JP3572488B2 - Flame retardant styrenic resin composition - Google Patents
Flame retardant styrenic resin composition Download PDFInfo
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- JP3572488B2 JP3572488B2 JP20238894A JP20238894A JP3572488B2 JP 3572488 B2 JP3572488 B2 JP 3572488B2 JP 20238894 A JP20238894 A JP 20238894A JP 20238894 A JP20238894 A JP 20238894A JP 3572488 B2 JP3572488 B2 JP 3572488B2
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- Prior art keywords
- epoxy resin
- halogenated
- alkyl glycidyl
- flame
- resin
- Prior art date
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 32
- 239000003063 flame retardant Substances 0.000 title claims description 32
- 239000011342 resin composition Substances 0.000 title claims description 15
- 229920001890 Novodur Polymers 0.000 title claims description 11
- 239000003822 epoxy resin Substances 0.000 claims description 61
- 229920000647 polyepoxide Polymers 0.000 claims description 61
- -1 alkyl glycidyl ether compound Chemical class 0.000 claims description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 150000002989 phenols Chemical class 0.000 claims description 12
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229920005990 polystyrene resin Polymers 0.000 claims description 6
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-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 8
- 238000000034 method Methods 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 6
- 230000000694 effects Effects 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 5
- 229920005669 high impact polystyrene Polymers 0.000 description 4
- 239000004797 high-impact polystyrene Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 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 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- CABDEMAGSHRORS-UHFFFAOYSA-N oxirane;hydrate Chemical compound O.C1CO1 CABDEMAGSHRORS-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- FNAKEOXYWBWIRT-UHFFFAOYSA-N 2,3-dibromophenol Chemical compound OC1=CC=CC(Br)=C1Br FNAKEOXYWBWIRT-UHFFFAOYSA-N 0.000 description 1
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 1
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 description 1
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- GPLIMIJPIZGPIF-UHFFFAOYSA-N 2-hydroxy-1,4-benzoquinone Chemical compound OC1=CC(=O)C=CC1=O GPLIMIJPIZGPIF-UHFFFAOYSA-N 0.000 description 1
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 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
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005055 alkyl alkoxy group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、難燃性スチレン系樹脂組成物に関し、高度の難燃性と共に耐光性、耐熱性、流動性に優れ、及び押出機や射出成形機のスクリュ−、シリンダ−、金型などに対する付着性を低減する難燃性スチレン系樹脂組成物に関するものである。
【０００２】
【従来の技術】
ハイインパックトポリスチレン（ＨＩＰＳ）、ＡＢＳなどスチレン系樹脂は機械特性がよく、電気絶縁性、成形加工性に優れている。近年、ＯＡ機器や家電製品のハウジング、自動車部品など多用されている。しかし、スチレン系樹脂は易燃性であるため、安全面から難燃化が要求されている。さらにＯＡ機器、家電製品などの分野では、室内で使用されるが、蛍光灯や外から入る光にさらされるため、耐光性が重視されている。
【０００３】
従来より、スチレン系樹脂に難燃性を付与するため、種々のハロゲン化有機化合物が提案されている。代表的にはテトラブロモビスフェノ−ルＡ（ＴＢＡ）やデカブロモジフェニルエ−テル（ＤＢＤＰＥ）や臭素化エポキシ樹脂、及びこの臭素化エポキシ樹脂のエポキシ基をトリブロモフェノ−ル（ＴＢＰ）で封鎖したものなどが知られている。特に前の二者が安価なため、多く用いられている。
しかし、ＴＢＡはスチレン系樹脂と配合した場合、耐熱性と耐光性を大幅に低下させる欠点があり、ＤＢＤＰＥ及びＴＢＰで封鎖したエポキシ樹脂は耐光性を低下させる欠点がある。また、臭素化エポキシ樹脂では、溶融混練時の押出機や成形時の射出成形機等のスクリュ−に対し、付着性を有するため、連続生産を行うと、付着物が長時間に渡って高温にさらされ、変色劣化してしまい、異物としてコンパウンドや成形品に混入してしまうという欠点があった。
【０００４】
【発明が解決しょうとする問題点】
本発明者らは鋭意研究の結果、ハロゲン化エポキシ樹脂、特に臭素化エポキシ樹脂にアルキルグリシジルエ−テル及び／又はアルキルグリシジルエ−テルとフェノ−ル類との反応物、もしくはアルキルグリシジルエ−テルとエポキシ樹脂中のフェノ−ル末端との反応物を含有させたものは、スチレン系樹脂の難燃剤として極めて有効であることを見出し、本発明を完成したもので、本発明は高度の難燃性と共に、耐光性、耐熱性、流動性に優れ、及び押出機や射出成形機のスクリュ−、シリンダ−、金型等の金属部分に対する付着性を低減した難燃性スチレン系樹脂組成物を提供することを目的とする。
【０００５】
【問題点を解決するための手段】
本発明の要旨は、ポリスチレン系樹脂（Ａ）と、炭素数が１８個のアルキルグリシジルエ−テル化合物を含有するハロゲン化エポキシ系樹脂（Ｂ）とからなることを特徴とする難燃性スチレン系樹脂組成物である。
即ち、本発明は炭素数が１８個のアルキルグリシジルエ−テル化合物を含有するハロゲン化エポキシ系樹脂（Ｂ）を使用することによってポリスチレン系樹脂（Ａ）を難燃化するものであって、その配合量としては、ポリスチレン系樹脂１００重量部に対して、炭素数が１８個のアルキルグリシジルエ−テル化合物を含有するハロゲン化エポキシ樹脂（Ｂ）１０〜５０重量部である。
更に必要に応じて難燃助剤を併用することが好ましく、１〜１０重量部程度を含有させることが好ましい。更に、必要に応じて臭素化エポキシ樹脂のエポキシ基をハロゲン化フェノ−ル類で封鎖した化合物と他の添加剤とを併用することが好ましい。
【０００６】
以下、本発明を更に詳細に説明する。
本発明に用いるポリスチレン系樹脂とはスチレン、α−メチルスチレン、ビニルトルエン、ｏ−クロロスチレン等のスチレン化合物の単独重合体又は共重合体、必要に応じてこれらの単量体とアクリロニトリル、ポリブタジエンゴム等のアクリレ−ト系共重合体、マレイミド、Ｎ−フェニルマレイミド等のマレイミド系共重合体などが挙げられる。代表的にはポリスチレン、ＨＩＰＳ（耐衝撃性ポリスチレン系樹脂）、ＡＳ樹脂、ＡＢＳ樹脂、ＡＥＳ樹脂、ＭＢＳ樹脂などがある。更に、これらポリスチレン系樹脂を含有するポリマ−アロイなどを挙げることができる。
【０００７】
本発明において使用する難燃剤は炭素数が１８個のアルキルグリシジルエ−テル化合物を含有するハロゲン化エポキシ系樹脂（Ｂ）である。
アルキルグリシジルエ−テル化合物を含有するハロゲン化エポキシ系樹脂（Ｂ）とは：−−
（１）ハロゲン化エポキシ系樹脂とアルキルグリシジルエ−テル化合物との混合物、
（２）ハロゲン化エポキシ系樹脂又はハロゲン化ビスフェノ−ルと、エピハロヒドリンと、アルキルグリシジルエ−テル化合物の反応生成物、又は該反応生成物とハロゲン化エポキシ系樹脂との混合物、
（３）アルキルグリシジルエ−テル化合物とフェノ−ル類の付加物及びこれとハロゲン化エポキシ系樹脂の混合物
の何れであってもよい。
そして、ハロゲン化エポキシ系樹脂については、必要に応じて、例えばブロミン含有量を高めるために、ハロゲン化エポキシ樹脂のエポキシ基の０〜６０％をハロゲン化フェノ−ル類で封鎖してもよい。又は、ハロゲン化エポキシ樹脂のエポキシ基を８０％以上に封鎖した化合物を０〜６０重量部と、炭素数１８個のアルキルグリシジルエ−テル化合物を含有するハロゲン化エポキシ樹脂１００〜４０重量部とを溶融混合してもよい。ハロゲン化フェノ−ル類で封鎖した構造を有するハロゲン化エポキシ樹脂の含有量は特に限定されるものではないが、６０重量部以下が好ましく、５０重量部以下は更に好ましい。６０重量部以上では耐光性が期待できない。
【０００８】
また、炭素数１８個のアルキルグリシジルエ−テル化合物とは炭素数１８個のアルキルグリシジルエ−テル、炭素数１８個のアルキルグリシジルエ−テルとフェノ−ル類との反応物及び炭素数１８個のアルキルグリシジルエ−テルとエポキシ樹脂中のフェノ−ル末端との反応物からなる群から選ばれた少なくとも一種をいうのであって、炭素数が１８個のアルキルグリシジルエ−テル化合物の含有量は特に限定される物ではないが、難燃剤全量の０．１〜１０重量部が好ましく、０．５〜８重量部がさらに好ましい。０．１重量部未満では金属に対する付着性の低減効果が期待できず、１０重量部を越えると難燃性樹脂組成物の難燃効果と熱変形温度が低下する傾向にあるからである。上記化合物には必要に応じて、他の離型剤や滑剤とを併用することもできる。
【０００９】
ここで用いるハロゲン化エポキシ系樹脂とは、ハロゲン化ビスフェノ−ル類とエピハロヒドリンとの反応生成物、ハロゲン化フェノ−ルノボラックとエピハロヒドリンとの反応生成物、又はこれらの反応生成物のハロゲン化エポキシ樹脂とハロゲン化ビスフェノ−ル類との付加反応物などが挙げられる。
ハロゲン化エポキシ樹脂の具体例としてはテトラクロロビスフェノ−ルＡのジグリシジルエ−テル、テトラブロモビスフェノ−ルＡのジグリシジルエ−テル、テトラブロモビスフェノ−ルＳのジグリシジルエ−テル、テトラクロロビスフェノ−ルＳのジグリシジルエ−テル、ジブロモフェノ−ルノボラックのポリグリシジルエ−テルなどを挙げることが出来る。
【００１０】
ハロゲン化エポキシ樹脂のエポキシ基を封鎖するハロゲン化フェノ−ル類とは２，４，６−トリブロモフェノ−ル、ジブロモフェノ−ル、モノブロモフェノ−ル、２，４，６−トリクロロフェノ−ル、ジクロロフェノ−ル、モノクロロフェノ−ルなどが挙げられる。
【００１２】
また、アルキルグリシジルエ−テルと反応し得る末端フェノ−ルのエポキシ樹脂とはビスフェノ−ル型エポキシ樹脂、ハロゲン化エポキシ樹脂、ヒドロキシキノン型エポキシ樹脂、ノボラック型エポキシ樹脂、オルソクレゾ−ル型エポキシ樹脂、ビフェニル型エポキシ樹脂、フルオレン型エポキシ樹脂、ナフタレン型エポキシ樹脂などのエポキシ樹脂の末端基の一部乃至全部がフェノ−ル基であるものを用いた。
また、アルキルグリシジルエ−テルと反応し得るフェノ−ル類とは、上記エポキシ樹脂の原料であるフェノ−ル類が挙げられる。もちろん、グリシジル基と反応し得る全般のフェノ−ルも使用可能である。
【００１３】
また、上記エポキシ樹脂のエポキシ基と炭素数１８個のアルキルアルコ−ルや、分岐アルキルアルコ−ルとの反応物も使用出来る。アルキルアルコ−ルとしてはオクタデシルアルコ−ル、などが挙げられる。
【００１４】
本発明に用いる難燃剤であるアルキルグリシジルエ−テル化合物を含有するハロゲン化エポキシ系樹脂の製造方法としては、ハロゲン化ビスフェノ−ル類とエピハロヒドリンとを水酸化アルカリ金属及び非反応性溶媒の存在下に、反応させて得られたハロゲン化エポキシ樹脂にアルキルグリシジルエ−テルを添加する方法、或いは低分子量ハロゲン化エポキシ樹脂とハロゲン化ビスフェノ−ル類とを触媒の存在下で８０℃〜２２０℃に加熱反応させ、得られた中高分子量ハロゲン化エポキシ樹脂にアルキルグリシジルエ−テルを添加する方法などがある。必要に応じて上記ハロゲン化エポキシ樹脂の６０％以下のエポキシ基をさらにハロゲン化フェノ−ルで封鎖してもよい。或いは、予めハロゲン化フェノ−ル類で封鎖したハロゲン化エポキシ樹脂を６０重量部以下で混合することもできる。
【００１５】
また、アルキルグリシジルエ−テル、又はアルキルアルコ−ルとハロゲン化ビスフェノ−ル類とエピハロヒドリンとを水酸化アルカリ金属及び非反応性溶媒の存在下に反応させて得られる方法、或いはアルキルグリシジルエ−テル、又はアルキルアルコ−ルとハロゲン化ビスフェノ−ル類とハロゲン化エポキシ樹脂とを触媒の存在下で反応させて得られる方法、或いはアルキルグリシジルエ−テルと前記末端フェノ−ル基のエポキシ樹脂類やエポキシ樹脂の原料フェノ−ル類とを予め触媒の存在下で反応させて得られた化合物を上記ハロゲン化エポキシ樹脂に添加する方法などがある。もちろん、必要に応じてハロゲン化フェノ−ル類で封鎖したハロゲン化エポキシ樹脂を添加することもできる。
【００１６】
反応触媒としては、水酸化アルカリ金属類、三級アミン類、イミタゾ−ル類、四級アモニウム塩類、ホスフィン類、ホスホニウム塩類などが知られている。難燃剤の製造方法は特に制限されるものではなく、公知の方法で容易に製造することが出来る。
【００１７】
上記スチレン系樹脂（Ａ）と本発明の難燃剤（Ｂ）とを配合したスチレン系樹脂組成物に難燃助剤（Ｃ）として、例えば三酸化アンチモン、五酸化アンチモン、酸化モリブテンなどを併用することにより難燃効果がより一層高められる。
更に、本発明の組成物には、必要に応じて、一般に使用されている紫外線吸収剤、酸化防止剤、滑剤、着色剤、離型剤、充填剤、染顔料などを添加することが出来る。
【００１８】
【実施例及び比較例】
以下、実施例及び比較例を挙げて、本発明の効果を更に具体的に説明するが、本発明の難燃剤の製造方法及び組成物の製造方法は特に限定されるものではない。また、例中の部及び％の表示はいずれも重量基準である。
【００１９】
各実施例における試験方法は次に記載する方法で行った。
試験方法
（１）エポキシ当量：ＪＩＳ Ｋ−７２３４
（２）軟化点：ＪＩＳ Ｋ−７２３６
（３）耐光性△Ｅ：サンシャインウェザ−メ−タ−を用いて、６３℃で４８時間曝露試験（雨なし）を行った。曝露前後の試験片の色差を色差計（東京電色社製）で測定した。
（４）燃焼性試験：ＵＬ−９４試験法に準拠した。
（５）付着性試験：金属製熱ロ−ルに於いて、第一ロ−ルを２００℃、第二ロ−ルを６０℃にそれぞれ設定し、試験片を第一ロ−ルに３分間軽く圧着後３分間作動させたのちに、試験片を引き剥がし、ロ−ルへの付着状態を観察した。
【００２０】
合成例１
エポキシ当量６５０ｇ／ｅｑ．のテトラブロモビスフェノ−ルＡ（以下ＴＢＡと略す）型のエポキシ樹脂ＹＤＢ−４０６（臭素含有量５０％、東都化成（株）製）９８０ｇを温度計、撹拌機、コンデンサ−の付いた１リットルセパラブルフラスコに入れ、内部を窒素ガス置換してから１５０℃に加熱溶融したのちに、オキシラン酸素含有量４．０％のアルキルグリシジルエ−テル（日本油脂（株）製エピオ−ルＳＫ、以下同様）を２０ｇ添加し、１時間撹拌してから混合物をステンレスバットに入れ、冷却、粉砕して、難燃剤−ａを得た。その性状を表１に示す。
【００２２】
合成例３
難燃剤−Ｉ、３５０ｇに、トリブロモフェノ−ルでエポキシ基を封鎖した臭素化エポキシ樹脂ＴＢ−６２（臭素含有量５８％、東都化成（株）製、以下ＴＢ−６２と略す）１５０ｇとを合成例１と同様に溶融ブレンドを行った。得られた難燃剤−ｃの性状を表１に示す。
【００２４】
合成例５
ＴＢＡ９０ｇとオキシラン酸素４．０％のアルキルグリシジルエ−テル１５ｇ及びＹＤ−４００、４００ｇとを合成例−２と同様に仕込み、窒素パ−ジしながら１６０℃で５時間反応させた。得られた難燃剤−ｅの性状を表１に示す。
【００２５】
合成例６
ＹＤＢ−４００、４００ｇとオクタデシルアルコ−ル１５ｇとＴＢＡ９０ｇとを仕込み合成例２と同様に反応を行った。得られた難燃剤−ｆの性状を表１に示す。
【００２７】
合成例９
ＹＤＢ−４０６、６５０ｇと２，４，６−トリブロモフェノ−ル１００ｇとを仕込み、合成例８と同様に反応を行なってから、オキシラン酸素４．０％のアルキルグリシジルエ−テル２３ｇをブレンドし、難燃剤−ｉとした。
合成例１０
ＹＤＢ−４０６、５００ｇとＴＢ−６２、５００ｇとを溶融ブレンドし、難燃剤−ｊとした。
【００２８】
実施例１、３、５、６、９及び比較例１〜３
合成例１、３、５、６、９より得られた難燃剤と合成例１０の難燃剤及びＹＤＢ−４０６、ＴＢ−６２をそれぞれ表２に示す組成で配合し、ヘンシェルミキサ−で混合した後に、二軸押出機（池貝ＰＣＭ−３０）にて、溶融混合し、コンパウンドを得た。得られたコンパウンドをさらに射出成形により試験片を作成した。この試験片を用いて燃焼性，付着性，耐光性を測定した。その結果を表２に示す。
【００２９】
【表１】
【表２】
【発明の効果】
本発明の難燃性スチレン系樹脂組成物に、難燃剤として、ハロゲン化エポキシ樹脂にアルキルグリシジルエ−テル、又はその化合物の導入により、優れた耐光性及び押出機や射出成型機のスクリュ−やシリンダ−部分に付着性の改善効果を発揮できると共に、連続生産性の向上に有用である。[0001]
[Industrial applications]
The present invention relates to a flame-retardant styrenic resin composition, which is highly flame-retardant and has excellent light resistance, heat resistance and fluidity, and adheres to screws, cylinders, dies and the like of extruders and injection molding machines. The present invention relates to a flame-retardant styrenic resin composition having reduced properties.
[0002]
[Prior art]
Styrene-based resins such as high-impact polystyrene (HIPS) and ABS have good mechanical properties, and are excellent in electrical insulation and moldability. 2. Description of the Related Art In recent years, OA equipment, housing of home electric appliances, automobile parts, and the like have been widely used. However, since styrene resins are flammable, flame retardancy is required for safety. Further, in fields such as OA equipment and home electric appliances, they are used indoors. However, since they are exposed to fluorescent lights and light entering from outside, light resistance is emphasized.
[0003]
Conventionally, various halogenated organic compounds have been proposed for imparting flame retardancy to styrene resins. Typically, tetrabromobisphenol A (TBA), decabromodiphenyl ether (DBDPE), a brominated epoxy resin, and the epoxy group of the brominated epoxy resin are blocked with tribromophenol (TBP). Are known. In particular, the former two are widely used because they are inexpensive.
However, when TBA is blended with a styrene-based resin, there is a drawback that heat resistance and light resistance are significantly reduced, and an epoxy resin blocked with DBDPE and TBP has a drawback that light resistance is reduced. In addition, since the brominated epoxy resin has an adhesive property to screws such as an extruder at the time of melt-kneading and an injection molding machine at the time of molding, if the continuous production is performed, the adhered substance may be exposed to a high temperature for a long time. Exposure causes discoloration and deterioration, and has the disadvantage of being mixed as foreign matter into compounds and molded products.
[0004]
[Problems to be solved by the invention]
As a result of intensive studies, the present inventors have found that alkyl glycidyl ethers and / or reactants of alkyl glycidyl ethers with phenols or alkyl glycidyl ethers are added to halogenated epoxy resins, especially brominated epoxy resins. It was found that a product containing a reaction product of styrene and a phenolic terminal in an epoxy resin was extremely effective as a flame retardant for a styrenic resin, and the present invention was completed. Provide flame-retardant styrene-based resin composition with excellent light resistance, heat resistance, and fluidity as well as reduced adhesion to metal parts such as screws, cylinders, dies and the like of extruders and injection molding machines. The purpose is to do.
[0005]
[Means for solving the problem]
The gist of the present invention is to provide a flame-retardant styrene resin comprising a polystyrene resin (A) and a halogenated epoxy resin (B) containing an alkyl glycidyl ether compound having 18 carbon atoms. It is a resin composition.
That is, the present invention makes the polystyrene resin (A) flame-retardant by using a halogenated epoxy resin (B) containing an alkyl glycidyl ether compound having 18 carbon atoms. The compounding amount is 10 to 50 parts by weight of a halogenated epoxy resin (B) containing an alkyl glycidyl ether compound having 18 carbon atoms with respect to 100 parts by weight of a polystyrene resin.
Further, it is preferable to use a flame retardant auxiliary as needed, and it is preferable to contain about 1 to 10 parts by weight. Further, if necessary, it is preferable to use a compound in which the epoxy group of the brominated epoxy resin is blocked with a halogenated phenol and another additive.
[0006]
Hereinafter, the present invention will be described in more detail.
The polystyrene resin used in the present invention is a homopolymer or a copolymer of a styrene compound such as styrene, α-methylstyrene, vinyltoluene and o-chlorostyrene, and if necessary, these monomers and acrylonitrile and polybutadiene rubber. And acrylate copolymers such as maleimide and maleimide copolymers such as N-phenylmaleimide. Typically, there are polystyrene, HIPS (high impact polystyrene resin), AS resin, ABS resin, AES resin, MBS resin and the like. Further, there may be mentioned polymer alloys containing these polystyrene resins.
[0007]
The flame retardant used in the present invention is a halogenated epoxy resin (B) containing an alkyl glycidyl ether compound having 18 carbon atoms.
The halogenated epoxy resin (B) containing the alkyl glycidyl ether compound is as follows:
(1) a mixture of a halogenated epoxy resin and an alkyl glycidyl ether compound,
(2) a reaction product of a halogenated epoxy resin or a halogenated bisphenol, epihalohydrin, and an alkyl glycidyl ether compound, or a mixture of the reaction product and a halogenated epoxy resin;
(3) Any of an adduct of an alkyl glycidyl ether compound and a phenol and a mixture of the adduct with a halogenated epoxy resin may be used.
As to the halogenated epoxy resin, if necessary, for example, in order to increase the bromine content, 0 to 60% of the epoxy groups of the halogenated epoxy resin may be blocked with halogenated phenols. Alternatively, 0 to 60 parts by weight of a compound in which the epoxy group of the halogenated epoxy resin is blocked to 80% or more, and 100 to 40 parts by weight of a halogenated epoxy resin containing an alkyl glycidyl ether compound having 18 carbon atoms. It may be melt-mixed. The content of the halogenated epoxy resin having a structure blocked by halogenated phenols is not particularly limited, but is preferably 60 parts by weight or less, more preferably 50 parts by weight or less. If it is more than 60 parts by weight, light resistance cannot be expected.
[0008]
The number 18 alkyl glycidyl et carbon - ether compound with an alkyl glycidyl et eighteen carbon atoms - ether, having 18 carbon alkyl glycidyl et - ether and phenol - reaction product of Le acids and having 18 carbon At least one selected from the group consisting of a reaction product of the alkyl glycidyl ether of the above and a phenol terminal in the epoxy resin, wherein the content of the alkyl glycidyl ether compound having 18 carbon atoms is Although not particularly limited, 0.1 to 10 parts by weight of the total amount of the flame retardant is preferable, and 0.5 to 8 parts by weight is more preferable. If the amount is less than 0.1 part by weight, the effect of reducing the adhesion to metal cannot be expected. If the amount exceeds 10 parts by weight, the flame retardant effect and the heat distortion temperature of the flame retardant resin composition tend to decrease. The above compound may be used in combination with another releasing agent or lubricant, if necessary.
[0009]
The halogenated epoxy resin used herein refers to a reaction product of a halogenated bisphenol and an epihalohydrin, a reaction product of a halogenated phenol-novolak and an epihalohydrin, or a halogenated epoxy resin of these reaction products. Addition products with halogenated bisphenols are exemplified.
Specific examples of the halogenated epoxy resin include diglycidyl ether of tetrachlorobisphenol A, diglycidyl ether of tetrabromobisphenol A, diglycidyl ether of tetrabromobisphenol S, and tetrachlorobisphenol. And dibromophenol-novolak polyglycidyl ether.
[0010]
Halogenated phenols which block the epoxy group of the halogenated epoxy resin include 2,4,6-tribromophenol, dibromophenol, monobromophenol and 2,4,6-trichlorophenol. , Dichlorophenol, monochlorophenol and the like.
[0012]
The terminal phenolic epoxy resin capable of reacting with the alkyl glycidyl ether includes bisphenol type epoxy resin, halogenated epoxy resin, hydroxyquinone type epoxy resin, novolac type epoxy resin, orthocresol type epoxy resin, An epoxy resin such as a biphenyl-type epoxy resin, a fluorene-type epoxy resin, or a naphthalene-type epoxy resin in which some or all of the terminal groups are phenol groups was used.
Examples of the phenols that can react with the alkyl glycidyl ether include phenols that are raw materials for the epoxy resin. Of course, any phenol that can react with glycidyl groups can be used.
[0013]
Further, a reaction product of the epoxy group of the epoxy resin and an alkyl alcohol having 18 carbon atoms or a branched alkyl alcohol can also be used. Alkylalkoxy - as Le octadecyl alcohol - include Le,, etc..
[0014]
As a method for producing a halogenated epoxy resin containing an alkylglycidyl ether compound as a flame retardant used in the present invention, a halogenated bisphenols and epihalohydrin are prepared in the presence of an alkali metal hydroxide and a non-reactive solvent. A method of adding an alkyl glycidyl ether to a halogenated epoxy resin obtained by the reaction, or a method in which a low molecular weight halogenated epoxy resin and a halogenated bisphenol are heated to 80 ° C to 220 ° C in the presence of a catalyst. There is a method in which an alkyl glycidyl ether is added to the resulting medium-molecular-weight halogenated epoxy resin after the heat reaction. If necessary, 60% or less of the epoxy groups of the halogenated epoxy resin may be blocked with a halogenated phenol. Alternatively, a halogenated epoxy resin previously blocked with halogenated phenols may be mixed at 60 parts by weight or less.
[0015]
Also, a method obtained by reacting an alkyl glycidyl ether or an alkyl alcohol with a halogenated bisphenol and epihalohydrin in the presence of an alkali metal hydroxide and a non-reactive solvent, or an alkyl glycidyl ether Or a method obtained by reacting an alkyl alcohol with a halogenated bisphenol and a halogenated epoxy resin in the presence of a catalyst, or an epoxy resin having an alkyl glycidyl ether and the terminal phenol group, There is a method in which a compound obtained by previously reacting a raw material phenol of an epoxy resin with a phenol in the presence of a catalyst is added to the halogenated epoxy resin. Of course, a halogenated epoxy resin blocked with halogenated phenols can be added as needed.
[0016]
Known reaction catalysts include alkali metal hydroxides, tertiary amines, imitasols, quaternary amonium salts, phosphines, phosphonium salts and the like. The method for producing the flame retardant is not particularly limited, and can be easily produced by a known method.
[0017]
For example, antimony trioxide, antimony pentoxide, molybdenum oxide, or the like is used in combination as a flame retardant aid (C) in a styrene resin composition obtained by mixing the styrene resin (A) and the flame retardant (B) of the present invention. This further enhances the flame retardant effect.
Further, the composition of the present invention may contain, if necessary, commonly used ultraviolet absorbers, antioxidants, lubricants, coloring agents, release agents, fillers, dyes and pigments.
[0018]
[Examples and Comparative Examples]
Hereinafter, the effects of the present invention will be described more specifically with reference to Examples and Comparative Examples, but the method for producing the flame retardant and the method for producing the composition of the present invention are not particularly limited. In the examples, all parts and percentages are based on weight.
[0019]
The test method in each example was performed by the method described below.
Test method (1) Epoxy equivalent: JIS K-7234
(2) Softening point: JIS K-7236
(3) Light resistance ΔE: An exposure test (no rain) was conducted at 63 ° C. for 48 hours using a sunshine weather meter. The color difference of the test piece before and after the exposure was measured with a color difference meter (manufactured by Tokyo Denshoku Co., Ltd.).
(4) Flammability test: Based on UL-94 test method.
(5) Adhesion test: In a metal heat roll, the first roll was set at 200 ° C and the second roll was set at 60 ° C, and the test piece was placed on the first roll for 3 minutes. After gently pressing for 3 minutes, the test piece was peeled off and the state of adhesion to the roll was observed.
[0020]
Synthesis Example 1
Epoxy equivalent 650 g / eq. 980 g of a tetrabromobisphenol A (hereinafter abbreviated as TBA) type epoxy resin YDB-406 (bromine content: 50%, manufactured by Toto Kasei Co., Ltd.) of 1 liter equipped with a thermometer, a stirrer, and a condenser The mixture was placed in a separable flask, the inside of which was replaced with nitrogen gas, and heated and melted at 150 ° C., and then an alkylglycidyl ether having an oxirane oxygen content of 4.0% (Epiol SK manufactured by NOF Corporation, hereinafter After stirring for 1 hour, the mixture was placed in a stainless steel vat, cooled and pulverized to obtain a flame retardant-a. The properties are shown in Table 1.
[0022]
Synthesis Example 3
To 350 g of the flame retardant I, 150 g of a brominated epoxy resin TB-62 (bromine content: 58%, manufactured by Toto Kasei Co., Ltd .; hereinafter, abbreviated as TB-62) in which the epoxy group was blocked with tribromophenol was added. Melt blending was performed in the same manner as in Synthesis Example 1. Table 1 shows the properties of the obtained flame retardant-c.
[0024]
Synthesis Example 5
90 g of TBA, 15 g of alkyl glycidyl ether containing 4.0% of oxirane oxygen, and 400 g of YD-400 were charged in the same manner as in Synthesis Example 2, and reacted at 160 ° C. for 5 hours while purging with nitrogen. Table 1 shows the properties of the obtained flame retardant-e.
[0025]
Synthesis Example 6
400 g of YDB-400, 15 g of octadecyl alcohol and 90 g of TBA were charged and reacted in the same manner as in Synthesis Example 2. Table 1 shows the properties of the obtained flame retardant-f.
[0027]
Synthesis Example 9
After 650 g of YDB-406 and 100 g of 2,4,6-tribromophenol were charged and reacted in the same manner as in Synthesis Example 8, 23 g of alkylglycidyl ether containing 4.0% of oxirane oxygen was blended. , Flame retardant-i.
Synthesis Example 10
500 g of YDB-406 and 500 g of TB-62 were melt-blended to obtain a flame retardant-j.
[0028]
Examples 1, 3, 5, 6, 9 and Comparative Examples 1 to 3
After blending the flame retardant obtained from Synthesis Examples 1, 3, 5, 6, and 9, the flame retardant of Synthesis Example 10, YDB-406, and TB-62 in the compositions shown in Table 2, and mixing them with a Henschel mixer, The mixture was melt-mixed with a twin screw extruder (Ikegai PCM-30) to obtain a compound. A test piece was prepared from the obtained compound by injection molding. Flammability, adhesion, and light resistance were measured using this test piece. Table 2 shows the results.
[0029]
[Table 1]
[Table 2]
【The invention's effect】
The flame-retardant styrenic resin composition of the present invention is provided with a halogenated epoxy resin as a flame retardant, by introducing an alkyl glycidyl ether or a compound thereof into the flame-retardant styrenic resin composition, thereby obtaining excellent light resistance and the use of screws for extruders and injection molding machines. The effect of improving the adhesion to the cylinder portion can be exhibited, and it is useful for improving the continuous productivity.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20238894A JP3572488B2 (en) | 1994-08-26 | 1994-08-26 | Flame retardant styrenic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20238894A JP3572488B2 (en) | 1994-08-26 | 1994-08-26 | Flame retardant styrenic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0859927A JPH0859927A (en) | 1996-03-05 |
| JP3572488B2 true JP3572488B2 (en) | 2004-10-06 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20238894A Expired - Lifetime JP3572488B2 (en) | 1994-08-26 | 1994-08-26 | Flame retardant styrenic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3572488B2 (en) |
-
1994
- 1994-08-26 JP JP20238894A patent/JP3572488B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0859927A (en) | 1996-03-05 |
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