°C for 8 hours.
反応終了後、冷却、粉砕して、淡黄色粉末の生成物を得
た。この生成物は、酸価０ 、５ （１１ｇＫＯＨ／ｇ
）、エポキシ当量７９２０、軟化点１８１’Ｃ１平均重
合度ｎ＝１２、臭素含有量５２．９１ｔｊ１％であった
。After the reaction was completed, the mixture was cooled and pulverized to obtain a pale yellow powder product. This product has an acid value of 0,5 (11 gKOH/g
), the epoxy equivalent was 7920, the softening point was 181'C1, the average degree of polymerization n was 12, and the bromine content was 52.91tj1%.
次に、比較のため、重合度の低い難燃剤の合成を以下の
とおり行った。Next, for comparison, a flame retardant with a low degree of polymerization was synthesized as follows.
合成例４
臭素化ビスフェノールＡ型エポキシ樹脂（ＳＲ−ＴＢＡ
４００、エポキシ当１１３９５（版本薬品工業））７９
０ｇ （１モル）と、 ＴＢＡ３９４ｇ（０，７２５モ
ル）をセパラブル四つロフラスコにとり、テトラメチル
アンモニウムクロライド０．５ｇを添加した後、窒素気
流下１４０〜１７０”Ｃで８時間反応した０反応終了後
、冷却、粉砕して、淡黄色粉末の生成物を得た。この生
成物は、酸価０．３ （、ＫＯ）１／ｇ）、エポキシ当
ｊ１２１５０． 軟化点１６３．５℃、臭素含有量５
２．２１ｉ量％であった。Synthesis Example 4 Brominated bisphenol A type epoxy resin (SR-TBA
400, Epoxy 11395 (Hanhon Yakuhin Kogyo)) 79
0 g (1 mole) and 394 g (0,725 mole) of TBA were placed in a separable four-bottle flask, and after adding 0.5 g of tetramethylammonium chloride, they were reacted for 8 hours at 140 to 170"C under a nitrogen stream. After the completion of the reaction. , cooled and pulverized to obtain a pale yellow powder product.This product had an acid value of 0.3 (,KO)1/g), an epoxy content of 12150, a softening point of 163.5°C, and a bromine content. 5
The content was 2.21i%.
合成例６
臭素化ビスフェノールＡ型エポキシ樹脂（ＳＲ−ＢＳ、
エポキシ当量３３１（版本薬品工業））６６２ｇ （１
モル）と、 トリブロモフェノール（以下ＴＢＰと略す
）５９６ｇ（１，９モル）をセパラブル四つロフラスコ
にとり、 トリブチルアミン０．８ｇｌ？−添加した後
、窒素気流下１２０〜１３０℃で７時間反応し、その後
１４０〜１６０’Ｃで更に２時間反応した０反応終了後
、冷却、粉砕して、淡黄色粉末の・生成物を得た。この
生成物は、酸価０ 、１ （ｍｇ ＫＯＨ／ｇ）、エポ
キシ当ｆｆ１１３０３０、軟化点９４℃、臭素含有量６
０．０重量％であった。Synthesis Example 6 Brominated bisphenol A epoxy resin (SR-BS,
Epoxy equivalent: 331 (Hanhon Yakuhin Kogyo)) 662 g (1
mol) and 596 g (1.9 mol) of tribromophenol (hereinafter abbreviated as TBP) in a separable four-bottle flask, and 0.8 g of tributylamine. - After the addition, the reaction was carried out for 7 hours at 120-130°C under a nitrogen stream, and then for another 2 hours at 140-160'C. Ta. This product has an acid value of 0.1 (mg KOH/g), an epoxy weight of 113030, a softening point of 94°C, and a bromine content of 6.
It was 0.0% by weight.
実施例１〜３
ＡＢＳ／ＰＣアロイ樹脂（マルチロンＴ−１０００（奇
人化成））、合成例１〜３で得られた化合物、二酸化ア
ンチモンを第１表の割合で配合し、押出機にてペレタイ
ズし、射出成型機にてそれぞれｔＪ Ｌ −９４燃焼試
験、アイゾツト衝撃試験、ビカット軟化点、熱安定性試
験の各種試験片を成型し、各試験を行フた。その結果を
第１表に示した。Examples 1 to 3 ABS/PC alloy resin (Multilon T-1000 (Kijin Kasei)), the compounds obtained in Synthesis Examples 1 to 3, and antimony dioxide were blended in the proportions shown in Table 1, and pelletized using an extruder. Various test pieces for the tJ L-94 combustion test, Izod impact test, Vicat softening point, and thermal stability tests were molded using an injection molding machine, and each test was conducted. The results are shown in Table 1.
比較例１〜３
実施例１〜３と同様に合成例４〜５の化合物及び臭素化
ポリカーボネートを第１表の割合で配合して試験片を成
型し、各試験を行った。その結果を第１表に示した。Comparative Examples 1 to 3 Similarly to Examples 1 to 3, the compounds of Synthesis Examples 4 to 5 and brominated polycarbonate were blended in the proportions shown in Table 1, test pieces were molded, and each test was conducted. The results are shown in Table 1.
実施例４〜６及び比較例４〜５
スチレン６１部、アクリロニトリル１９部、メタクリル
酸メチル９部のうち、メタクリル酸メチル９部とスチレ
ン６ ＩＩＢをポリブタジェン２１部の存在下でグラフ
ト共重合し、残りのスチレン４５部とアクリロニトリル
１９％を共重合して得られた共重合樹脂（ａ）又はポリ
ブタジェン９部の存在下でアクリル酸ブチル３６部を重
合して得られるゴム成分と共にアクリロニトリル１６部
とスチレン３９部をグラフト共重合して得られた共重合
樹脂（ｂ）とポリカーボネート樹脂、合成例２で得られ
た化合物、二酸化アンチモンを実施例１〜３と同様に第
２表の割合で配合して試験片を成型し、各試験を行った
。その結果を第２表に示した。Examples 4 to 6 and Comparative Examples 4 to 5 Among 61 parts of styrene, 19 parts of acrylonitrile, and 9 parts of methyl methacrylate, 9 parts of methyl methacrylate and styrene 6 IIB were graft copolymerized in the presence of 21 parts of polybutadiene, and the remaining Copolymer resin (a) obtained by copolymerizing 45 parts of styrene and 19% of acrylonitrile or 16 parts of acrylonitrile and 39% of styrene together with a rubber component obtained by polymerizing 36 parts of butyl acrylate in the presence of 9 parts of polybutadiene. The copolymer resin (b) obtained by graft copolymerizing the above parts, the polycarbonate resin, the compound obtained in Synthesis Example 2, and antimony dioxide were mixed in the proportions shown in Table 2 in the same manner as Examples 1 to 3, and the test was conducted. Pieces were molded and tested. The results are shown in Table 2.
各試験方法
アイゾツト衝撃試験はＪＩＳ Ｋ７１１０（Ｖノツチ
つき、ｌ／８”）、ビカット軟化点はＪＩＳＫ７２０６
、燃焼性試験はＵ Ｌ −９４に準じて行なった。また
、熱安定性については、試験片を２００℃の乾燥機内に
３０分間放置後の色及び形を観測し、下記の３段階評価
で表わした。Each test method Izot impact test is JIS K7110 (with V notch, l/8”), Vicat softening point is JIS K7206
The flammability test was conducted according to UL-94. Regarding thermal stability, the color and shape of the test pieces were observed after leaving them in a dryer at 200° C. for 30 minutes, and the results were evaluated using the following three-level evaluation.
Ｏ・・・着色が少なく、杉の変形も少ない。O: There is little discoloration and little deformation of the cedar.
Δ・・・着色が少しあり、形の変形も少しある。Δ: There is some coloring and some deformation of the shape.
×・・・着色があり、形が大きく変形している。×: There is coloration and the shape is greatly deformed.
以上、本発明による一般式（１）で表される化合物を使
用することにより、難燃効果が良く、耐熱性に優れ、し
かも衝撃性の低下の少ない難燃性樹脂組成物が得られる
。As described above, by using the compound represented by the general formula (1) according to the present invention, a flame-retardant resin composition having good flame retardant effect, excellent heat resistance, and less decrease in impact strength can be obtained.
Claims (1)
一部もしくは全部をゴム成分存在下で共重合した樹脂（
Ａ）及びポリカーボネート樹脂（Ｂ）から成る熱可塑性
樹脂組成物（Ｃ）１００重量部に対し、 一般式 ▲数式、化学式、表等があります▼（ I ） （式中Ｒ＿２及びＲ＿３は炭素数１〜４のアルキリデン
基又はアルキレン基、−ＳＯ＿２−基、Ｒ＿１及びＲ＿
４はグリシジル基又は▲数式、化学式、表等があります
▼基、水素基、 Ｘ及びＹ、Ｚはハロゲン原子、ｐ及びｑ、ｒ、ｓは０〜
４の整数、ｔは０〜５の整数、ｋ、ｌ、ｍは整数であり
、（ｋ＋ｌ）×ｍ＝ｎが平均重合度で１１以上の整数を
示す。）で表されハロゲン含有率が２０重量％であるハ
ロゲン含有エポキシ変性物３〜５０重量部、難燃助剤０
．１〜２０重量部を配合してなる難燃性樹脂組成物。[Claims] A copolymer of vinyl monomers or their polymers, some or all of which are copolymerized in the presence of a rubber component (
For 100 parts by weight of a thermoplastic resin composition (C) consisting of A) and a polycarbonate resin (B), there are general formulas, numerical formulas, chemical formulas, tables, etc. (I) (In the formula, R_2 and R_3 have a carbon number of 1 to 4 alkylidene group or alkylene group, -SO_2- group, R_1 and R_
4 is a glycidyl group or a ▲ mathematical formula, chemical formula, table, etc. ▼ group, a hydrogen group, X, Y, and Z are halogen atoms, p, q, r, and s are 0 to 4.
4 is an integer, t is an integer of 0 to 5, k, l, and m are integers, and (k+l)×m=n represents an average degree of polymerization, which is an integer of 11 or more. ) with a halogen content of 20% by weight, 3 to 50 parts by weight of a halogen-containing epoxy modified product, and 0 flame retardant aids.
．． A flame-retardant resin composition containing 1 to 20 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27400289A JPH03134049A (en) | 1989-10-20 | 1989-10-20 | Flame-retardant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27400289A JPH03134049A (en) | 1989-10-20 | 1989-10-20 | Flame-retardant resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03134049A true JPH03134049A (en) | 1991-06-07 |
Family
ID=17535581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27400289A Pending JPH03134049A (en) | 1989-10-20 | 1989-10-20 | Flame-retardant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03134049A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03259946A (en) * | 1990-03-12 | 1991-11-20 | Sumitomo Dow Ltd | Flame-retardant resin composition |
-
1989
- 1989-10-20 JP JP27400289A patent/JPH03134049A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03259946A (en) * | 1990-03-12 | 1991-11-20 | Sumitomo Dow Ltd | Flame-retardant resin composition |
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