JP2019073577A - Styrene resin composition - Google Patents
Styrene resin composition Download PDFInfo
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- JP2019073577A JP2019073577A JP2017198723A JP2017198723A JP2019073577A JP 2019073577 A JP2019073577 A JP 2019073577A JP 2017198723 A JP2017198723 A JP 2017198723A JP 2017198723 A JP2017198723 A JP 2017198723A JP 2019073577 A JP2019073577 A JP 2019073577A
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000011342 resin composition Substances 0.000 title claims abstract description 32
- 229920001971 elastomer Polymers 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 38
- 239000005060 rubber Substances 0.000 claims abstract description 29
- -1 brominated phthalimide compound Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract 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 abstract description 11
- 239000007983 Tris buffer Substances 0.000 claims abstract description 10
- 239000003063 flame retardant Substances 0.000 claims abstract description 10
- 150000003440 styrenes Chemical class 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 229920001890 Novodur Polymers 0.000 claims description 43
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- BDFBPPCACYFGFA-UHFFFAOYSA-N 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine Chemical compound BrC1=CC(Br)=CC(Br)=C1OC1=NC(OC=2C(=CC(Br)=CC=2Br)Br)=NC(OC=2C(=CC(Br)=CC=2Br)Br)=N1 BDFBPPCACYFGFA-UHFFFAOYSA-N 0.000 claims description 4
- DYIZJUDNMOIZQO-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[2-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1CCN1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O DYIZJUDNMOIZQO-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 3
- 239000000155 melt Substances 0.000 abstract 1
- 241000282376 Panthera tigris Species 0.000 description 8
- 239000005064 Low cis polybutadiene Substances 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000005063 High cis polybutadiene Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- BLAWBHWPYNVRFN-UHFFFAOYSA-N 4-[2-(1,3-dioxoisoindol-4-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1NC(=O)C2=C1C=CC=C2CCC1=CC=CC2=C1C(=O)NC2=O BLAWBHWPYNVRFN-UHFFFAOYSA-N 0.000 description 2
- OIPGCJHDZQHXOT-UHFFFAOYSA-N 4-[4-(1,3-dioxoisoindol-4-yl)butyl]isoindole-1,3-dione Chemical compound C(CCCC1=C2C(C(=O)NC2=O)=CC=C1)C1=C2C(C(=O)NC2=O)=CC=C1 OIPGCJHDZQHXOT-UHFFFAOYSA-N 0.000 description 2
- RRZDSQWTGZNJFM-UHFFFAOYSA-N 4-[5-(1,3-dioxoisoindol-4-yl)pentyl]isoindole-1,3-dione Chemical compound O=C1NC(=O)c2c1cccc2CCCCCc1cccc2C(=O)NC(=O)c12 RRZDSQWTGZNJFM-UHFFFAOYSA-N 0.000 description 2
- IJTZNPJNLORUJM-UHFFFAOYSA-N 4-[6-(1,3-dioxoisoindol-4-yl)hexyl]isoindole-1,3-dione Chemical compound O=C1NC(=O)C2=C1C=CC=C2CCCCCCC1=CC=CC2=C1C(=O)NC2=O IJTZNPJNLORUJM-UHFFFAOYSA-N 0.000 description 2
- HYAMCXBBOVHCNL-UHFFFAOYSA-N C(C(C)C1=C2C(C(=O)NC2=O)=CC=C1)C1=C2C(C(=O)NC2=O)=CC=C1 Chemical compound C(C(C)C1=C2C(C(=O)NC2=O)=CC=C1)C1=C2C(C(=O)NC2=O)=CC=C1 HYAMCXBBOVHCNL-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical class C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- 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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VPICDQPHVNYUMI-UHFFFAOYSA-N 4-[(1,3-dioxoisoindol-4-yl)methyl]isoindole-1,3-dione Chemical compound O=C1NC(=O)C2=C1C=CC=C2CC1=CC=CC2=C1C(=O)NC2=O VPICDQPHVNYUMI-UHFFFAOYSA-N 0.000 description 1
- 239000005065 High vinyl polybutadiene Substances 0.000 description 1
- 101100023124 Schizosaccharomyces pombe (strain 972 / ATCC 24843) mfr2 gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 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 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- IYDYVVVAQKFGBS-UHFFFAOYSA-N c(cc1)ccc1Oc1nc(Oc2ccccc2)nc(Oc2ccccc2)n1 Chemical compound c(cc1)ccc1Oc1nc(Oc2ccccc2)nc(Oc2ccccc2)n1 IYDYVVVAQKFGBS-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
Description
本発明は、成形品の外観に優れるスチレン系樹脂組成物を提供する。 The present invention provides a styrenic resin composition excellent in the appearance of a molded article.
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。近年、プラスチック部品は複雑な形状を要求されおり、成形品の形状によっては、ゲート部から放射状に縞模様（タイガーストライプ）の外観不良が発生する。 Styrene resins are used in a wide range of applications because of their properties. In recent years, plastic parts are required to have a complicated shape, and depending on the shape of a molded article, appearance defects of stripes (tiger stripes) occur radially from the gate portion.
本発明は、成形品の外観が優れるスチレン系樹脂組成物を提供することである。 The present invention is to provide a styrenic resin composition which is excellent in the appearance of molded articles.
１，（Ａ）ゴム変性スチレン系樹脂がＭＦＲ2／ゴム粒子径が２５以上である事を特徴とするスチレン系樹脂組成物。
ＭＦＲは２００℃、４９Ｎ荷重で測定したメルトマスフローレート（ＭＦＲ）
ゴム粒子径はコールターマルチサイザー法で測定した体積基準の粒子径分布曲線の５０体積％粒子径
２．（Ａ）ゴム変性スチレン系樹脂、（Ｂ）ハロゲン系難燃剤を含有するスチレン系樹脂組成物であって、（Ａ）ゴム変性スチレン系樹脂がＭＦＲ2／ゴム粒子径が２５以上である事を特徴とするスチレン系樹脂組成物。
ＭＦＲは２００℃、４９Ｎ荷重で測定したメルトマスフローレート（ＭＦＲ）
ゴム粒子径はコールターマルチサイザー法で測定した体積基準の粒子径分布曲線の５０体積％粒子径
３．（Ａ）ゴム変性スチレン系樹脂１００質量部に対して、（Ｂ）ハロゲン系難燃剤１０〜２０質量部を含有する前記２に記載のスチレン系樹脂組成物。
４．（Ｂ）ハロゲン系難燃剤が下記一般式（１）で表される（Ｂ−１）臭素化フタルイミド化合物又は／或いは、下記一般式（２）で表される（Ｂ−２）トリス（ポリブロモフェノキシ）トリアジン化合物である事を特徴とする前記２又は３に記載のスチレン系樹脂組成物。
５．前記臭素化フタルイミド化合物が、エチレン−ビス−テトラブロモフタルイミドで、前記トリス（ポリブロモフェノキシ）トリアジン化合物が、トリス（トリブロモフェノキシ）トリアジンである事を特徴とする前記２〜４いずれかに記載のスチレン系樹脂組成物。
６．前記１〜５のいずれかに記載のスチレン系樹脂組成物からなる事を特徴とする成形体。
A styrene resin composition characterized in that 1, (A) rubber modified styrene resin has MFR 2 / rubber particle diameter of 25 or more.
MFR is melt mass flow rate (MFR) measured at 200 ° C, 49N load
The rubber particle size is 50% by volume particle size of the volume-based particle size distribution curve measured by Coulter Multisizer method. (A) A styrene-based resin composition containing a rubber-modified styrene resin and (B) a halogen-based flame retardant, wherein (A) the rubber-modified styrene-based resin has a MFR2 / rubber particle diameter of 25 or more Styrenic resin composition to be used.
MFR is melt mass flow rate (MFR) measured at 200 ° C, 49N load
The rubber particle size is 50% by volume particle size of volume-based particle size distribution curve measured by Coulter Multisizer method. The styrene resin composition according to 2 above, which comprises 10 to 20 parts by mass of the halogen-based flame retardant (B) relative to 100 parts by mass of the rubber-modified styrene resin (A).
4. (B) A brominated phthalimide compound represented by the following general formula (1) and / or a (B-2) tris (polybromo) represented by the following general formula (2): 2. The styrenic resin composition as described in 2 or 3 above, which is a phenoxy) triazine compound.
5. The brominated phthalimide compound is ethylene-bis-tetrabromophthalimide, and the tris (polybromophenoxy) triazine compound is tris (tribromophenoxy) triazine. Styrenic resin composition.
6. 7. A molded article comprising the styrene resin composition according to any one of 1 to 5 above.
本発明のスチレン系樹脂組成物は、成形品の外観に優れているため、容器・包装分野、家電・ＯＡ機器分野、雑貨分野、住宅設備分野、農林業分野等の多分野での使用が有利になる。 Since the styrenic resin composition of the present invention is excellent in the appearance of molded articles, its use in various fields such as container / packaging field, home electric appliance / OA equipment field, miscellaneous goods field, housing equipment field, agricultural and forestry field etc. is advantageous become.
本発明で用いる（Ａ）ゴム変性スチレン系樹脂とは、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、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。 The rubber-modified styrenic resin (A) used in the present invention is, for example, a rubber-like polymer dissolved in a mixture of an aromatic vinyl monomer and an inert solvent, and stirred to perform bulk polymerization, suspension polymerization, solution polymerization, and the like. The rubber-like polymer is a polymer obtained by dispersing the rubber-like polymer in the form of particles in the matrix of the aromatic vinyl polymer obtained by
上記の芳香族ビニル単量体としては、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、及びこれらの併用系を挙げることが出来るが、スチレンが最も好適である。 Examples of the above-mentioned aromatic vinyl monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene and the like, and combinations of these, but styrene is Most preferred.
（Ａ）ゴム変性スチレン系樹脂はＭＦＲ2／ゴム粒子径が２５以上である。２５未満だと、成形品にタイガーストライプの外観不良が発生する。 (A) The rubber-modified styrenic resin has an MFR 2 / rubber particle diameter of 25 or more. If it is less than 25, the appearance of the tiger stripe occurs in the molded article.
本発明でのタイガーストライプとは、成形品表面にゲート部より放射状に縞模様が発生するの外観不良の事を言う。 The tiger stripe in the present invention means an appearance defect in which a stripe pattern is generated radially on the surface of a molded article from the gate portion.
（Ａ）ゴム変性スチレン系樹脂のＭＦＲはＪＩＳ Ｋ７２１０に基づき２００℃、４９Ｎ荷重で測定した値を言う。ＭＦＲは特に限定されないが、好ましくは２〜１５ｇ／１０ｍｉｎがである。 (A) MFR of rubber-modified styrenic resin refers to a value measured at 200 ° C. and 49 N load based on JIS K 7210. The MFR is not particularly limited, but preferably 2 to 15 g / 10 min.
（Ａ）ゴム変性スチレン系樹脂のゴム粒子径とは（Ａ）ゴム変性スチレン系樹脂組成物を電解液（３％テトラ−ｎ−ブチルアンモニウム／９７％ジメチルホルムアミド溶液）に溶解させ、コールターマルチサイザー法（コールター社製マルチサイザーＩＩ：アパチャーチューブのオリフィス径３０μｍ）により測定して求めた体積基準の粒子径分布曲線の５０体積％粒子径の事を言う。ゴム粒子径は特に限定されないが、好ましくは０．３〜４．０μｍである。 (A) Rubber particle diameter of rubber-modified styrenic resin (A) A rubber-modified styrenic resin composition is dissolved in an electrolytic solution (3% tetra-n-butylammonium / 97% dimethylformamide solution) to obtain Coulter Multisizer The 50 volume% particle diameter of the volume-based particle diameter distribution curve determined by measurement according to the method (Coulter Multisizer II: orifice diameter of 30 μm of aperture tube). The rubber particle diameter is not particularly limited, but preferably 0.3 to 4.0 μm.
粒子径は使用するゴム変性ポリスチレンの種類により調整することができ、具体的には、ゴム変性ポリスチレンの重合工程においてゴム粒子の相転域での攪拌速度を調整する方法や、原料液中の連鎖移動開始剤の量を調整する方法などが挙げられる。 The particle diameter can be adjusted according to the type of rubber-modified polystyrene used. Specifically, the method of adjusting the stirring speed in the phase inversion zone of rubber particles in the polymerization step of rubber-modified polystyrene, the chain in the raw material liquid Methods such as adjusting the amount of transfer initiator may be mentioned.
（ａ）ゴム変性スチレン系樹脂中の芳香族ビニル重合体の分子量については特に制限はないが、還元粘度(ηｓｐ／Ｃ)で０．５〜１．０が好ましい。 (A) The molecular weight of the aromatic vinyl polymer in the rubber-modified styrenic resin is not particularly limited, but is preferably 0.5 to 1.0 in terms of reduced viscosity (ηsp / C).
（Ａ）ゴム変性スチレン系樹脂中のゴム状重合体の含有量については特に制限はないが、３〜１５質量％が好ましい。 The content of the rubbery polymer in the rubber-modified styrenic resin (A) is not particularly limited, but is preferably 3 to 15% by mass.
また、上記ゴム状重合体は、１，４−シス構造が９０モル％以上であり且つ１，２−ビニル構造が４モル%以下であるハイシスポリブタジエン、１，４−シス構造が６５〜９５モル%であり且つ１，２−ビニル構造が３０〜４モル%であるハイシス−ハイビニルポリブタジエン、１，４−シス構造が１５〜４０モル％のローシスポリブタジエン、スチレン−ブタジエン共重合体のいずれを用いても良く、混合物であっても良い。 The rubbery polymer is a high cis polybutadiene having a 1,4-cis structure of 90 mol% or more and a 1,2-vinyl structure of 4 mol% or less, and a 1,4-cis structure of 65 to 95 High cis-high vinyl polybutadiene having a mole% and a 1,2-vinyl structure of 30 to 4 mole%, low cis polybutadiene having a 1,4-cis structure of 15 to 40 mole%, and a styrene-butadiene copolymer Or a mixture.
本発明の（Ｂ）ハロゲン系難燃剤は、特に限定されないが、ハロゲン化ジフェニルエーテル化合物、ハロゲン化ジフェニルアルカン化合物、ハロゲン化フタルイミド化合物、トリス（ポリブロモフェノキシ）トリアジン化合物、ハロゲン化ビスフェノールＡ重合体、ハロゲン化スチレン・ブタジエンブロック共重合体、ハロゲン化スチレン・ブタジエンランダム共重合体、ハロゲン化スチレン・ブタジエングラフト共重合体等が挙げられる。下記一般式（１）で表される（Ｂ−１）ハロゲン化フタルイミド化合物又は／或いは、下記一般式（２）で表される（Ｂ−２）トリス（ポリブロモフェノキシ）トリアジン化合物である事が好ましい。
臭素化フタルイミド化合物は具体的には、メチレン−ビス−フタルイミド、エチレン−ビス−フタルイミド、プロピレン−ビス−フタルイミド、ブチレン−ビス−フタルイミド、ペンチレン−ビス−フタルイミド、ヘキシレン−ビス−フタルイミド等のジブロモ置換体、トリブロモ置換体、テトラブロモ置換体、ペンタブロモ置換体、ヘキサブロモ置換体、ヘプタブロモ置換体、オクタブロモ置換体が挙げられる。好ましくは、エチレン−ビス−フタルイミド、プロピレン−ビス−フタルイミド、ブチレン−ビス−フタルイミド、ペンチレン−ビス−フタルイミド、ヘキシレン−ビス−フタルイミドのオクタブロモ置換体である。特に好ましくは、エチレン−ビス−テトラブロモフタルイミドである。 Specifically, brominated phthalimide compounds are dibromo-substituted products such as methylene-bis-phthalimide, ethylene-bis-phthalimide, propylene-bis-phthalimide, butylene-bis-phthalimide, pentylene-bis-phthalimide, hexylene-bis-phthalimide, etc. And tribromo-substituted, tetrabromo-substituted, pentabromo-substituted, hexabromo-substituted, heptabromo-substituted and octabromo-substituted. Preferred are octabromo-substituted products of ethylene-bis-phthalimide, propylene-bis-phthalimide, butylene-bis-phthalimide, pentylene-bis-phthalimide and hexylene-bis-phthalimide. Particularly preferred is ethylene-bis-tetrabromophthalimide.
トリス（ポリブロモフェノキシ）トリアジン化合物は具体的には、トリフェノキシトリアジンのトリブロモ置換体、テトラブロモ置換体、ペンタブロモ置換体、ヘキサブロモ置換体、ヘプタブロモ置換体、オクタブロモ置換体、ノナブロモ置換体が挙げられる。好ましくは、トリフェノキシトリアジンのオクタブロモ置換体、ノナブロモ置換体であり、特に好ましくはトリス（トリブロモフェノキシ）トリアジンである。 Specific examples of the tris (polybromophenoxy) triazine compound include tribromo-substituted, tetrabromo-substituted, pentabromo-substituted, hexabromo-substituted, heptabromo-substituted, octabromo-substituted and nonabromo-substituted triphenoxy triazine compounds. Preferred are octabromo-substituted and nonabromo-substituted triphenoxytriazines, and particularly preferred is tris (tribromophenoxy) triazine.
（Ｂ）ハロゲン系難燃剤の添加量は特に限定されないが、（Ａ）ゴム変性スチレン系樹脂１００部に対して１０〜２０質量部が好ましい。 Although the addition amount of (B) a halogen-type flame retardant is not specifically limited, 10-20 mass parts is preferable with respect to 100 parts of (A) rubber-modified styrenic resin.
本発明のスチレン系樹脂組成物には、要旨を超えない範囲で各種添加物、例えば染顔料、着色防止剤、難燃助剤、滑剤、酸化防止剤、老化防止剤、光安定剤、帯電防止剤、充填剤、相溶化剤等の公知の添加剤、酸化チタンやカーボンブラックなどの着色剤などの改質剤を添加できる。これらの添加方法は特に限定される訳では無く、公知の方法、例えば、使用する（Ａ）ゴム変性スチレン系樹脂の重合開始前、重合途中の反応液に対して、または重合終了後、及び（Ｂ）ハロゲン系難燃剤を配合する際、更には、押出機や成形機においても添加することができる。 In the styrene resin composition of the present invention, various additives such as dyes and pigments, coloring inhibitors, flame retardant assistants, lubricants, antioxidants, anti-aging agents, light stabilizers, antistatic agents are included in the scope not exceeding the scope of the invention. Additives, fillers, known additives such as compatibilizer, and modifiers such as colorants such as titanium oxide and carbon black can be added. These addition methods are not particularly limited, and known methods, for example, before the start of polymerization of the (A) rubber-modified styrenic resin used, for the reaction liquid during polymerization, or after the completion of polymerization, B) When blending a halogen-based flame retardant, it can be added also in an extruder or a molding machine.
本発明のスチレン系樹脂組成物の原料の混合方法は、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樹脂組成物組成物とする。 The mixing method of the raw material of the styrenic resin composition of this invention can apply a well-known mixing technique. For example, the mixture which has been preliminarily mixed in advance by a mixer such as a mixer type mixer, a V-type other blender, and a tumbler type mixer is further melt-kneaded to obtain a uniform styrenic resin composition composition.
本発明のスチレン系樹脂組成物の溶融混練には、単軸押出機、二軸押出機、三軸押出機、四軸押出機などの押出機、単軸混練機、二軸混練機、三軸混練機、四軸混練機などの多軸混練機、バンバリーミキサー、ロール等の溶融混練装置を使用する。単軸式溶融混練装置と多軸式溶融混練装置をタンデム式に連結した溶融混練装置等を用いてもよい。 In the melt-kneading of the styrene resin composition of the present invention, an extruder such as a single screw extruder, a twin screw extruder, a three screw extruder, a four screw extruder, a single screw kneader, a twin screw kneader, a three screw kneader A kneader, a multi-screw kneader such as a four-axis kneader, a Banbury mixer, a melt-kneading apparatus such as a roll are used. You may use the melt-kneading apparatus etc. which connected the single-screw type melt-kneading apparatus and the multi-axial type melt-kneading apparatus in tandem.
本発明のスチレン系樹脂組成物の成形方法としては押出成形、圧縮成形、射出成形、ブロー成形、射出ブロー成形、カレンダー成形がある。 The styrene-based resin composition of the present invention can be molded by extrusion, compression molding, injection molding, blow molding, injection blow molding, or calendar molding.
以下に本発明を参考例、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 by way of reference examples, examples and comparative examples, but the present invention is not limited thereto.
以下の実施例及び比較例において使用した（Ａ）ゴム変性スチレン系樹脂は下記の特性を有する（Ａ−１）から（Ａ−８）を使用した。
（Ａ−１）：ゴム状重合体に１，４−シス構造が９０モル％以上であり且つ１，２−ビニル構造が４モル%以下であるハイシスポリブタジエンを使用したゴム変性スチレン系樹脂である。このゴム変性スチレン系樹脂は、ＭＦＲが７．１ｇ／１０ｍｉｎ、ゴム粒子径が１．７μｍである。
（Ａ−２）：ゴム状重合体に１，４−シス構造が１５〜４０モル％のローシスポリブタジエンを使用したゴム変性スチレン系樹脂である。このゴム変性スチレン系樹脂は、ＭＦＲが１１．０ｇ／１０ｍｉｎ、ゴム粒子径が２．５μｍである。
（Ａ−３）：ゴム状重合体に１，４−シス構造が１５〜４０モル％のローシスポリブタジエンを使用したゴム変性スチレン系樹脂である。このゴム変性スチレン系樹脂は、ＭＦＲが６．５ｇ／１０ｍｉｎ、ゴム粒子径が０．６μｍである。
（Ａ−４）：ゴム状重合体に１，４−シス構造が９０モル％以上であり且つ１，２−ビニル構造が４モル%以下であるハイシスポリブタジエンを使用したゴム変性スチレン系樹脂である。このゴム変性スチレン系樹脂は、ＭＦＲが４．４ｇ／１０ｍｉｎ、ゴム粒子径が２．９μｍである。
（Ａ−５）：ゴム状重合体に１，４−シス構造が９０モル％以上であり且つ１，２−ビニル構造が４モル%以下であるハイシスポリブタジエンを使用したゴム変性スチレン系樹脂である。このゴム変性スチレン系樹脂は、ＭＦＲが３．１ｇ／１０ｍｉｎ、ゴム粒子径が１．８μｍである。
（Ａ−６）：ゴム状重合体に１，４−シス構造が１５〜４０モル％のローシスポリブタジエンを使用したゴム変性スチレン系樹脂である。このゴム変性スチレン系樹脂は、ＭＦＲが３．４ｇ／１０ｍｉｎ、ゴム粒子径が２．５μｍである。
（Ａ−７）：ゴム状重合体に１，４−シス構造が１５〜４０モル％のローシスポリブタジエンを使用したゴム変性スチレン系樹脂である。このゴム変性スチレン系樹脂は、ＭＦＲが８．２ｇ／１０ｍｉｎ、ゴム粒子径が３．１μｍである。
（Ａ−８）：ゴム状重合体に１，４−シス構造が１５〜４０モル％のローシスポリブタジエンを使用したゴム変性スチレン系樹脂である。このゴム変性スチレン系樹脂は、ＭＦＲが２．６ｇ／１０ｍｉｎ、ゴム粒子径が０．６μｍである。
The rubber-modified styrenic resin (A) used in the following examples and comparative examples used (A-1) to (A-8) having the following characteristics.
(A-1): A rubber-modified styrenic resin using, as a rubbery polymer, a high cis polybutadiene having a 1,4-cis structure of 90 mol% or more and a 1,2-vinyl structure of 4 mol% or less is there. This rubber-modified styrenic resin has an MFR of 7.1 g / 10 min and a rubber particle diameter of 1.7 μm.
(A-2): A rubber-modified styrenic resin in which low cis polybutadiene having a 1,4-cis structure of 15 to 40 mol% is used as a rubbery polymer. This rubber-modified styrenic resin has an MFR of 11.0 g / 10 min and a rubber particle diameter of 2.5 μm.
(A-3): A rubber-modified styrenic resin in which low cis polybutadiene having a 1,4-cis structure of 15 to 40 mol% is used as a rubbery polymer. This rubber-modified styrenic resin has an MFR of 6.5 g / 10 min and a rubber particle diameter of 0.6 μm.
(A-4) A rubber-modified styrenic resin using a high cis polybutadiene having a 1,4-cis structure of 90 mol% or more and a 1,2-vinyl structure of 4 mol% or less as the rubbery polymer is there. This rubber-modified styrenic resin has an MFR of 4.4 g / 10 min and a rubber particle diameter of 2.9 μm.
(A-5): A rubber-modified styrenic resin using a high cis polybutadiene having a 1,4-cis structure of 90 mol% or more and a 1,2-vinyl structure of 4 mol% or less as the rubbery polymer is there. This rubber-modified styrenic resin has an MFR of 3.1 g / 10 min and a rubber particle diameter of 1.8 μm.
(A-6): A rubber-modified styrenic resin in which low cis polybutadiene having a 1,4-cis structure of 15 to 40 mol% is used as a rubbery polymer. This rubber-modified styrenic resin has an MFR of 3.4 g / 10 min and a rubber particle diameter of 2.5 μm.
(A-7): A rubber-modified styrenic resin in which low cis polybutadiene having a 1,4-cis structure of 15 to 40 mol% is used as a rubbery polymer. This rubber-modified styrenic resin has an MFR of 8.2 g / 10 min and a rubber particle diameter of 3.1 μm.
(A-8): A rubber-modified styrenic resin in which low cis polybutadiene having a 1,4-cis structure of 15 to 40 mol% is used as a rubbery polymer. This rubber-modified styrenic resin has an MFR of 2.6 g / 10 min and a rubber particle diameter of 0.6 μm.
（Ａ）ゴム変性スチレン系樹脂のＭＦＲ及び、ゴム粒子径は以下の方法で測定した。 (A) MFR and rubber particle diameter of rubber modified styrene resin were measured by the following method.
メルトマスフローレート（ＭＦＲ）はＪＩＳ Ｋ７２１０に基づき２００℃、４９Ｎ荷重の条件により求めた。 Melt mass flow rate (MFR) was determined under the conditions of 200 ° C. and 49 N load based on JIS K 7210.
ゴム粒子径は（Ａ）ゴム変性スチレン系樹脂組成物を電解液（３％テトラ−ｎ−ブチルアンモニウム／９７％ジメチルホルムアミド溶液）に溶解させ、コールターマルチサイザー法（コールター社製マルチサイザーＩＩ：アパチャーチューブのオリフィス径３０μｍ）により測定して求めた体積基準の粒子径分布曲線の５０体積％粒子径とした。 For the rubber particle diameter, (A) a rubber-modified styrenic resin composition is dissolved in an electrolytic solution (3% tetra-n-butylammonium / 97% dimethylformamide solution), Coulter multisizer method (Coulter Multisizer II: Aperture) The 50% by volume particle diameter of the volume-based particle diameter distribution curve determined by measuring the orifice diameter of the tube (30 μm) was used.
（Ｂ）難燃剤には、（Ｂ−１）臭素化フタルイミド化合物としては、アルベマール日本株式会社製「ＳＡＹＴＥＸ−ＢＴ９３」（エチレン−ビス−テトラブロモフタルイミド）を使用し、（Ｂ−２）トリス（ポリブロモフェノキシ）トリアジン化合物としては、第一工業製薬社製「ＳＲ２４５」（トリス（トリブロモフェノキシ）トリアジン）を使用した。 For the flame retardant (B-1) as the brominated phthalimide compound, “SAYTEX-BT 93” (ethylene-bis-tetrabromophthalimide) manufactured by Albemarle Japan Co., Ltd. is used, and (B-2) tris (B-2) is used. As the polybromophenoxy) triazine compound, “SR245” (tris (tribromophenoxy) triazine) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. was used.
スチレン系樹脂組成物の製造は（Ａ）ゴム変性スチレン系樹脂、（Ｂ−１）臭素化フタルイミド化合物又は（Ｂ−２）トリス（ポリブロモフェノキシ）トリアジン化合物を表１に示す配合比率にて添加し、ミキサー型混練器で予備混練した後、二軸押出機に定量供給して溶融混合し、スチレン系樹脂組成物を得た。 The styrene resin composition was prepared by adding (A) a rubber-modified styrenic resin, (B-1) a brominated phthalimide compound or (B-2) a tris (polybromophenoxy) triazine compound at a blending ratio shown in Table 1 After prekneading with a mixer type kneader, a fixed amount was supplied to a twin-screw extruder and melt mixing was performed to obtain a styrene resin composition.
二軸押出機は東芝機械株式会社製「ＴＥＭ−２６ＳＳ」（スクリュー径Φ２６ｍｍ、１４バレル）であり、運転条件は下記の通りである。
（１）シリンダー設定温度：１８０℃（搬送部位）〜２３０℃（混練部位〜計量部位）
（２）スクリュー回転数：３００ｒｐｍ
（３）押出速度：３０ｋｇ／ｈ
（４）樹脂温度：２４０〜２５０℃
The twin-screw extruder is “TEM-26SS” (screw diameter φ 26 mm, 14 barrels) manufactured by Toshiba Machine Co., Ltd., and the operating conditions are as follows.
(1) Cylinder set temperature: 180 ° C. (conveying site) to 230 ° C. (kneading site to measurement site)
(2) Screw rotational speed: 300 rpm
(3) Extrusion rate: 30 kg / h
(4) Resin temperature: 240 to 250 ° C
実施例及び比較例に示した測定は以下の方法により実施した。 The measurements shown in the Examples and Comparative Examples were carried out by the following methods.
タイガーストライプの評価方法は上記にて得られたスチレン系樹脂組成物のペレットを７０℃で３時間加熱乾燥後、射出成形機（日本製鋼所株式会社製「Ｊ１００Ｅ−Ｆ」にて図１に示す試験片をシリンダー設定温度２３０℃、金型設定温度３０℃、射出速度３０％、射出圧力５０％、保持圧力３０％、射出及び保圧時間１０秒、冷却時間４０秒、計量完了位置90ｍｍ、射出保圧切替位置１５ｍｍで作成した。
得られた試験片の表面を目視観察を行い、タイガーストライプの判定を下記基準にて行った。
◎：縞模様が無い。
○：縞模様が少しあるが、問題無いレベル。
×：縞模様がある。
××：縞模様が著しくある。
The evaluation method of the tiger stripe is shown in FIG. 1 with an injection molding machine (“J100 E-F” manufactured by Japan Steel Works, Ltd.) after drying by heating the pellet of the styrene resin composition obtained above at 70 ° C. for 3 hours. Test piece cylinder setting temperature 230 ° C, mold setting temperature 30 ° C, injection speed 30%, injection pressure 50%, holding pressure 30%, injection and holding time 10 seconds, cooling time 40 seconds, weighing completion position 90mm, injection Created at holding pressure switching position 15 mm.
The surface of the obtained test piece was visually observed, and determination of the tiger stripe was performed on the following reference | standard.
◎: There is no stripe pattern.
○: There are a few stripes but no problem.
X: There is a stripe pattern.
××: There is a marked stripe pattern.
下記表１および２に結果を示した。 The results are shown in Tables 1 and 2 below.
表１の実施例より、本発明の規定を満たしたスチレン系樹脂組成物は、タイガーストライプの発生が無く成形品外観に優れていることがわかる。 From the examples in Table 1, it is understood that the styrenic resin composition satisfying the definition of the present invention is excellent in appearance of molded articles without occurrence of tiger stripe.
一方、表２の比較例より、本発明の規定を満足しないスチレン系樹脂組成物は、タイガーストライプが発生し成形品外観に劣る。 On the other hand, from the comparative example of Table 2, the styrenic resin composition which does not satisfy the definition of the present invention generates tiger stripes and is inferior in the appearance of a molded article.
本発明のスチレン系樹脂組成物は、成形品外観に優れているため、家電・ＯＡ機器分野、雑貨分野、住宅設備分野、農林業分野等の様々な分野での使用が有利になる。
Since the styrenic resin composition of the present invention is excellent in the appearance of molded articles, it is advantageously used in various fields such as the home appliance / OA equipment field, the general merchandise field, the housing equipment field and the agroforestry field.
Claims (6)
ＭＦＲは２００℃、４９Ｎ荷重で測定したメルトマスフローレート（ＭＦＲ）
ゴム粒子径はコールターマルチサイザー法で測定した体積基準の粒子径分布曲線の５０体積％粒子径 (A) A styrene resin composition characterized in that the rubber modified styrene resin has MFR 2 / rubber particle diameter of 25 or more.
MFR is melt mass flow rate (MFR) measured at 200 ° C, 49N load
The rubber particle size is 50% by volume of the volume-based particle size distribution curve measured by Coulter Multisizer method.
ＭＦＲは２００℃、４９Ｎ荷重で測定したメルトマスフローレート（ＭＦＲ）
ゴム粒子径はコールターマルチサイザー法で測定した体積基準の粒子径分布曲線の５０体積％粒子径 (A) A styrene-based resin composition containing a rubber-modified styrene resin and (B) a halogen-based flame retardant, wherein (A) the rubber-modified styrene-based resin has a MFR 2 / rubber particle diameter of 25 or more Styrene resin composition characterized by the above.
MFR is melt mass flow rate (MFR) measured at 200 ° C, 49N load
The rubber particle size is 50% by volume of the volume-based particle size distribution curve measured by Coulter Multisizer method.
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