JPH01287132A - Nonflammable resin composition - Google Patents
Nonflammable resin compositionInfo
- Publication number
- JPH01287132A JPH01287132A JP11683688A JP11683688A JPH01287132A JP H01287132 A JPH01287132 A JP H01287132A JP 11683688 A JP11683688 A JP 11683688A JP 11683688 A JP11683688 A JP 11683688A JP H01287132 A JPH01287132 A JP H01287132A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- weight
- halogen
- unsaturated nitrile
- copolymer
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 30
- -1 nitrile compound Chemical group 0.000 claims abstract description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 12
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 150000001491 aromatic compounds Chemical group 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 150000002825 nitriles Chemical class 0.000 claims abstract description 5
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 239000003063 flame retardant Substances 0.000 claims description 13
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 229910052801 chlorine Chemical group 0.000 claims description 3
- 239000000460 chlorine Chemical group 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 29
- 150000002367 halogens Chemical class 0.000 abstract description 29
- 150000001875 compounds Chemical class 0.000 abstract description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 13
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 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 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920001890 Novodur Polymers 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 3
- 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
- CKNCVRMXCLUOJI-UHFFFAOYSA-N 3,3'-dibromobisphenol A Chemical compound C=1C=C(O)C(Br)=CC=1C(C)(C)C1=CC=C(O)C(Br)=C1 CKNCVRMXCLUOJI-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- UPZFLZYXYGBAPL-UHFFFAOYSA-N 2-ethyl-2-methyl-1,3-dioxolane Chemical compound CCC1(C)OCCO1 UPZFLZYXYGBAPL-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 241000909456 Oregus Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000033228 biological regulation Effects 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
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000005060 rubber Substances 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
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、耐衝撃性に優れ、高度な耐光性及び難燃性を
有するスチレン系樹脂組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a styrenic resin composition having excellent impact resistance, high light resistance and flame retardancy.
スチレン系樹脂、取分けＡＢＳ樹脂は、安価な上に、優
れた耐衝撃性、耐熱性、機械特性、電気特性、成形加工
性を有し、外観が美しい等の多くの特長を有するため、
広く家庭電気製品、事務機器、家庭用品等に多量に使用
されている。併し、スチレン系樹脂は燃え易いと云う性
質のため、ＵＬ規格などの難燃化に関する各種規制が義
務づけられ、強化されており、多くの使用上の制限を受
けている。Styrenic resins, especially ABS resins, are inexpensive and have many features such as excellent impact resistance, heat resistance, mechanical properties, electrical properties, moldability, and beautiful appearance.
It is widely used in large quantities in household electrical appliances, office equipment, household goods, etc. However, since styrene resins are easily flammable, various regulations regarding flame retardation such as UL standards are required and are being strengthened, and they are subject to many restrictions on use.
スチレン系樹脂のＮ燃比は、主にハロゲン、リン等を含
有する化合物や三酸化７ンチモン等の難燃剤を添加する
ことにより行われているが、これらの難燃剤を配合する
ことにより目的とする難燃性が得られるものの、その反
面、他の物性に悪い影響を及ぼすことが多い。The N-flame ratio of styrenic resins is mainly controlled by adding compounds containing halogens, phosphorus, etc., and flame retardants such as 7thimony trioxide. Although flame retardancy can be obtained, on the other hand, it often has a negative effect on other physical properties.
又、近年コンピュータやファクシミリ等の事務機器の普
及に伴い、難燃性と耐衝撃性に加え、螢光灯などの光に
よる変色を軽減させるため、優れた耐光性も強く求めら
れている。In addition, with the spread of office equipment such as computers and facsimiles in recent years, in addition to flame retardancy and impact resistance, there is a strong demand for excellent light resistance in order to reduce discoloration caused by light such as fluorescent lights.
従来、耐久性や耐候性を改良するためにハロゲン含有芳
香族ジオールのエーテル誘導体をＡＢＳ樹脂等のスチレ
ン系樹脂に配合することは公知である。特開昭５０−２
７８４３号公報には、ハロゲン含有芳香族ジオールのエ
ーテル誘導体をＡＢＳ樹脂に用いる場合には、物性低下
が比較的小さく、耐久性に富むＨ燃剤となることが示さ
れている。又、特開昭６１−２１１３５４号公報には、
ハロゲン含有芳香族ジオールのエーテル誘導体及び他の
ハロゲン含有化合物をＡＢＳ樹脂に配合し、耐衝撃性と
耐熱性に優れ、良好な熱安定性と耐候性及び高度の難燃
性を有するスチレン系樹脂組成物を得ることが示されて
いる。BACKGROUND ART Conventionally, it has been known to blend ether derivatives of halogen-containing aromatic diols into styrenic resins such as ABS resins in order to improve durability and weather resistance. Unexamined Japanese Patent Application 1975-2
Publication No. 7843 discloses that when an ether derivative of a halogen-containing aromatic diol is used in an ABS resin, the deterioration in physical properties is relatively small and a highly durable H fuel agent is obtained. Also, in Japanese Patent Application Laid-open No. 61-211354,
A styrenic resin composition containing an ether derivative of a halogen-containing aromatic diol and other halogen-containing compounds and having excellent impact resistance and heat resistance, good thermal stability and weather resistance, and a high degree of flame retardancy. It has been shown to get things.
しかしながら、ＡＢＳ樹脂にハロケン含有芳香族ジオー
ルのエーテル誘導体を難燃剤として用いた場合、耐候性
あるいは耐光性が改良されても、ＡＢＳ＋Ｈ脂との相溶
性あるいは分散性が悪いために耐衝撃性が低下し、必要
な衝撃強度を得ようとすると、ゴム含有量を多くせねば
ならず、そのために熱安定性、流動性、剛性、更には難
燃性が損なわれ、ただ単にハロゲン含有芳香族ジオール
のエーテル誘導体をＡＢＳ樹脂に配合しただけでは、優
れた品質バランスを有する難燃性ＡＢＳ樹脂組成物を得
るのは極めて困難なのが実情であった。However, when an ether derivative of an aromatic diol containing a halokene is used as a flame retardant in ABS resin, even if the weather resistance or light resistance is improved, the impact resistance decreases due to poor compatibility or dispersibility with ABS+H resin. However, in order to obtain the necessary impact strength, the rubber content must be increased, which impairs thermal stability, fluidity, rigidity, and even flame retardancy, and simply reduces the effectiveness of halogen-containing aromatic diols. The reality is that it is extremely difficult to obtain a flame-retardant ABS resin composition with an excellent quality balance simply by blending an ether derivative with an ABS resin.
本発明者らは、かかる状況に鑑み、耐衝撃性を良好に保
持し、しかも優れた耐光性とＨ燃性を有する樹脂組成物
を得るべく鋭意検討した結果、特定の組成を有する樹脂
組成物に特定の構造のハロゲン含有化合物を配合するこ
とにより達成されることを見いだし、本発明を成すに至
った。In view of this situation, the present inventors conducted extensive studies to obtain a resin composition that maintains good impact resistance, and also has excellent light resistance and H flammability, and as a result, a resin composition having a specific composition. It was discovered that this can be achieved by blending a halogen-containing compound with a specific structure, and the present invention was completed.
即ち、本発明は、ゴム状物質の存在下、モノビニル芳香
族単量体及び不飽和ニトリル単量体を重合させてなる樹
脂組成物であって、ゴム状物質含有量が８〜２４重量％
であり、モノビニル芳香族化合物単位及び不飽和ニトリ
ル化合物単位からなる共重合体含有量が７６〜９２重量
％であって、かつ、該共重合体中の不飽和ニトリル化合
物単位の割合が２０〜２７重量％である樹脂組成物（Ａ
） １００重量部及び式（２）
（Ｘは、臭素又は塩素、ａ、ｂ、ｃ及びｄは、１〜４の
自然数、ｎは自然数である。）
で表され、８０〜１１０°Ｃの軟化点を有し、両末端に
エポキシ基を有するハロゲン含有化合物（Ｂ）１２〜２
６重量部とからなる離燃性樹脂組成物に関するものであ
る。That is, the present invention provides a resin composition obtained by polymerizing a monovinyl aromatic monomer and an unsaturated nitrile monomer in the presence of a rubbery substance, the resin composition having a rubbery substance content of 8 to 24% by weight.
and the content of the copolymer consisting of monovinyl aromatic compound units and unsaturated nitrile compound units is 76 to 92% by weight, and the proportion of unsaturated nitrile compound units in the copolymer is 20 to 27%. Resin composition (A
) 100 parts by weight and formula (2) (X is bromine or chlorine, a, b, c and d are natural numbers of 1 to 4, n is a natural number), and softening at 80 to 110 °C Halogen-containing compound (B) 12-2 having a dot and an epoxy group at both ends
6 parts by weight of the flame retardant resin composition.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明におけるモノビニル芳香族単量体とは、スチレン
、α−メチルスチレンのようなα−置換スチレン、ビニ
ルトルエン、ｍ−クロルスチレン、ｐ−クロルスチレン
、ｐ−メチルスチレンのような核置換スチレンなどを云
い、これらの１種又は２種以上が用いられる。スチレン
が最も好ましい。The monovinyl aromatic monomer in the present invention includes styrene, α-substituted styrene such as α-methylstyrene, vinyltoluene, nuclear substituted styrene such as m-chlorostyrene, p-chlorostyrene, p-methylstyrene, etc. One or more of these may be used. Styrene is most preferred.
本発明における不飽和ニトリル単量体としては、アクリ
ロニトリル、メタクリロニトリルなどが挙げられ、アク
リロニトリルが好適に用いられる。Examples of the unsaturated nitrile monomer in the present invention include acrylonitrile and methacrylonitrile, with acrylonitrile being preferably used.
モノビニル芳香族化合物単位及び不飽和具ｌ−ＩＪル化
合物単位からなる共重合体中の不飽和具）−リル化合物
単位の割合は２０〜２７重量％であることが必要であり
、好ましくは２２〜２５重量％である。−般にＡＢＳ樹
脂では、アクリロニトリル含有量が多いほど耐衝撃性や
機械特性が優れることが知られているが、意外にも本発
明では、特定のハロゲン含有化合物を配合した場合、不
飽和ニトリル化合物単位の割合が比較的低い２０〜２７
重量％で最も衝撃強度が高くなることを見いだした。即
ち、不飽和二） ＩＪル化合物単位が２７重量％より多
いと衝撃強度が低下する。又、２０重量％より少なくて
も同様に衝撃強度は低下する。その理由は明らかではな
いが、特定の樹脂組成物（Ａ）と特定のハロゲン含有化
合物（Ｂ）との相溶性が関係しているものと推測される
。The proportion of unsaturated compound units in the copolymer consisting of monovinyl aromatic compound units and unsaturated compound units must be 20 to 27% by weight, preferably 22 to 27% by weight. It is 25% by weight. - Generally, it is known that the higher the acrylonitrile content in ABS resin, the better the impact resistance and mechanical properties, but surprisingly, in the present invention, when a specific halogen-containing compound is blended, unsaturated nitrile compounds relatively low proportion of units 20-27
It has been found that the impact strength is highest at the weight percentage. That is, if the unsaturated compound unit is more than 27% by weight, the impact strength decreases. Furthermore, if the amount is less than 20% by weight, the impact strength will similarly decrease. Although the reason is not clear, it is presumed that it is related to the compatibility between the specific resin composition (A) and the specific halogen-containing compound (B).
本発明のゴム状物質としては、天然ゴム、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、ポリクロロプレン、アクリルゴ
ム、エチレン−プロピレンゴム、エチレン−プロピレン
−ジエンモノマーゴム、エチレン−酢酸ビニル共重合体
等が含まれる。The rubbery substances of the present invention include natural rubber, polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, polychloroprene, acrylic rubber, ethylene-propylene rubber, ethylene-propylene-diene monomer rubber, and ethylene-acetic acid. Includes vinyl copolymers, etc.
樹脂組成物（Ａ）中のモノビニル芳香族化合物単位及び
不飽和二） ＩＪル化合物単位からなる共重合体含有量
が７６〜９２重量％であるのに対し、ゴム状物質含有量
は８〜２４重量％であることが必要である。ゴム状物質
含有量が８重量％より少ないと衝撃強度が低下し、２４
重量％より多いと難燃性、耐光性、流動性、肩１１性、
熱安定性などの特性が低下し、本発明のバランスの優れ
た難燃性樹脂組成物を得ることができない。The content of the copolymer consisting of monovinyl aromatic compound units and unsaturated IJ compound units in the resin composition (A) is 76 to 92% by weight, while the rubbery substance content is 8 to 24% by weight. It is necessary that the amount is % by weight. When the rubbery substance content is less than 8% by weight, the impact strength decreases, and 24
If it is more than % by weight, flame retardancy, light resistance, fluidity, shoulder 11 properties,
Properties such as thermal stability deteriorate, making it impossible to obtain the well-balanced flame-retardant resin composition of the present invention.
樹脂組成物（Ａ）は、通常の乳化重合、塊状重合、塊状
−懸濁重合などで製造することができる。The resin composition (A) can be produced by conventional emulsion polymerization, bulk polymerization, bulk-suspension polymerization, etc.
又、必要に応じて、別に製造したゴム状物質を含まない
モノビニル芳香族単量体と不飽和ニトリル単量体の共重
合体を混合しても良い。Further, if necessary, a copolymer of a monovinyl aromatic monomer and an unsaturated nitrile monomer which does not contain a rubbery substance and is produced separately may be mixed.
ゴム状物質含有量や共重合体中の不飽和ニトリル化合物
単位の割合は、通常行われる方法、例えば赤外分光光度
針を用いて測定できる。The rubbery substance content and the proportion of unsaturated nitrile compound units in the copolymer can be measured by a commonly used method, for example, using an infrared spectrophotometric needle.
本発明における両末端にエポキシ基を有するハロゲン含
有化合物は一般的に次の式で表される。The halogen-containing compound having epoxy groups at both ends in the present invention is generally represented by the following formula.
上記式中、Ｘば臭素又は塩素、ａ ％ ｂ 、ｃ及びｄ
は、１〜４の自然数、ｎは自然数である。In the above formula, X is bromine or chlorine, a% b, c and d
is a natural number from 1 to 4, and n is a natural number.
両末端にエポキシ基を有するハロゲン含有化合物の軟化
点は、８０〜１１０°Ｃの範囲になければならない。軟
化点が８０°Ｃより低いとｎ燃樹脂組成物の耐熱性が劣
り、１１０°Ｃより高いと耐光性及び耐衝撃性が低下す
る。軟化点が８０〜１１０℃の範囲にあれば、−紋穴の
繰り返し数ｎの値の異なるもの２種以上の混合物を用い
ても差支えない。The softening point of the halogen-containing compound having epoxy groups at both ends must be in the range of 80-110°C. If the softening point is lower than 80°C, the heat resistance of the n-flame resin composition will be poor, and if it is higher than 110°C, the light resistance and impact resistance will be reduced. As long as the softening point is in the range of 80 to 110°C, a mixture of two or more types having different values of the number n of repeated holes may be used.
両末端にエポキシ基を有するハロゲン含有化合物（Ｂ）
は樹脂組成物（Ａ） １００重量部に対し、１２〜２６
重量部配合される。１２重量部より少ないと必要な難燃
性を得ることができず、２６重量部を超えると経済的に
不利であるだけでなく、耐衝撃性が著しく低下する。Halogen-containing compound (B) having epoxy groups at both ends
is 12 to 26 parts by weight based on 100 parts by weight of the resin composition (A).
Parts by weight are added. If it is less than 12 parts by weight, the necessary flame retardancy cannot be obtained, and if it exceeds 26 parts by weight, it is not only economically disadvantageous, but also the impact resistance is significantly reduced.
両末端にエポキシ基を有するハロゲン含有化合物は、含
ハロゲンビスフェノール八と含ハロゲンビスフェノール
Ａ型エポキシ樹脂の反応生成物として得られる。又は、
含ハロゲンビスフェノールＡとエビハロヒドリンとの反
応生成物として得られる。The halogen-containing compound having epoxy groups at both ends is obtained as a reaction product of halogen-containing bisphenol 8 and halogen-containing bisphenol A-type epoxy resin. Or
It is obtained as a reaction product of halogen-containing bisphenol A and shrimp halohydrin.
含ハロゲンビスフェノールＡの例としては、テトラブロ
モビスフェノールＡ１ジクロロビスフエノールＡ、テト
ラクロロビスフェノールＡ１ジブロモビスフェノールＡ
等がある。又、含ハロゲンビスフェノールＡ型エポキシ
樹脂の具体例としては、テトラブロモビスフェノールへ
のジグリシジルエーテル、テトラクロロビスフェノール
Ａのジグリシジルエーテル、ジクロロビスフェノールへ
のジグリシジルエーテル、ジブロモビスフェノールＡの
ジグリシジルエーテル等がある。特に好ましくは、テト
ラブロモビスフェノールＡとテトラブロモビスフェノー
ルＡのジグリンジルエーテルとの反応生成物、或いはテ
トラブロモビスフェノールＡとエピクロルヒドリンとの
反応生成物であり、式中の繰返し数ｎが２のものである
。Examples of halogen-containing bisphenol A include tetrabromobisphenol A1 dichlorobisphenol A, tetrachlorobisphenol A1 dibromobisphenol A
etc. Further, specific examples of halogen-containing bisphenol A type epoxy resins include diglycidyl ether of tetrabromobisphenol, diglycidyl ether of tetrachlorobisphenol A, diglycidyl ether of dichlorobisphenol, diglycidyl ether of dibromobisphenol A, etc. be. Particularly preferred are the reaction products of tetrabromobisphenol A and diglyndyl ether of tetrabromobisphenol A, or the reaction products of tetrabromobisphenol A and epichlorohydrin, where the number of repeats n in the formula is 2. .
両末端にエポキシ基を有するハロゲン含有化合物（Ｂ）
の軟化点は、環球法による固形樹脂の軟化点を云い、Ｊ
ＩＳ Ｋ ２５３１に基づいて測定される。Halogen-containing compound (B) having epoxy groups at both ends
The softening point of J
Measured according to IS K 2531.
本発明では、前記の樹脂組成物（Ａ）と両末端にエポキ
シ基を有するハロゲン含有化合物（Ｂ）の両方が組み合
わされて始めて耐光性、耐衝撃性の優れた難燃性樹脂組
成物が得られるのであって、どちらか一つだけでは本発
明は達成されない。In the present invention, a flame-retardant resin composition with excellent light resistance and impact resistance can only be obtained by combining both the resin composition (A) and the halogen-containing compound (B) having epoxy groups at both ends. However, the present invention cannot be achieved by using either one alone.
本発明の難燃性樹脂組成物の製造方法は、樹脂組成物（
Ａ）に両末端にエポキシ基を有するハロゲン含有化合物
（Ｂ）を配合することによる。配合方法は特に制限がな
く、タンブラ−ミキサー、スーパーミキサー、バンバリ
ーミキサ−、ニーダ−、ロール、単軸押出機、二軸押出
機等の方法がある。The method for producing a flame-retardant resin composition of the present invention includes a method for producing a flame-retardant resin composition (
By blending A) with a halogen-containing compound (B) having epoxy groups at both ends. The blending method is not particularly limited, and methods such as a tumbler mixer, super mixer, Banbury mixer, kneader, roll, single-screw extruder, and twin-screw extruder are available.
本発明組成物には必要に応じて本発明の目的を損なわな
い範囲で他の難燃剤や添加剤を添加できる。他のＨ燃剤
としては、三酸化アンチモンがあり、樹脂組成物（Ａ）
１００重量部に対し、３〜１０重量部使用される。又
、塩素化ポリエチレンも同様に用いることができ、２〜
１２重量部の範囲で使用される。各種添加剤として、可
塑剤、滑剤、安定剤、紫外線吸収剤、充填剤、補強剤、
着色剤等が添加できる。Other flame retardants and additives can be added to the composition of the present invention, as necessary, within a range that does not impair the purpose of the present invention. Other H refueling agents include antimony trioxide, and resin composition (A)
It is used in an amount of 3 to 10 parts by weight per 100 parts by weight. In addition, chlorinated polyethylene can also be used in the same way, and 2-
It is used in a range of 12 parts by weight. Various additives include plasticizers, lubricants, stabilizers, ultraviolet absorbers, fillers, reinforcing agents,
Colorants etc. can be added.
本発明の難燃性樹脂組成物は、良好な耐光性を有してい
ながら耐衝撃性に優れた難燃性樹脂組成物であり、工業
材料特に事務機器、電気機器のハウジング材として産業
上極めて有用である。The flame-retardant resin composition of the present invention is a flame-retardant resin composition that has good light resistance and excellent impact resistance, and is industrially extremely useful as an industrial material, particularly as a housing material for office equipment and electrical equipment. Useful.
以下に、実施例及び比較例を挙げて本発明を説明する。 The present invention will be explained below with reference to Examples and Comparative Examples.
難燃性樹脂組成物の評価は次に示す方法で行った。メル
トフローレートの試験にはベレットを用い、その他の試
験には射出成形試験片を用いた。Evaluation of the flame-retardant resin composition was performed by the following method. A pellet was used for the melt flow rate test, and injection molded specimens were used for the other tests.
アイゾ・ ドパ： ＡＳＴＭ Ｄ２５６ 、試験片厚さ
６．４ｍｍ 、ノツチ付、
■服孜嘉、俺グ： ＡＳＴＭ Ｄ６３８による。Izo-Dopa: ASTM D256, test piece thickness 6.4 mm, with notch, ■Takayoshi Fuku, Oregu: According to ASTM D638.
メルトフローレート： ＩＳＯＲ１１３３、ａ度２００
°Ｃ１荷重５Ｋｇ、
加ｌ■」后１度： ＡＳＴＭ ０６４８ 、試験片厚さ
６ 、４ｍｍ、アニール無し、曲げ応力１８．６Ｋｇ／
ｃｎ、旦太仕：キセノンアークウェザーオメータの２０
０時間後の試験片の変色度合を色差計で測定し、未曝露
サンプルとの差ΔＥで表す、盟盛性：ＵＬ９４、試験片
厚さ１／８．１／１２インチ、Ｖ−Ｏランクを判定する
。Melt flow rate: ISOR1133, a degree 200
°C1 load 5Kg, 1 degree after applying: ASTM 0648, specimen thickness 6, 4mm, no annealing, bending stress 18.6Kg/
cn, tantaishi: xenon arc weather meter 20
The degree of discoloration of the test piece after 0 hours was measured with a color difference meter, and expressed as the difference ΔE from the unexposed sample. judge.
（ＡＢＳ樹脂の重合例）
重合例１
平均粒子径３０００λのポリブダジエンラテソクス、ス
チレン、アクリロニトリルの他、通常用いられる連鎖移
動剤、乳化剤、イオン交換水を用いて、常法により乳化
重合して第１表に示すＡ−１からＡ−７までのＡＢＳ樹
脂を得た。共重合体中のアクリロニトリル（ＡＮ）単位
の割合及びＡＢＳ樹脂中のゴム状物質含有量は、それぞ
れ第１表に示す通りであった。上記により得られたＡＢ
Ｓ樹脂を実施例に５及び比較例１〜９に用いた。(Polymerization example of ABS resin) Polymerization example 1 Polybutadiene latex having an average particle size of 3000λ, styrene, acrylonitrile, and a commonly used chain transfer agent, emulsifier, and ion-exchanged water were used to carry out emulsion polymerization in a conventional manner. ABS resins A-1 to A-7 shown in Table 1 were obtained. The proportion of acrylonitrile (AN) units in the copolymer and the rubbery substance content in the ABS resin were as shown in Table 1, respectively. AB obtained above
S resin was used in Example 5 and Comparative Examples 1 to 9.
第１表
（ハロゲン含有化合物の性状）
実施例１〜５及び比較例１〜１０に用いたハロゲン含有
化合物の性状を第２表に示す。Ｂ−１〜Ｂ−５は、テト
ラブロモビスフェノールＡとテトラビスフェノールＡの
ジグリシジルエーテルから合成され、両末端にエポキシ
基を有している構造をしている。又、Ｂ−６はテトラブ
ロモビスフェノールＡとテトラビスフェノールＡのジグ
リシジルエーテルから合成されるが、両末端には水酸基
を有した構造をしている。Ｂ−７はテトラブロモビスフ
ェノールＡである。以下にそれぞれの構造式％式％：
Ｂ−６＝
第２表
実施例Ｉ
Ａ、ＢＳ樹脂Ａ−３、ハロゲン含有化合物Ｂ−３、その
他を以下に示す配合割合でドラムブレンダーで混合後、
４０ｍｍφベント付二軸押出機で２１０’ｃで混練し、
ベレット化した。Table 1 (Properties of halogen-containing compounds) Table 2 shows the properties of the halogen-containing compounds used in Examples 1 to 5 and Comparative Examples 1 to 10. B-1 to B-5 are synthesized from tetrabromobisphenol A and diglycidyl ether of tetrabisphenol A, and have an epoxy group at both ends. Further, B-6 is synthesized from tetrabromobisphenol A and diglycidyl ether of tetrabisphenol A, and has a structure having hydroxyl groups at both ends. B-7 is tetrabromobisphenol A. Each structural formula % formula % is shown below: B-6 = Table 2 Example I After mixing A, BS resin A-3, halogen-containing compound B-3, and others in a drum blender in the proportions shown below,
Kneaded at 210'c in a 40mmφ vented twin-screw extruder,
Made into a beret.
重量部
ＡＢＳ樹脂（Ａ−３） １００ハ
ロゲン含有化合物（Ｂ−３） １８三酸
化アンチモン ６塩素化ポリ
エチレン ８錫系熱安定剤
０．５エチレンビスステアロ
アミド ０．４得られたペレットは、シリ
ンダー温度２２０℃、金型温度６０℃で射出成形し、各
種の物性を測定した。その結果を第３表に示す。Part by weight ABS resin (A-3) 100 Halogen-containing compound (B-3) 18 Antimony trioxide 6 Chlorinated polyethylene 8 Tin-based heat stabilizer
0.5 Ethylene bisstearamide 0.4 The obtained pellets were injection molded at a cylinder temperature of 220°C and a mold temperature of 60°C, and various physical properties were measured. The results are shown in Table 3.
実施例２〜５及び比較例１〜９
第３表及び第４表に示すようなＡＢＳ樹脂、ハロゲン含
有化合物、及び配合割合にした他は、実施例１と同様に
行った。それらの結果を第３表及び第４表に示す。Examples 2 to 5 and Comparative Examples 1 to 9 The same procedure as in Example 1 was conducted except that the ABS resin, halogen-containing compound, and blending ratio were as shown in Tables 3 and 4. The results are shown in Tables 3 and 4.
Claims (1)
び不飽和ニトリル単量体を重合させてなる樹脂組成物で
あって、ゴム状物質含有量が８〜２４重量％であり、モ
ノビニル芳香族化合物単位及び不飽和ニトリル化合物単
位からなる共重合体含有量が７６〜９２重量％であって
、かつ、該共重合体中の不飽和ニトリル化合物単位の割
合が２０〜２７重量％である樹脂組成物（Ａ）１００重
量部及び式（２）▲数式、化学式、表等があります▼ （Ｘは、臭素又は塩素、ａ、ｂ、ｃ及びｄは、１〜４の
自然数、ｎは自然数である。） で表され、８０〜１１０℃の軟化点を有し、両末端にエ
ポキシ基を有するハロゲン含有化合物（Ｂ）１２〜２６
重量部とからなる難燃性樹脂組成物。(1) A resin composition obtained by polymerizing a monovinyl aromatic monomer and an unsaturated nitrile monomer in the presence of a rubbery substance, in which the rubbery substance content is 8 to 24% by weight, and the monovinyl The content of a copolymer consisting of aromatic compound units and unsaturated nitrile compound units is 76 to 92% by weight, and the proportion of unsaturated nitrile compound units in the copolymer is 20 to 27% by weight. 100 parts by weight of resin composition (A) and formula (2) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (X is bromine or chlorine, a, b, c and d are natural numbers from 1 to 4, n is a natural number ), has a softening point of 80 to 110°C, and has an epoxy group at both ends (B) 12 to 26
A flame retardant resin composition consisting of parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63116836A JPH0735464B2 (en) | 1988-05-16 | 1988-05-16 | Flame-retardant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63116836A JPH0735464B2 (en) | 1988-05-16 | 1988-05-16 | Flame-retardant resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01287132A true JPH01287132A (en) | 1989-11-17 |
| JPH0735464B2 JPH0735464B2 (en) | 1995-04-19 |
Family
ID=14696826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63116836A Expired - Lifetime JPH0735464B2 (en) | 1988-05-16 | 1988-05-16 | Flame-retardant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0735464B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8067497B2 (en) | 2003-01-13 | 2011-11-29 | Bromine Compounds Ltd. | Flame-retardant for engineering thermoplastic applications |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5311017A (en) * | 1976-07-19 | 1978-02-01 | Mitsubishi Chem Ind | Foam photosensitive element |
| JPS5838746A (en) * | 1981-09-01 | 1983-03-07 | Denki Kagaku Kogyo Kk | Flame-retardant abs resin composition |
| JPS59166552A (en) * | 1983-03-11 | 1984-09-19 | Japan Synthetic Rubber Co Ltd | Self-extinguishing resin composition |
| JPS59196310A (en) * | 1983-04-22 | 1984-11-07 | Japan Synthetic Rubber Co Ltd | Thermoplastic resin composition |
| JPS60147462A (en) * | 1984-01-12 | 1985-08-03 | Japan Synthetic Rubber Co Ltd | Self-extinguishable resin composition |
| JPS6131451A (en) * | 1984-07-25 | 1986-02-13 | Japan Synthetic Rubber Co Ltd | Flame-retardant resin composition |
| JPS61241322A (en) * | 1986-04-04 | 1986-10-27 | Asahi Chem Ind Co Ltd | Flame-retardant for synthetic resin |
| JPS6372749A (en) * | 1986-09-16 | 1988-04-02 | Hitachi Chem Co Ltd | Flame-retardant resin composition |
| JPH01101350A (en) * | 1987-10-14 | 1989-04-19 | Dainippon Ink & Chem Inc | Flame-retardant resin composition |
| JPH01198655A (en) * | 1988-02-03 | 1989-08-10 | Sumitomo Naugatuck Co Ltd | Flame-retardant resin composition having excellent color-developing property and thermal stability |
-
1988
- 1988-05-16 JP JP63116836A patent/JPH0735464B2/en not_active Expired - Lifetime
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5311017A (en) * | 1976-07-19 | 1978-02-01 | Mitsubishi Chem Ind | Foam photosensitive element |
| JPS5838746A (en) * | 1981-09-01 | 1983-03-07 | Denki Kagaku Kogyo Kk | Flame-retardant abs resin composition |
| JPS59166552A (en) * | 1983-03-11 | 1984-09-19 | Japan Synthetic Rubber Co Ltd | Self-extinguishing resin composition |
| JPS59196310A (en) * | 1983-04-22 | 1984-11-07 | Japan Synthetic Rubber Co Ltd | Thermoplastic resin composition |
| JPS60147462A (en) * | 1984-01-12 | 1985-08-03 | Japan Synthetic Rubber Co Ltd | Self-extinguishable resin composition |
| JPS6131451A (en) * | 1984-07-25 | 1986-02-13 | Japan Synthetic Rubber Co Ltd | Flame-retardant resin composition |
| JPS61241322A (en) * | 1986-04-04 | 1986-10-27 | Asahi Chem Ind Co Ltd | Flame-retardant for synthetic resin |
| JPS6372749A (en) * | 1986-09-16 | 1988-04-02 | Hitachi Chem Co Ltd | Flame-retardant resin composition |
| JPH01101350A (en) * | 1987-10-14 | 1989-04-19 | Dainippon Ink & Chem Inc | Flame-retardant resin composition |
| JPH01198655A (en) * | 1988-02-03 | 1989-08-10 | Sumitomo Naugatuck Co Ltd | Flame-retardant resin composition having excellent color-developing property and thermal stability |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8067497B2 (en) | 2003-01-13 | 2011-11-29 | Bromine Compounds Ltd. | Flame-retardant for engineering thermoplastic applications |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0735464B2 (en) | 1995-04-19 |
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