JP2014095026A - Styrenic flame-retardant resin composition and molded article - Google Patents
Styrenic flame-retardant resin composition and molded article Download PDFInfo
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- JP2014095026A JP2014095026A JP2012246664A JP2012246664A JP2014095026A JP 2014095026 A JP2014095026 A JP 2014095026A JP 2012246664 A JP2012246664 A JP 2012246664A JP 2012246664 A JP2012246664 A JP 2012246664A JP 2014095026 A JP2014095026 A JP 2014095026A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 40
- 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 39
- 239000011342 resin composition Substances 0.000 title claims abstract description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011787 zinc oxide Substances 0.000 claims abstract description 18
- 239000000454 talc Substances 0.000 claims abstract description 17
- 229910052623 talc Inorganic materials 0.000 claims abstract description 17
- -1 ester compound Chemical class 0.000 claims abstract description 15
- 229920001971 elastomer Polymers 0.000 claims abstract description 7
- 239000005060 rubber Substances 0.000 claims abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 12
- 229920005990 polystyrene resin Polymers 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 17
- 239000011347 resin Substances 0.000 abstract description 17
- 229910052736 halogen Inorganic materials 0.000 abstract description 9
- 150000002367 halogens Chemical class 0.000 abstract description 9
- 150000002894 organic compounds Chemical class 0.000 abstract description 8
- 230000000704 physical effect Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 5
- 238000001746 injection moulding Methods 0.000 abstract description 2
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229910019142 PO4 Inorganic materials 0.000 description 11
- 239000010452 phosphate Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 150000003440 styrenes Chemical class 0.000 description 9
- 150000003014 phosphoric acid esters Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920001890 Novodur Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 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 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、スチレン系難燃性樹脂組成物、及びその組成物から得られる成形体に関する。詳しくはハロゲン含有有機化合物を含有せず難燃性に優れ、流動性、耐熱性、面衝撃強度の物性バランスに優れ、電子・電気機器、ＯＡ機器等に好適なスチレン系難燃性樹脂組成物及びその組成物から得られる成形体に関するものである。 The present invention relates to a styrene-based flame retardant resin composition and a molded body obtained from the composition. Specifically, it does not contain a halogen-containing organic compound, has excellent flame retardancy, has excellent fluidity, heat resistance, and surface impact strength balance, and is suitable for electronic / electrical equipment, OA equipment, etc. And a molded body obtained from the composition.
スチレン系樹脂はその特性を生かし広範囲な用途に使用されている。中でも高度な難燃性を付与させた難燃性樹脂はパーソナルコンピュータ、プリンター、複写機等のＯＡ機器、ＴＶ、オーディオ等の家電製品等を初めとする多岐の分野で使用されている。 Styrenic resins are used in a wide range of applications by taking advantage of their properties. Among these, flame retardant resins imparted with a high degree of flame retardancy are used in various fields including OA equipment such as personal computers, printers and copiers, and home appliances such as TVs and audios.
従来から、スチレン系樹脂に難燃性を付与するために、種々の難燃剤が提案されており、中でも安価で物性バランスに優れているハロゲン含有有機化合物が多く使用されている。代表的なものとしてはテトラブロモビスフェノールＡ、デカブロモジフェニルエーテル、デカブロモジフェニルエタン、臭素化エポキシ、及び臭素化エポキシ樹脂のエポキシ基をトリブロモフェノールで封止したもの等が知られている。難燃助剤として使われるアンチモン系化合物としては三酸化アンチモンが主として使われる。 Conventionally, various flame retardants have been proposed to impart flame retardancy to styrene resins, and among them, halogen-containing organic compounds that are inexpensive and excellent in balance of physical properties are often used. Typical examples include tetrabromobisphenol A, decabromodiphenyl ether, decabromodiphenyl ethane, brominated epoxy, and brominated epoxy resins whose epoxy groups are sealed with tribromophenol. Antimony trioxide is mainly used as an antimony compound used as a flame retardant aid.
しかしながら、ハロゲン含有有機化合物は加工時にハロゲン化水素ガスが発生し金型腐食等の不具合発生の可能性があることや、使用済み電気製品を廃棄処理する場合自然環境に悪影響を及ぼすことが考えられ、更に近年、ハロゲン含有有機化合物を規制する動きが欧州を中心として活発に行われており、ハロゲン元素を含まない難燃性樹脂組成物の需要が高まっている。 However, halogen-containing organic compounds may generate hydrogen halide gas during processing and may cause defects such as mold corrosion, and may have a negative impact on the natural environment when used electrical products are disposed of. Furthermore, in recent years, movements for regulating halogen-containing organic compounds have been actively carried out mainly in Europe, and the demand for flame-retardant resin compositions containing no halogen element is increasing.
ハロゲン含有有機化合物の代替難燃剤としてリン系難燃剤が検討されている。例えばスチレン系樹脂の難燃性樹脂組成物としては、スチレン系樹脂とリン系難燃剤からなる難燃性スチレン系樹脂組成物（特開２００１−２０７０１２号公報）等を挙げることができる。また、ポリフェニレンエーテルを併用した難燃性樹脂組成物も検討され、例えば、ポリフェニレンエーテル、スチレン系樹脂、リン酸エステル、および充填剤より成る樹脂組成物等がある（特開２０１１−２５２１１４号公報）。 Phosphorus flame retardants have been studied as alternative flame retardants for halogen-containing organic compounds. For example, as a flame retardant resin composition of a styrene resin, a flame retardant styrene resin composition (Japanese Patent Laid-Open No. 2001-207012) composed of a styrene resin and a phosphorus flame retardant can be exemplified. Further, a flame retardant resin composition using polyphenylene ether in combination is also studied, and examples thereof include a resin composition comprising polyphenylene ether, a styrene resin, a phosphate ester, and a filler (Japanese Patent Laid-Open No. 2011-252114). .
しかしながら、リン系難燃剤を用いた難燃性スチレン系樹脂組成物は難燃性、成形加工時に必要な流動性、耐熱性及び機械的強度として重要な面衝撃強度を必ずしも満足させるものではない。 However, a flame-retardant styrene resin composition using a phosphorus-based flame retardant does not necessarily satisfy an important surface impact strength as flame retardancy, fluidity required at the time of molding, heat resistance, and mechanical strength.
本発明は、この様な現状を鑑み、上記の問題点を解決し、ハロゲン含有有機化合物を含有せず難燃性に優れ、流動性、耐熱性、面衝撃強度の物性バランスに優れ、電子・電気機器、ＯＡ機器等に好適なスチレン系難燃性樹脂組成物を提供するものである。 In view of such a current situation, the present invention solves the above problems, does not contain a halogen-containing organic compound, has excellent flame retardancy, excellent fluidity, heat resistance, and physical property balance of surface impact strength. The present invention provides a styrene-based flame retardant resin composition suitable for electrical equipment, OA equipment, and the like.
本発明者は、上記課題について鋭意検討した結果、特定のゴム変性スチレン系樹脂に、特定のリン酸エステルとタルク、及び酸化亜鉛を添加する事によって本発明を完成させた。 As a result of intensive studies on the above problems, the present inventor has completed the present invention by adding a specific phosphate ester, talc, and zinc oxide to a specific rubber-modified styrene resin.
すなわち、本発明は以下のとおりである。
１．（Ａ）ゴム変性ポリスチレン樹脂１００質量部に対して、（Ｂ）式（１）で表されるリン酸エステル化合物９〜１３質量部、（Ｃ）タルクを１〜６質量部、（Ｄ）酸化亜鉛を１〜４質量部を含有することを特徴とする難燃性樹脂組成物。
３．（Ｄ）酸化亜鉛の空気透過法で測定したときの平均粒子径が０．３μm以下であることを特徴とする前記１に記載のスチレン系難燃性樹脂組成物。
４．前記１〜３のいずれか１項に記載の難燃性樹脂組成物から得られる成形体。
That is, the present invention is as follows.
1. (A) For 100 parts by mass of the rubber-modified polystyrene resin, (B) 9 to 13 parts by mass of the phosphoric acid ester compound represented by the formula (1), (C) 1 to 6 parts by mass of talc, (D) oxidation A flame-retardant resin composition containing 1 to 4 parts by mass of zinc.
3. (D) The styrene-based flame retardant resin composition as described in 1 above, wherein the average particle size is 0.3 μm or less as measured by an air permeation method of zinc oxide.
4). The molded object obtained from the flame-retardant resin composition of any one of said 1-3.
本発明は、ハロゲン含有有機化合物を含有せず難燃性に優れ、流動性、耐熱性、面衝撃強度の物性バランスに優れた、スチレン系難燃性樹脂組成物を提供したものである。また、この難燃性樹脂組成物を射出成形して自己消炎性が要求される成形体を得ることが出来る。更にこの難燃性樹脂組成物を用いて得られる成形体は、トナーカートリッジ、プリンター、パソコン等の筐体等の電子・電気機器、ＯＡ機器等に好適に使用することができる。 The present invention provides a styrene-based flame-retardant resin composition that does not contain a halogen-containing organic compound, has excellent flame retardancy, and has excellent fluidity, heat resistance, and surface impact strength. Moreover, the flame-retardant resin composition can be injection-molded to obtain a molded body requiring self-extinguishing properties. Furthermore, a molded article obtained using this flame retardant resin composition can be suitably used for electronic / electrical equipment such as a housing of a toner cartridge, printer, personal computer, etc., OA equipment, and the like.
本発明の（Ａ）ゴム変性スチレン系樹脂としては、芳香族ビニル重合体のマトリックス中にゴム状重合体が粒子状に分散してなる重合体を言う。例えば、芳香族ビニル単量体と不活性溶媒の混合液にゴム状重合体を溶解し、攪拌して塊状重合、懸濁重合、溶液重合等を行うことにより得られる（ａ）重合体がある。なお、（ａ）重合体は重合法には限定されるものではない。更には、芳香族ビニル単量体と不活性溶媒の混合液にゴム状重合体を溶解して得られた（ａ）重合体に、別途得られた（ｂ）芳香族ビニル重合体を混合した混合物であってもよい。 The (A) rubber-modified styrenic resin of the present invention refers to a polymer in which a rubber-like polymer is dispersed in the form of particles in an aromatic vinyl polymer matrix. For example, there is (a) a polymer obtained by dissolving a rubber-like polymer in a mixture of an aromatic vinyl monomer and an inert solvent and stirring to perform bulk polymerization, suspension polymerization, solution polymerization, or the like. . The (a) polymer is not limited to the polymerization method. Furthermore, (b) the aromatic vinyl polymer obtained separately was mixed with the (a) polymer obtained by dissolving the rubber-like polymer in a mixed liquid of the aromatic vinyl monomer and the inert solvent. It may be a mixture.
なお、マトリックス部分の分子量は、還元粘度(ηｓｐ／Ｃ)で０．５５〜０．８５ｄｌ／ｇである。なお、還元粘度は、ポリマー濃度０．４％（質量／体積）のトルエン溶液を、温度３０℃にてウベローデ型粘度計を使用し測定した。還元粘度が０．８５ｄｌ／ｇを超えると、組成物の流動性が低くなるため成形に支障をきたし易く、また０．５５ｄｌ／ｇ未満だと実用的に十分な強度が発揮でき難くなる等の問題がある。ゴム含有量は、ゴム変性スチレン系樹脂としては、一般的に使用される４〜１５質量％である。ゴム含有量は、成形品に必要な耐衝撃強度と剛性のバランス等を勘案して決めることが望ましい。 The molecular weight of the matrix portion is 0.55 to 0.85 dl / g in terms of reduced viscosity (ηsp / C). The reduced viscosity was measured with a toluene solution having a polymer concentration of 0.4% (mass / volume) at a temperature of 30 ° C. using an Ubbelohde viscometer. If the reduced viscosity exceeds 0.85 dl / g, the fluidity of the composition will be low, so that it will be difficult to mold, and if it is less than 0.55 dl / g, it will be difficult to exhibit practically sufficient strength. There's a problem. Rubber content is 4-15 mass% generally used as rubber-modified styrene resin. The rubber content is preferably determined in consideration of the balance between impact strength and rigidity necessary for the molded product.
上記の芳香族ビニル単量体としては、例えば、スチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、２，４−ジメチルスチレン等が挙げられる。これらの中でもスチレンが好ましく、またこれらの単量体を併用して使用することも出来る。また、上記のゴム状重合体としては、ポリブタジエンゴム、スチレン・ブタジエン共重合体、スチレン・ブタジエン・スチレンブロック共重合体等が挙げられ、中でもポリブタジエンが好ましい。 Examples of the aromatic vinyl monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, and the like. Among these, styrene is preferable, and these monomers can be used in combination. Examples of the rubbery polymer include polybutadiene rubber, styrene / butadiene copolymer, styrene / butadiene / styrene block copolymer, and among them, polybutadiene is preferable.
難燃剤としては、下記の式（１）、好ましくは式（２）で表される（Ｂ）リン酸エステルを使用する。難燃剤の添加量は、（Ａ）ゴム変性スチレン系樹脂１００質量部に対して９〜１３質量部、好ましくは１０〜１２質量部が好適である。難燃剤の添加量が（Ａ）ゴム変性スチレン系樹脂に対して９質量部未満だと難燃性に劣るようになり、試験片厚み０．８ｍｍでＵＬ９４燃焼試験でのＶ−２レベルが確保できない。１３質量部を超えると面衝撃強度及び耐熱性が低下するようになり、好ましくない。 As the flame retardant, phosphoric acid ester (B) represented by the following formula (1), preferably formula (2) is used. The addition amount of the flame retardant is 9 to 13 parts by mass, preferably 10 to 12 parts by mass with respect to (A) 100 parts by mass of the rubber-modified styrene resin. When the amount of flame retardant added is less than 9 parts by mass with respect to (A) rubber-modified styrene resin, the flame retardancy becomes inferior, and a test piece thickness of 0.8 mm ensures a V-2 level in the UL94 combustion test. Can not. If it exceeds 13 parts by mass, the surface impact strength and the heat resistance are lowered, which is not preferable.
無機充填剤としては、（Ｃ）タルクを使用する。タルクの添加量は、（Ａ）ゴム変性スチレン系樹脂１００質量部に対して１〜６質量部、好ましくは３〜５質量部が好適である。タルクが、（Ａ）ゴム変性スチレン系樹脂に対して１質量部未満だと難燃性が低下し、６質量部を超えると面衝撃強度が低下するので好ましくない。 As the inorganic filler, (C) talc is used. The amount of talc added is 1 to 6 parts by weight, preferably 3 to 5 parts by weight, based on 100 parts by weight of the (A) rubber-modified styrene resin. If the talc is less than 1 part by mass relative to the (A) rubber-modified styrene resin, the flame retardancy decreases, and if it exceeds 6 parts by mass, the surface impact strength decreases, which is not preferable.
また、（Ｄ）酸化亜鉛を使用する。酸化亜鉛の添加量は、（Ａ）ゴム変性スチレン系樹脂１００質量部に対して１〜４質量部、好ましくは２〜３質量部が好適である。酸化亜鉛が、（Ａ）ゴム変性スチレン系樹脂に対して１質量部未満だと難燃性が低下し、４質量部を超えると面衝撃強度が低下するので好ましくない。また酸化亜鉛の粒径は、空気透過法で測定したときの平均粒子径が０．３μｍ以下のものが好ましい。０．３μｍを超える場合難燃性、面衝撃強度が低下する。 Further, (D) zinc oxide is used. The addition amount of zinc oxide is 1 to 4 parts by mass, preferably 2 to 3 parts by mass with respect to 100 parts by mass of (A) rubber-modified styrene resin. If the zinc oxide is less than 1 part by mass relative to the (A) rubber-modified styrene-based resin, the flame retardancy decreases, and if it exceeds 4 parts by mass, the surface impact strength decreases, which is not preferable. Further, the zinc oxide preferably has an average particle size of 0.3 μm or less as measured by an air permeation method. When it exceeds 0.3 μm, flame retardancy and surface impact strength are lowered.
本発明のスチレン系難燃性樹脂組成物において、難燃性、耐熱性、流動性、面衝撃強度及びこれらの物性バランス等の点で好ましい範囲は、（Ａ）ゴム変性ポリスチレン樹脂１００質量部に対して、（Ｂ）式（１）で表されるリン酸エステル化合物９〜１３質量部、（Ｃ）タルクを１〜６質量部、（Ｄ）酸化亜鉛を１〜４質量部を含有する配合割合である。 In the styrene-based flame retardant resin composition of the present invention, the preferable range in terms of flame retardancy, heat resistance, fluidity, surface impact strength, balance of physical properties, etc. is (A) 100 parts by mass of rubber-modified polystyrene resin. On the other hand, (B) 9-13 parts by mass of a phosphoric acid ester compound represented by formula (1), (C) 1-6 parts by mass of talc, (D) 1-4 parts by mass of zinc oxide It is a ratio.
また本発明のスチレン系難燃性樹脂組成物には、本発明の目的を損なわない範囲で他の添加剤、例えば可塑剤、溶剤、安定剤、紫外線吸収剤、充填剤、着色剤、補強剤等を添加することができる。 The styrene-based flame retardant resin composition of the present invention includes other additives such as a plasticizer, a solvent, a stabilizer, an ultraviolet absorber, a filler, a colorant, and a reinforcing agent as long as the object of the present invention is not impaired. Etc. can be added.
本発明のスチレン系難燃性樹脂組成物の混合方法は、公知の混合技術を適用することが出来る。例えばミキサー型混合機、Ｖ型他ブレンダー、及びタンブラー型混合機等の混合装置であらかじめ予備混合しておいた混合物を、更に溶融混練することで均一なスチレン系難燃性樹脂組成物とすることが出来る。溶融混練にも特に制限はなく公知の溶融技術を適用出来る。好適な溶融混練装置として、バンバリー型ミキサー、ニーダー、ロール、単軸押出機、特殊単軸押出機、及び二軸押出機等がある。更に押出機等の溶融混練装置の途中から難燃化剤等の添加剤を別途に添加する方法がある。 A known mixing technique can be applied to the method for mixing the styrene-based flame retardant resin composition of the present invention. For example, a uniform styrene-based flame retardant resin composition is obtained by further melt-kneading a mixture preliminarily mixed with a mixing apparatus such as a mixer-type mixer, a V-type blender, and a tumbler-type mixer. I can do it. There is no particular limitation on melt kneading, and a known melting technique can be applied. Suitable melt kneaders include Banbury mixers, kneaders, rolls, single screw extruders, special single screw extruders, and twin screw extruders. Furthermore, there is a method of separately adding an additive such as a flame retardant from the middle of a melt-kneading apparatus such as an extruder.
以下に本発明を実施例及び比較例によって詳しく説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
実施例及び比較例で使用したゴム変性ポリスチレン樹脂は、マトリックス部分のポリスチレンの還元粘度が０．７ｄｌ／ｇ、ゴム状重合体含有量が７．１質量％の組成であるものを作成して使用した。なお、後で掲載する表１〜表２中では、ここで得たゴム変性ポリスチレン樹脂をＨＩ−ＰＳと略記した。 The rubber-modified polystyrene resins used in the examples and comparative examples were prepared by using a composition having a polystyrene reduced viscosity of 0.7 dl / g and a rubbery polymer content of 7.1% by mass. did. In Tables 1 and 2 described later, the rubber-modified polystyrene resin obtained here was abbreviated as HI-PS.
ゴム変性ポリスチレン樹脂の還元粘度（ηｓｐ／Ｃ）の測定は、上記で得たゴム変性ポリスチレン樹脂１ｇにメチルエチルケトン１５ｍｌとアセトン１５ｍｌの混合溶媒を加え、温度２５℃で２時間振とう溶解した後、遠心分離で不溶分を沈降させ、デカンテーションにより上澄み液を取り出し、５００ｍｌのメタノールを加えて樹脂分を析出させ、不溶分を濾過乾燥した。同操作で得られた樹脂分をトルエンに溶解してポリマー濃度０．４％（質量／体積）の試料溶液を作製した。この試料溶液、及び純トルエンを温度３０℃の恒温でウベローデ型粘度計により溶液流下秒数を測定して、下式にて算出した。
ηｓｐ／Ｃ＝（ｔ１／ｔ０−１）／Ｃ
ｔ０：純トルエン流下秒数
ｔ１：試料溶液流下秒数
Ｃ：ポリマー濃度
The reduced viscosity (ηsp / C) of the rubber-modified polystyrene resin was measured by adding a mixed solvent of 15 ml of methyl ethyl ketone and 15 ml of acetone to 1 g of the rubber-modified polystyrene resin obtained above, and dissolving by shaking for 2 hours at a temperature of 25 ° C. The insoluble matter was settled by separation, the supernatant was taken out by decantation, 500 ml of methanol was added to precipitate the resin, and the insoluble matter was filtered and dried. The resin component obtained by the same operation was dissolved in toluene to prepare a sample solution having a polymer concentration of 0.4% (mass / volume). This sample solution and pure toluene were measured at a constant temperature of 30 ° C. using a Ubbelohde viscometer, and the number of seconds during which the solution flowed was measured.
ηsp / C = (t1 / t0-1) / C
t0: Pure toluene flow down seconds
t1: Sample solution flow down seconds
C: Polymer concentration
ゴム状重合体含有量の測定は、ゴム変性スチレン系樹脂をクロロホルムに溶解させ、一定量の一塩化ヨウ素／四塩化炭素溶液を加え暗所に約１時間放置後、１５％（質量／体積）のヨウ化カリウム溶液と純水５０ｍｌを加え、過剰の一塩化ヨウ素を０．１Ｎチオ硫酸ナトリウム／エタノール水溶液で滴定し、付加した一塩化ヨウ素量から算出した。 The rubber-like polymer content was measured by dissolving a rubber-modified styrene resin in chloroform, adding a certain amount of iodine monochloride / carbon tetrachloride solution and leaving it in the dark for about 1 hour, then 15% (mass / volume). A potassium iodide solution and 50 ml of pure water were added, and excess iodine monochloride was titrated with a 0.1N sodium thiosulfate / ethanol aqueous solution and calculated from the amount of iodine monochloride added.
（Ｂ−１）式（１）に対応するリン酸エステルには、ＡＤＥＫＡ株式会社製の商品名ＦＰ−８００を使用した。また、比較用難燃剤（Ｂ−２）リン酸エステルには、１，３−フェニレンレゾルシンビス（ジフェニルホスフェート）である大八化学工業株式会社製の商品名ＣＲ-７３３Ｓを使用した。 (B-1) The trade name FP-800 manufactured by ADEKA Corporation was used as the phosphate ester corresponding to the formula (1). In addition, as a comparative flame retardant (B-2) phosphate ester, trade name CR-733S manufactured by Daihachi Chemical Industry Co., Ltd., which is 1,3-phenylene resorcinbis (diphenyl phosphate), was used.
（Ｃ）タルクには、富士タルク社製の商品名ＫＰタルクを使用した。 (C) The brand name KP talc manufactured by Fuji Talc was used for talc.
（Ｄ）酸化亜鉛には、堺化学工業社製の商品名微細酸化亜鉛（Ｄ−１）（空気透過法による平均粒子径が０．２９μｍ）及び同社製の商品名酸化亜鉛１種（Ｄ−２）（空気透過法による平均粒子径が０．６μｍ）を使用した。 (D) Zinc oxide includes trade name Fine Zinc Oxide (D-1) manufactured by Sakai Chemical Industry Co., Ltd. (average particle size by air permeation method is 0.29 μm) and trade name Zinc Oxide 1 type (D- 2) (average particle diameter by air permeation method is 0.6 μm) was used.
次に、本発明のスチレン系難燃性樹脂組成物の混合方法を述べる。（Ａ）ゴム変性ポリスチレン樹脂、（Ｂ）リン酸エステル系難燃剤、（Ｃ）タルク、及び（Ｄ）酸化亜鉛を表１〜表２に示す配合量にて、これら全成分をヘンシェルミキサー（三井三池化工社製、ＦＭ２０Ｂ）にて予備混合し、二軸押出機（東芝機械社製、ＴＥＭ２６ＳＳ）に供給してストランドとし、水冷してからペレタイザーへ導きペレット化した。この際、シリンダー温度２３０℃、供給量３０ｋｇ／時間とした。 Next, a method for mixing the styrene-based flame retardant resin composition of the present invention will be described. (A) Rubber-modified polystyrene resin, (B) Phosphate ester flame retardant, (C) talc, and (D) Zinc oxide were blended in the amounts shown in Tables 1 and 2 and all these components were mixed with a Henschel mixer (Mitsui The mixture was premixed by Miike Chemical Co., Ltd. (FM20B) and supplied to a twin screw extruder (Toshiki Machine Co., Ltd., TEM26SS) to form a strand, which was cooled with water and led to a pelletizer to be pelletized. At this time, the cylinder temperature was 230 ° C. and the supply amount was 30 kg / hour.
実施例及び比較例に示した各種測定は以下の方法により実施した。 Various measurements shown in Examples and Comparative Examples were performed by the following methods.
燃焼試験用の試験片は、射出成形機（東芝社製、ＩＳ８０ＥＰ）にてシリンダー温度１７０℃で成形した。 The test piece for the combustion test was molded at a cylinder temperature of 170 ° C. with an injection molding machine (Toshiba, IS80EP).
難燃性の測定は、米国アンダーライターズ・ラボラトリーズ社（ＵＬ）のサブジェクト９４号の垂直燃焼試験方法に準拠し、試験片厚さ０．８ｍｍの燃焼性を評価した。なお、表中のＮＧとは、Ｖ−２、Ｖ−１及びＶ−０のいずれをも満足させないものを示す。 The flame retardancy was measured according to the vertical combustion test method of Subject No. 94 of Underwriters Laboratories (UL), USA, and the flammability of a specimen having a thickness of 0.8 mm was evaluated. In addition, NG in a table | surface shows what does not satisfy any of V-2, V-1, and V-0.
面衝撃強度の測定は、ＪＩＳ Ｋ ７２１１−１ パンクチャー衝撃試験に準拠した。試験片は２ｍｍ厚の９０ｍｍ角板、錘先端形状は直径１０ｍｍのものを使用した。５０％破壊エネルギーが０．６Ｊ以上は合格、０．６Ｊ未満は不合格とした。 The surface impact strength was measured in accordance with JIS K 7211-1 puncture impact test. The test piece used was a 90 mm square plate with a thickness of 2 mm, and the weight tip shape was 10 mm in diameter. A 50% fracture energy of 0.6J or higher was accepted and less than 0.6J was rejected.
耐熱性：耐熱性の評価尺度とした荷重たわみ温度は、ＪＩＳ Ｋ ７１９１に準拠し、昇温速度１２０℃／ｈｒで試験を行った。荷重たわみ温度は、温度６９℃以上を合格とした。６９℃未満であると耐熱性が不十分となり熱変形することがある。 Heat resistance: The deflection temperature under load as an evaluation scale of heat resistance was tested according to JIS K 7191 at a heating rate of 120 ° C./hr. The deflection temperature under load was a temperature of 69 ° C. or higher. If it is less than 69 ° C., the heat resistance may be insufficient and thermal deformation may occur.
流動性：流動特性としてメルトマスフローレイト（ＭＦＲ）を測定した。メルトマスフローレイトは、ＪＩＳ Ｋ−７２１０に準拠し、温度２００℃、４９Ｎ荷重の条件で測定した。メルトマスフローレイトは、１０ｇ/ｍｉｎ以上を合格とした。１０ｇ/ｍｉｎ未満であると流動性が不十分となり、成形時にショートショットなどの不具合が生じることがある。 Flowability: Melt mass flow rate (MFR) was measured as flow characteristics. The melt mass flow rate was measured according to JIS K-7210 under the conditions of a temperature of 200 ° C. and a load of 49 N. The melt mass flow rate was determined to be 10 g / min or more. If it is less than 10 g / min, the fluidity becomes insufficient, and problems such as short shots may occur during molding.
表１の実施例に示したとおり、本願発明の組成及び規定量を満たすことによって難燃性、流動性、耐熱性、面衝撃強度の物性バランスに優れていることがわかる。 As shown in the examples of Table 1, it can be seen that satisfying the composition and specified amount of the present invention is excellent in the physical property balance of flame retardancy, fluidity, heat resistance, and surface impact strength.
しかし表２の比較例に示したとおり、本発明の規定を満足しない比較例で得られたスチレン系難燃性樹脂組成物では、何れかに優れることはあっても、その全てに優れていることはないことがわかる。 However, as shown in the comparative examples of Table 2, the styrene-based flame retardant resin composition obtained in the comparative example that does not satisfy the provisions of the present invention is excellent in all, if any. It turns out that there is nothing.
例えば、タルク（Ｃ）、酸化亜鉛（Ｄ）のどちらも添加しない場合、またはどちらか一方のみを規定量添加した場合、リン酸エステル（Ｂ−１）を規定量添加しても、ＵＬ９４垂直燃焼試験で難燃性はＮＧとなる（比較例１、比較例２、比較例３）。また、タルク（Ｃ）、酸化亜鉛（Ｄ）を規定量添加した場合でも、リン酸エステル（Ｂ−１）を規定量を超える量添加すれば荷重たわみ温度、面衝撃強度が低下するので好ましくなく（比較例４）、またリン酸エステル（Ｂ−１）を規定量未満しか添加しないと難燃性はＮＧとなり、またメルトマスフローレートが低くなり好ましくない（比較例５）。リン酸エステル（Ｂ−１）、タルク（Ｃ）が規定量存在しても、酸化亜鉛（Ｄ）の添加量が規定量より多い、あるいはリン酸エステル（Ｂ−１）、酸化亜鉛（Ｄ）が規定量存在しても、タルク（Ｃ）の添加量が規定量より多いと面衝撃強度が低下するので好ましくない（比較例６、比較例７）。更に、タルク（Ｃ）、酸化亜鉛（Ｄ）を規定量添加した場合において、リン酸エステル（Ｂ−１）の替わりにリン酸エステル（Ｂ−２）を添加しても、難燃性はＵＬ９４垂直燃焼試験でＶ−２に達するが、荷重たわみ温度が低くなるので好ましくない（比較例８）。 For example, when neither talc (C) nor zinc oxide (D) is added, or when only one of them is added in a specified amount, even if a specified amount of phosphate ester (B-1) is added, UL94 vertical combustion In the test, the flame retardancy is NG (Comparative Example 1, Comparative Example 2, Comparative Example 3). Moreover, even when a prescribed amount of talc (C) or zinc oxide (D) is added, if the amount of phosphate ester (B-1) exceeds the specified amount, the deflection temperature under load and the surface impact strength are lowered, which is not preferable. (Comparative Example 4) If the phosphoric acid ester (B-1) is added in less than the specified amount, the flame retardancy becomes NG, and the melt mass flow rate is lowered (Comparative Example 5). Even if phosphate ester (B-1) and talc (C) are present in specified amounts, the amount of zinc oxide (D) added is greater than the specified amount, or phosphate ester (B-1) and zinc oxide (D) Even if the specified amount is present, if the amount of talc (C) added is more than the specified amount, the surface impact strength is lowered (Comparative Example 6 and Comparative Example 7). Furthermore, when talc (C) and zinc oxide (D) are added in specified amounts, the flame retardancy is UL94 even if phosphate ester (B-2) is added instead of phosphate ester (B-1). Although it reaches V-2 in the vertical combustion test, it is not preferable because the deflection temperature under load becomes low (Comparative Example 8).
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| WO2003078522A1 (en) * | 2002-03-19 | 2003-09-25 | Songwon Industrial Co., Ltd. | Oligomer-type flame-retardant compound and flame-retardant resin composition comprising same |
| WO2009153934A1 (en) * | 2008-06-16 | 2009-12-23 | 株式会社Adeka | Non-halogen flame-retardant synthetic resin composition |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003078522A1 (en) * | 2002-03-19 | 2003-09-25 | Songwon Industrial Co., Ltd. | Oligomer-type flame-retardant compound and flame-retardant resin composition comprising same |
| WO2009153934A1 (en) * | 2008-06-16 | 2009-12-23 | 株式会社Adeka | Non-halogen flame-retardant synthetic resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016003241A (en) * | 2014-06-13 | 2016-01-12 | 東洋スチレン株式会社 | Styrenic flame-retardant resin composition and molded article made using the same |
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| JP6100507B2 (en) | 2017-03-22 |
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