JP7470301B2 - Resin composition, molded body, electronic component, and electronic device - Google Patents
Resin composition, molded body, electronic component, and electronic device Download PDFInfo
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- 239000011342 resin composition Substances 0.000 title claims description 57
- 229920005989 resin Polymers 0.000 claims description 93
- 239000011347 resin Substances 0.000 claims description 93
- 150000001875 compounds Chemical class 0.000 claims description 50
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 36
- 229910052698 phosphorus Inorganic materials 0.000 claims description 31
- 239000011574 phosphorus Substances 0.000 claims description 31
- 239000004417 polycarbonate Substances 0.000 claims description 28
- -1 phosphazene compound Chemical class 0.000 claims description 26
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 21
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 8
- 229920005668 polycarbonate resin Polymers 0.000 claims description 6
- 239000004431 polycarbonate resin Substances 0.000 claims description 6
- 238000004898 kneading Methods 0.000 description 23
- 229920000515 polycarbonate Polymers 0.000 description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 20
- 239000004793 Polystyrene Substances 0.000 description 17
- 229920002223 polystyrene Polymers 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 229910019142 PO4 Inorganic materials 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000010452 phosphate Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 6
- 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 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 229920005990 polystyrene resin Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- XAIZOTQTRJYNHC-UHFFFAOYSA-N 4-[2-(3,5-diethyl-4-hydroxyphenyl)propan-2-yl]-2,6-diethylphenol Chemical compound CCC1=C(O)C(CC)=CC(C(C)(C)C=2C=C(CC)C(O)=C(CC)C=2)=C1 XAIZOTQTRJYNHC-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 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
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-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
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004420 Iupilon Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 101100203980 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) SPS100 gene Proteins 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000004650 carbonic acid diesters Chemical class 0.000 description 1
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 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
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、樹脂組成物、成形体、電子部品、及び電子機器に関する。 The present invention relates to a resin composition, a molded body, an electronic component, and an electronic device.
一般に有機物である高分子樹脂材料は火災時に燃焼するので、難燃剤を添加した難燃性樹脂が、自動車材料、電気電子機器材料、住宅材料、その他の加工分野における部品製造用材料等に幅広く使用されている。このような樹脂材料について、難燃性だけでなく機械的強度も良好である事が求められており、とりわけ衝撃強度に耐える必要がある。これを実現するためには、良好な外観を射出成形で容易に得ることができるために市場で普及しているポリカーボネート（ＰＣ）樹脂に、ＡＢＳ樹脂やポリスチレン（ＰＳ）樹脂を配合した樹脂組成物が知られている。特に、コストダウンを目的とした場合、ＰＣ／ＰＳアロイを用いることが既に知られている。 Since organic polymer resin materials generally burn in the event of a fire, flame-retardant resins containing added flame retardants are widely used in automobile materials, electrical and electronic equipment materials, housing materials, and materials for manufacturing parts in other processing fields. Such resin materials are required to have not only flame retardancy but also good mechanical strength, and in particular to withstand impact strength. To achieve this, resin compositions are known that combine ABS resin or polystyrene (PS) resin with polycarbonate (PC) resin, which is popular on the market because it can easily achieve a good appearance by injection molding. In particular, the use of PC/PS alloys is already known when the goal is to reduce costs.
特許文献１には、難燃性と剛性、及び耐衝撃性に特に優れた樹脂組成物の提供する目的で、ポリカーボネート（ＰＣ）樹脂とその他樹脂と、リン含有化合物とを含有する樹脂組成物が開示されている。この樹脂組成物は前記リン含有化合物としてホスファゼン誘導体、及びリン酸エステルを含有しており、難燃性と剛性、及び耐衝撃性に優れた樹脂組成物となっている。特許文献１には、樹脂１００質量部に対してＰＣ樹脂８０質量部、ＡＢＳ樹脂１６重量部、ＰＳ樹脂４質量部の構成が開示されている。 Patent Document 1 discloses a resin composition containing polycarbonate (PC) resin, other resins, and a phosphorus-containing compound, with the aim of providing a resin composition that is particularly excellent in flame retardancy, rigidity, and impact resistance. This resin composition contains a phosphazene derivative and a phosphate ester as the phosphorus-containing compound, and is a resin composition that is excellent in flame retardancy, rigidity, and impact resistance. Patent Document 1 discloses a composition of 80 parts by weight of PC resin, 16 parts by weight of ABS resin, and 4 parts by weight of PS resin per 100 parts by weight of resin.
本発明は、コスト、機械的強度、難燃性のすべてが優れる樹脂組成物を提供することを目的とする。 The present invention aims to provide a resin composition that is excellent in terms of cost, mechanical strength, and flame retardancy.
上記課題を解決する本発明の樹脂組成物は以下の通りである。
ＰＣ樹脂、ＰＳ樹脂、ＡＢＳ樹脂、およびリン系化合物を含有する樹脂組成物であって、
前記ＰＣ樹脂を、樹脂合計１００質量部に対して４５質量部以上７０質量部未満含有し、
前記ＰＣ樹脂とＡＢＳ樹脂とを合計で、樹脂合計１００質量部に対し７０質量部以上８５質量部以下含有し、
前記ＰＳ樹脂を、樹脂合計１００質量部に対し１５質量部以上３０質量部以下含有し、
前記リン系化合物は、そのうち少なくとも一種がホスファゼン系化合物であり、
前記ホスファゼン系化合物を樹脂合計１００質量部に対し０．１質量部以上４．０質量部以下含有する樹脂組成物。
The resin composition of the present invention which solves the above problems is as follows.
A resin composition containing a PC resin, a PS resin, an ABS resin, and a phosphorus-based compound,
The PC resin is contained in an amount of 45 parts by mass or more and less than 70 parts by mass per 100 parts by mass of the total resin,
The PC resin and the ABS resin are contained in a total amount of 70 parts by mass or more and 85 parts by mass or less per 100 parts by mass of the total resin,
The PS resin is contained in an amount of 15 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the total resin,
At least one of the phosphorus-based compounds is a phosphazene-based compound,
The resin composition contains the phosphazene compound in an amount of 0.1 parts by mass or more and 4.0 parts by mass or less per 100 parts by mass of the total resin.
本発明により、コストを抑え、機械的強度、難燃性が低下しない樹脂組成物を提供できる。 The present invention provides a resin composition that reduces costs and does not reduce mechanical strength or flame retardancy.
上記の本発明の特徴について、以下詳細に解説する。
（ＰＣ樹脂）
ポリカーボネート樹脂は、例えば、芳香族二価フェノール系化合物とホスゲンまたは炭酸ジエステルとを反応させることにより得られる、芳香族ホモポリカーボネート樹脂またはコポリカーボネート樹脂であってもよい。芳香族二価フェノール系化合物の例としては、２，２－ビス（４－ヒドロキシフェニル）プロパン、２，２－ビス（４－ヒドロキシ－３，５－ジメチルフェニル）プロパン、ビス（４－ヒドロキシフェニル）メタン、１，１－ビス（４－ヒドロキシフェニル）エタン、２，２－ビス（４－ヒドロキシフェニル）ブタン、２，２－ビス（４－ヒドロキシ－３，５－ジフェニル）ブタン、２，２－ビス（４－ヒドロキシ－３，５－ジエチルフェニル）プロパン、２，２－ビス（４－ヒドロキシ－３，５－ジエチルフェニル）プロパン、１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン、および１－フェニル－１，１－ビス（４－ヒドロキシフェニル）エタン等が挙げられ、これらを単独あるいは混合物として使用してもよい。
The above-mentioned features of the present invention will be explained in detail below.
(PC resin)
The polycarbonate resin may be, for example, an aromatic homopolycarbonate resin or a copolycarbonate resin obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester. Examples of the aromatic dihydric phenol compound include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxy-3,5-diphenyl)butane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, and 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane, which may be used alone or in mixture.
ポリカーボネート樹脂は、合成したものを用いてもよいし、市販品を用いてもよい。市販品としては、例えば、帝人化成社製の「Ｌ－１２５０Ｙ」、「ＡＤ５５０３」、出光興産社製の「Ａ２２００」、三菱エンジニアリングプラスチック社製の「ユーピロンＳ２０００」（芳香族ポリカーボネート樹脂）等が挙げられる。また、ポリカーボネート樹脂は、１種単独で用いてもよいし、２種以上を併用してもよい。 The polycarbonate resin may be a synthetic product or a commercially available product. Examples of commercially available products include "L-1250Y" and "AD5503" manufactured by Teijin Chemicals, "A2200" manufactured by Idemitsu Kosan, and "Iupilon S2000" (aromatic polycarbonate resin) manufactured by Mitsubishi Engineering Plastics. The polycarbonate resin may be used alone or in combination of two or more types.
また、ポリカーボネート樹脂は、市場から回収した市場回収材であってもよく、例えば、廃ＣＤ等の廃ディスク、ウォータサーバのガロンボトル等の廃ボトル等の再生材を含んでいてもよい。 The polycarbonate resin may also be recycled materials collected from the market, and may contain recycled materials such as waste discs such as waste CDs and waste bottles such as gallon bottles for water servers.
本発明の樹脂組成物は、ＰＣ樹脂を樹脂合計１００質量部に対して４５質量部以上７０質量部未満含有し、５０質量部以上７０質量部未満含有することが好ましく、６０質量部以上７０質量部未満含有することがより好ましい。ＰＣ樹脂の含有量が樹脂合計１００質量部に対して４５質量部以上７０質量部未満であると、難燃性Ｖ－０を得つつ、必要な機械的強度が得られ、コストダウンを図ることができる。
前記樹脂合計１００質量部に対する質量部数は、樹脂組成物に含有される全ての樹脂の合計を１００質量部とした時の質量部数である。
The resin composition of the present invention contains 45 parts by mass or more and less than 70 parts by mass of PC resin per 100 parts by mass of total resin, preferably 50 parts by mass or more and less than 70 parts by mass, and more preferably 60 parts by mass or more and less than 70 parts by mass. When the content of PC resin is 45 parts by mass or more and less than 70 parts by mass per 100 parts by mass of total resin, it is possible to obtain flame retardancy V-0 while obtaining necessary mechanical strength and reducing costs.
The number of parts by mass relative to 100 parts by mass of the total resin is the number of parts by mass when the total of all the resins contained in the resin composition is taken as 100 parts by mass.
（ＰＳ樹脂）
ポリスチレン樹脂は、下記一般式（１）で表される構成単位を有し、ゴム成分を含むことが好ましい。
The polystyrene resin preferably has a structural unit represented by the following general formula (1) and contains a rubber component.
ポリスチレン樹脂の具体例としては、スチレン系単量体にゴム成分を溶解させ、塊状重合法や懸濁重合法など公知の重合法により得られたゴム変性スチレン重合体や、スチレン系単量体とゴム成分とを公知の方法にて物理混合し、スチレン系単量体とゴム成分との混合物を形成したものが挙げられる。 Specific examples of polystyrene resins include rubber-modified styrene polymers obtained by dissolving a rubber component in a styrene monomer and subjecting it to known polymerization methods such as bulk polymerization and suspension polymerization, and mixtures of a styrene monomer and a rubber component formed by physically mixing the styrene monomer and the rubber component using known methods.
上記のスチレン系単量体としては、スチレンが好適に用いられる。必要に応じて、例えば、α－メチルスチレン、α－メチル－ｐ－メチルスチレン、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、エチルスチレン、ｐ－ｔ－ブチルスチレン、１，１－ジフェニルエチレン、ブロモスチレン、ジブロモスチレン、クロロスチレン、ジクロロスチレンなどをスチレン系単量体としてスチレンと組み合わせて用いることもできる。２種類以上のスチレン系単量体を用いる場合はスチレンを５０質量部以上含有することが好ましい。 As the styrene-based monomer, styrene is preferably used. If necessary, for example, α-methylstyrene, α-methyl-p-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-t-butylstyrene, 1,1-diphenylethylene, bromostyrene, dibromostyrene, chlorostyrene, dichlorostyrene, etc. can also be used in combination with styrene as a styrene-based monomer. When using two or more types of styrene-based monomers, it is preferable to contain 50 parts by mass or more of styrene.
上記ゴム成分としては、例えば、ポリブタジエン、スチレン－ブタジエン共重合体、アクリロニトリル－ブタジエン共重合体、ポリイソプレン、スチレン－イソプレン共重合体、ブタジエン－メタアクリル酸エステル共重合体、アクリル系ゴム、エチレン－プロピレンゴム、エチレン－プロピレン－ジエンゴム、水素添加ジエン系ゴムなどが挙げられる。これらのゴム成分は、単独もしくは２種以上を用いても良く、２種類以上のゴム成分を用いる場合、その混合比は特に限定されるものではない。 Examples of the rubber component include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, polyisoprene, styrene-isoprene copolymer, butadiene-methacrylate copolymer, acrylic rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, hydrogenated diene rubber, etc. These rubber components may be used alone or in combination of two or more kinds, and when two or more kinds of rubber components are used, the mixing ratio is not particularly limited.
また、ポリスチレン樹脂は、市場から回収した市場回収材であってもよく、例えば、エアコン、テレビ、冷蔵庫、洗濯機など家電製品や使用済みのＯＡ機器等の再生材を含んでいてもよい。
本発明の樹脂組成物は、ＰＳ樹脂を含有することにより、低コスト化することができる。
樹脂組成物におけるＰＳ樹脂の含有量は、多いほど低コスト化が可能であるが、低コスト化かつ良好な機械的強度、難燃性が得られる範囲を考慮すると、樹脂合計１００質量部に対して、２０質量部以上３０質量部以下含有することが好ましく、そのうち、２０質量部以上２５質量部未満がより好ましい。
The polystyrene resin may also be a recycled material collected from the market, and may include recycled materials from home appliances such as air conditioners, televisions, refrigerators, and washing machines, and used office equipment.
The resin composition of the present invention can be made less expensive by containing a PS resin.
The higher the content of PS resin in the resin composition, the more cost-effective it is. However, taking into consideration the range in which low cost and good mechanical strength and flame retardancy can be obtained, it is preferable for the resin composition to contain 20 parts by mass or more and 30 parts by mass or less, per 100 parts by mass of the total resin, and of this, 20 parts by mass or more but less than 25 parts by mass is more preferable.
（ＡＢＳ樹脂）
ＡＢＳ樹脂の製造方法は特に制限されないが、乳化状態のゴムに乳化状態のスチレン、アクリルニトリルの単量体を混ぜて重合させる乳化重合法；ゴムをスチレン、アクリルニトリルの単量体に溶解させて塊状重合させ、重合の途中でこの重合液を水中に懸濁させて懸濁重合条件下に重合を継続する塊状懸濁重合法等により製造することができる。なお、ＰＣ樹脂、ＰＳ樹脂及びＡＢＳ樹脂をアロイ化する際には、使用されるＡＢＳ樹脂の特性に応じた重合方法が選択されるが、一般には、乳化重合法および塊状懸濁重合法のいずれの重合方法において製造されたＡＢＳ樹脂でも、アロイ化は可能である。
(ABS resin)
The method for producing ABS resin is not particularly limited, but it can be produced by an emulsion polymerization method in which emulsified rubber is mixed with emulsified styrene and acrylonitrile monomers and polymerized; a bulk suspension polymerization method in which rubber is dissolved in styrene and acrylonitrile monomers and bulk polymerized, and the polymerization liquid is suspended in water during the polymerization to continue polymerization under suspension polymerization conditions, etc. When alloying PC resin, PS resin, and ABS resin, a polymerization method is selected according to the characteristics of the ABS resin used, but generally, ABS resin produced by either emulsion polymerization method or bulk suspension polymerization method can be alloyed.
また、ＡＢＳ樹脂は、市場から回収した市場回収材であってもよく、例えば、エアコン、テレビ、冷蔵庫、洗濯機など家電製品や使用済みのＯＡ機器等の再生材を含んでいてもよい。 The ABS resin may also be recycled material collected from the market, for example, recycled materials from home appliances such as air conditioners, televisions, refrigerators, and washing machines, or used office equipment.
（その他の樹脂）
本発明の樹脂組成物は、ＰＣ樹脂、ＰＳ樹脂、ＡＢＳ樹脂に加え、難燃性、剛性、耐衝撃性等を著しく低下させない範囲において、ＰＰ樹脂、ＰＥ樹脂を含有することができる。
(Other resins)
The resin composition of the present invention may contain, in addition to PC resin, PS resin and ABS resin, PP resin and PE resin to the extent that the flame retardancy, rigidity, impact resistance and the like are not significantly reduced.
ＰＣ樹脂とＡＢＳ樹脂の合計含有量は、樹脂合計１００質量部に対して７０質量部以上８５質量部以下であり、７５質量部以上８５質量部以下含有することが好ましい。ＰＣ樹脂とＡＢＳ樹脂の合計含有量が、樹脂合計１００質量部に対して７０質量部未満の場合、難燃性、耐衝撃強度が低下し、ＰＣ樹脂とＡＢＳ樹脂の合計含有量が、樹脂合計１００質量部に対して８５質量部を超えると、コストダウン効果が十分に得られない。 The total content of PC resin and ABS resin is 70 parts by mass or more and 85 parts by mass or less per 100 parts by mass of total resin, and preferably 75 parts by mass or more and 85 parts by mass or less. If the total content of PC resin and ABS resin is less than 70 parts by mass per 100 parts by mass of total resin, the flame retardancy and impact strength will decrease, and if the total content of PC resin and ABS resin is more than 85 parts by mass per 100 parts by mass of total resin, the cost reduction effect will not be sufficient.
（ホスファゼン系化合物）
前記ホスファゼン系化合物については、下記一般式（２）で表されるホスファゼン系化合物が、製造容易性及び化合物の安定性の点で好ましい。
さらに、前記ホスファゼン系化合物はその製造法により、環状の構成数が増加することがあるが、特に制限はなく、目的に応じて適宜選択することができる。
前記一般式（２）における側鎖基Ｘの脂肪族鎖、芳香族鎖はアルコキシ基構造を有しても良いし、末端にハロゲン元素を有しても良い。
アルコキシ基を形成する化合物は、脂肪族系化合物、芳香族系化合物など何でも良いが、芳香族環を含む化合物がホスファゼン系化合物の安定性のためとリン系化合物への溶解性のために好ましい。
これらの中でも、Ｘは、フェノキシ基が好ましい。
(Phosphazene compounds)
Of the phosphazene compounds, those represented by the following general formula (2) are preferred in terms of ease of production and compound stability.
Furthermore, the number of ring structures in the phosphazene compound may increase depending on the production method, but there is no particular restriction and can be appropriately selected depending on the purpose.
The aliphatic chain or aromatic chain of the side chain group X in the general formula (2) may have an alkoxy group structure or a halogen element at the terminal.
The compound that forms the alkoxy group may be any compound, such as an aliphatic compound or an aromatic compound, but a compound containing an aromatic ring is preferred for the stability of the phosphazene compound and for its solubility in the phosphorus compound.
Among these, X is preferably a phenoxy group.
このホスファゼン系化合物は、前記樹脂組成物の樹脂合計１００質量部に対し、０．１質量部以上４．０質量部以下含有される。好ましくは、樹脂合計１００質量部に対し、１．０質量部以上３．０質量部以下である。
前記含有率が、０．１質量部未満では、含有量が少なくて本発明の目的を達成できない。４．０質量部を超えて含有すると、混練時に樹脂組成物の中で凝集しやすくなるので好ましくない。前記含有率が、４．０質量部以下であると、樹脂組成物の中で凝集しにくくなり、本発明の目的を達成しやすくなる。
The phosphazene compound is contained in an amount of 0.1 to 4.0 parts by mass, preferably 1.0 to 3.0 parts by mass, per 100 parts by mass of the total resin of the resin composition.
If the content is less than 0.1 parts by mass, the content is too small to achieve the object of the present invention. If the content exceeds 4.0 parts by mass, the resin composition is likely to aggregate during kneading, which is not preferable. If the content is 4.0 parts by mass or less, the resin composition is unlikely to aggregate, making it easier to achieve the object of the present invention.
（ホスファゼン系化合物以外のリン系化合物）
本発明においてリン系化合物は、これまで述べたホスファゼン系化合物の凝集を防ぐためにホスファゼン系化合物以外のリン系化合物を併用することが好ましい。
ホスファゼン系化合物以外のリン系化合物としては赤燐、リン酸エステル、ポリリン酸アンモニウム、ポリリン酸ナトリウム、ホスフィン酸金属塩などが用いられ、赤燐、リン酸エステルが好ましく用いられる。なお、本発明におけるリン系化合物は燐の単体も含める。
中でも混練する温度で溶融するリン酸エステルを用いることが好ましい。
すなわちリン酸エステルは融点（Ｔｍ）を持つ化合物で、Ｔｍは３００℃未満が好ましく、２００℃未満がさらに好ましく、１００℃未満が特に好ましい。最も好ましいＴｍの下限は０℃以上であるが混練時に溶融状態になれば、Ｔｍの下限については本発明で制限しない。しかしＴｍが－４０℃未満であると樹脂に分散したときに時間が経過すると表面へ浮き出る現象、ブリードアウトが激しくなるので好ましくない。
前記リン酸エステルの中には、３次元化し混練時に溶融せずＴｍを持たない化合物も存在し、本発明でこのような化合物は好適ではない。
(Phosphorus compounds other than phosphazene compounds)
In the present invention, it is preferable to use the phosphorus-based compound in combination with a phosphorus-based compound other than the phosphazene-based compound in order to prevent the aggregation of the phosphazene-based compound described above.
Examples of phosphorus-based compounds other than phosphazene-based compounds include red phosphorus, phosphoric acid esters, ammonium polyphosphate, sodium polyphosphate, and metal phosphinates, with red phosphorus and phosphoric acid esters being preferred. The phosphorus-based compounds in the present invention include simple phosphorus.
Among these, it is preferable to use a phosphoric acid ester which melts at the kneading temperature.
That is, the phosphate ester is a compound having a melting point (Tm), and the Tm is preferably less than 300°C, more preferably less than 200°C, and particularly preferably less than 100°C. The most preferable lower limit of Tm is 0°C or higher, but if the phosphate ester is in a molten state during kneading, the lower limit of Tm is not limited in the present invention. However, if the Tm is less than -40°C, the phenomenon of the phosphate ester rising to the surface over time when dispersed in a resin becomes severe, which is called bleed-out, and is therefore undesirable.
Among the above-mentioned phosphate esters, there are some compounds which become three-dimensional, do not melt when kneaded, and have no Tm, and such compounds are not suitable for the present invention.
次に前記リン酸エステルを例示するが、この例示は本発明を特に制限するものではない。
例えばトリ（アルキルフェニル）ホスフェート、ジ（アルキルフェニル）モノフェニルホスフェート、ジフェニルモノ（アルキルフェニル）ホスフェートまたはトリフェニルホスフェートの中の一種または二種以上の混合物、あるいは下記一般式（３）で表される化合物の一種または二種以上の混合物である。
For example, it is one or a mixture of two or more of tri(alkylphenyl)phosphate, di(alkylphenyl)monophenyl phosphate, diphenyl mono(alkylphenyl) phosphate, or triphenyl phosphate, or one or a mixture of two or more of the compounds represented by the following general formula (3).
Ｒ3からＲ7までは、アリールまたはアルキル置換されたアリール基が好ましく、好ましいＲ3、Ｒ4、Ｒ6及びＲ7はフェニル基、またはメチル、エチル、イソプロピル、ｔ－ブチル、イソブチル、イソアミル、ｔ－アミルなどのアルキル基が置換されたフェニル基であり、この中でも、フェニル基、またはメチル、エチル、イソプロピルまたはｔ－ブチル基が置換されたフェニル基がより好ましく；Ｒ5は、アリールまたはアルキル置換されたアリール基誘導体が好ましく、レゾルシノール、ヒドロキノンまたはビスフェノール－Ａから誘導されたものがより好ましい。 R3 to R7 are preferably aryl or alkyl-substituted aryl groups, and preferred R3 , R4 , R6 and R7 are phenyl groups or phenyl groups substituted with alkyl groups such as methyl, ethyl, isopropyl, t-butyl, isobutyl, isoamyl, t-amyl, etc., and among these, phenyl groups or phenyl groups substituted with methyl, ethyl, isopropyl or t-butyl groups are more preferred; R5 is preferably an aryl or alkyl-substituted aryl group derivative, and more preferably one derived from resorcinol, hydroquinone or bisphenol-A.
リン系化合物の添加は、本発明の難燃性樹脂組成物の混練時に添加してもよいし、あらかじめＰＣ樹脂以外の高分子と混練し、この組成物を難燃性樹脂組成物の混練時に添加してもよい。 The phosphorus-based compound may be added when the flame-retardant resin composition of the present invention is kneaded, or it may be kneaded in advance with a polymer other than PC resin, and this composition may be added when the flame-retardant resin composition is kneaded.
前記リン系化合物のホスファゼン系化合物を含む総含有量は、機械的強度の低下防止のために、樹脂合計１００質量部に対し１６質量部未満であることが好ましく、３．５質量部以上１６質量部未満がより好ましい。１６質量部未満であると衝撃強度が低下しない。 The total content of the phosphorus-based compounds including the phosphazene-based compounds is preferably less than 16 parts by mass, and more preferably 3.5 parts by mass or more and less than 16 parts by mass, per 100 parts by mass of the total resin, in order to prevent a decrease in mechanical strength. If it is less than 16 parts by mass, the impact strength will not decrease.
ホスファゼン系化合物以外のリン系化合物の含有量は、リン酸エステルの場合は樹脂合計１００質量部に対して５質量部以上が好ましく、８質量部以上がより好ましい。赤燐の場合は、リン含有率が高いため、少量で難燃効果が得られる。樹脂合計１００質量に対して１質量部以上８質量部未満が好ましい。８質量部未満であると物性に影響しない。 The content of phosphorus-based compounds other than phosphazene-based compounds is preferably 5 parts by mass or more, and more preferably 8 parts by mass or more, per 100 parts by mass of total resin in the case of phosphoric acid esters. In the case of red phosphorus, the phosphorus content is high, so a small amount is enough to achieve flame retardant effects. It is preferable that the content is 1 part by mass or more and less than 8 parts by mass per 100 parts by mass of total resin. If it is less than 8 parts by mass, there is no effect on physical properties.
（その他添加剤）
本発明の一例の難燃性樹脂組成物は、難燃性、剛性、耐衝撃性等を著しく低下させない範囲において、リン系安定剤、フェノール系安定剤、染顔料等のその他の添加材を含んでよい。
(Other additives)
The flame-retardant resin composition of the present invention may contain other additives such as phosphorus-based stabilizers, phenol-based stabilizers, dyes and pigments, etc., within the range that does not significantly reduce the flame retardancy, rigidity, impact resistance, etc.
樹脂組成物から、含有される樹脂等を同定する方法としては、赤外分光法を用い、組成像により樹脂構造、リン系化合物を観察し、それぞれのスペクトルを取得することにより樹脂、リン系化合物を同定する方法等が挙げられる。
組成が一致した場合は、ＧＣＭＳを用いて各樹脂の検量線を作成し、各樹脂を定量することができる。
リン系化合物は溶媒抽出し、樹脂同様にＧＣＭＳにより定量することができる。
Examples of a method for identifying the resin and other components contained in a resin composition include a method in which infrared spectroscopy is used to observe the resin structure and the phosphorus-based compound from a composition image, and the resin and the phosphorus-based compound are identified by obtaining their respective spectra.
If the compositions match, a calibration curve for each resin can be created using GCMS, allowing each resin to be quantified.
Phosphorus compounds can be extracted with a solvent and quantified by GCMS in the same manner as resins.
本発明の樹脂組成物は、成形した試験片の２３℃におけるシャルピー衝撃強度が７．０ｋＪ／ｍ2以上であることが好ましい。シャルピー衝撃強度が７．０ｋＪ／ｍ2以上であると、靭性が高いと言える。シャルピー衝撃強度は、より好ましくは、８．０ｋＪ／ｍ2以上であり、さらに好ましくは１０．０ｋＪ／ｍ2以上である。
シャルピー衝撃強度は、ノッチ付き衝撃試験片を作製し、ＩＳＯ１７９－１に準拠して、シャルピー衝撃試験機を用いて２３℃で測定を行った。
また、本発明の樹脂組成物は、成形した試験片の２３℃における引張強度が４０ＭＰａ以上であることが好ましい。引張強度が４０ＭＰａ以上であると、剛性が高いと言える。
引張強度は、より好ましくは５０ＭＰａ以上であり、さらに好ましくは５５ＭＰａ以上である。
引張強度は、ＩＳＯ５２７－２に準拠して２３℃で測定を行った。
The resin composition of the present invention preferably has a Charpy impact strength of 7.0 kJ/ m2 or more at 23°C of a molded test piece. When the Charpy impact strength is 7.0 kJ/ m2 or more, it can be said that the toughness is high. The Charpy impact strength is more preferably 8.0 kJ/ m2 or more, and even more preferably 10.0 kJ/ m2 or more.
The Charpy impact strength was measured by preparing a notched impact test piece and measuring it at 23° C. using a Charpy impact tester in accordance with ISO 179-1.
Moreover, the resin composition of the present invention preferably has a tensile strength of 40 MPa or more at 23° C. when the molded test piece is used. When the tensile strength is 40 MPa or more, it can be said that the rigidity is high.
The tensile strength is more preferably 50 MPa or more, and further preferably 55 MPa or more.
The tensile strength was measured at 23° C. in accordance with ISO 527-2.
（樹脂組成物の製造方法）
本発明の樹脂組成物の製造方法の一例（以下、「一例の製造方法」ともいう）は、例えば、ＰＣ樹脂、ＰＳ樹脂、ＡＢＳ樹脂、リン系化合物、及び任意選択的に加えられる成分、並びに必要に応じて加えられるその他の添加剤を、溶融混練する溶融混練工程を含む。
(Method for producing resin composition)
An example of a method for producing the resin composition of the present invention (hereinafter also referred to as "an example of the production method") includes a melt-kneading step of melt-kneading, for example, a PC resin, a PS resin, an ABS resin, a phosphorus-based compound, and optionally added components, as well as other additives that are added as necessary.
＜溶融混練工程＞
一例の製造方法では、初めに、本発明に必要な成分、及び任意選択的に加えられる成分、並びに必要に応じて加えられるその他の添加剤を、溶融混練する（溶融混練工程）。
上記工程によれば、各成分を均一に混合することができる。
この工程では、上記各成分を、タンブラー、ヘンシェルミキサー、バンバリーミキサー、ロール、ブラベンダー、単軸混練押出機、二軸混練押出機、ニーダー等の当該技術分野において公知の混練機を用いて、混練速度、混練温度、混練時間等の条件を適宜調節しながら、混練する。
<Melt-kneading process>
In one example of the production method, first, the components necessary for the present invention, the components that are added optionally, and other additives that are added as necessary are melt-kneaded (melt-kneading step).
According to the above process, each component can be mixed uniformly.
In this step, the above-mentioned components are kneaded using a kneading machine known in the art, such as a tumbler, a Henschel mixer, a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader, while appropriately adjusting conditions such as the kneading speed, kneading temperature, and kneading time.
例えば、上記各成分を、タンブラー、ヘンシェルミキサー等を用いて、予め混合した後、バンバリーミキサー、ロール、ブラベンダー、単軸混練押出機、二軸混練押出機、ニーダー等の混練機で溶融混練してもよい。また、例えば、各成分を予め混合せずに、これらの成分をフィーダーを用いて押出機に投入し、溶融混練してもよい。更に、例えば、一部の成分のみを予め混合し、その後、溶融混練することによって得られる樹脂組成物をマスターバッチとし、このマスターバッチと再度残りの成分とを溶融混練してもよい。 For example, the above components may be mixed in advance using a tumbler, Henschel mixer, or the like, and then melt-kneaded using a kneading machine such as a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, or kneader. Alternatively, for example, the components may not be mixed in advance, but may be fed into an extruder using a feeder and melt-kneaded. Furthermore, for example, only some of the components may be mixed in advance, and then melt-kneaded to obtain a resin composition, which is used as a master batch, and the remaining components may be melt-kneaded again.
ここで、この工程では、特に限定されることなく、任意選択された成分を予め溶融混合させた後に、二軸混練押出機に添加することも好ましい。リン酸エステルが室温で液体の場合、ホスファゼン系化合物をこの成分に室温で溶解させることが可能である。また、リン酸エステルが室温で固体（例えば、粉末）の場合、これらの成分を乳鉢で混ぜた後、混合物を９０℃以上に加熱して溶融させ、この溶融状態の混合物を二軸混練押出機に添加することが可能である。 Here, in this step, it is also preferable to melt-mix the arbitrarily selected components in advance, without any particular limitation, and then add them to the twin-screw kneading extruder. If the phosphate ester is a liquid at room temperature, it is possible to dissolve the phosphazene compound in this component at room temperature. Also, if the phosphate ester is a solid (e.g., powder) at room temperature, it is possible to mix these components in a mortar, heat the mixture to 90°C or higher to melt it, and then add this molten mixture to the twin-screw kneading extruder.
なお、上記リン酸エステルとホスファゼン系化合物の予混合は、溶融混練工程の例示であり、リン系化合物の分散性を高める観点から、好ましい実施形態となるが、本発明の樹脂組成物の製造方法において必須となるものではない。また、上記乳鉢を用いた混合は、混合方法の例示であり、本発明の樹脂組成物の製造方法における混合方法は、これに限定されるものではなく、いかなる方法としてもよい。 The above premixing of the phosphoric acid ester and the phosphazene compound is an example of a melt-kneading process, and is a preferred embodiment from the viewpoint of increasing the dispersibility of the phosphorus compound, but is not essential in the method for producing the resin composition of the present invention. Furthermore, the mixing using the mortar is an example of a mixing method, and the mixing method in the method for producing the resin composition of the present invention is not limited to this, and any method may be used.
特に、混練温度は、ＰＣ樹脂の溶融温度（Ｔｍ）を基に決められる。Ｔｍの測定については、ガラス転移点（Ｔｇ）と同様にＤＳＣ、ＴＭＡ、ＤＴＡ、温度を変えられる粘弾性装置などどのような測定値を用いても良いが、これらの装置を用いて測定されたＴｍ温度付近で混練すれば本発明の樹脂組成物が容易に得られる。 In particular, the kneading temperature is determined based on the melting temperature (Tm) of the PC resin. As with the glass transition point (Tg), any measurement method may be used to measure Tm, such as DSC, TMA, DTA, or a viscoelastic device that can change the temperature. The resin composition of the present invention can be easily obtained by kneading near the Tm temperature measured using these devices.
また、このＴｍ温度未満では、剪断流動が効果的に働き、ホスファゼン系化合物のドメイン形成を阻害するので好ましい。特に混練温度をＴｍ未満からＴｇ＋２０℃の温度領域で本発明の好適な結果を得ることが可能である。 Below this Tm temperature, shear flow is effective and inhibits domain formation in the phosphazene compound, which is preferable. In particular, the preferred results of the present invention can be obtained by kneading at a temperature range from below Tm to Tg + 20°C.
ＴｍやＴｇについては測定方法で変わることが知られている。本発明では、ＤＳＣで計測されたＴｍやＴｇの値を用いるのが好ましい。 It is known that Tm and Tg vary depending on the measurement method. In the present invention, it is preferable to use the Tm and Tg values measured by DSC.
電子機器の説明
（成形体について）
本発明の一例の成形体（以下、「一例の成形体」ともいう）は、本発明の一例の樹脂組成物から成る。
一例の成形体としては、例えば、コンピューター、ノートブック型パソコン、タブレット端末、スマートフォン、携帯電話等の情報・モバイル機器やプリンター、複写機等のＯＡ機器等の部材等が挙げられる。特に、耐熱性を要する外装部材に好適に用いられる。
一例の成形体は、例えば、一例の樹脂組成物を常法に従って射出成形することによって得ることができる。
Explanation of electronic devices (molded products)
The molded article of the example of the present invention (hereinafter, also referred to as "example molded article") is made of the resin composition of the example of the present invention.
Examples of the molded article include components for information and mobile devices such as computers, notebook personal computers, tablet terminals, smartphones, and mobile phones, and office automation devices such as printers and copiers. In particular, the molded article is preferably used for exterior components that require heat resistance.
The example molded article can be obtained, for example, by injection molding the example resin composition according to a conventional method.
（電子部品、電子機器）
本発明の一例の電子部品は、本発明の前記成形体を有する。
本発明の一例の電子機器は、本発明の前記成形体を有する。
(Electronic parts, electronic devices)
An electronic device according to one embodiment of the present invention has the molded article according to the present invention.
An electronic device according to one embodiment of the present invention has the molded article according to the present invention.
前記電子部品としては、例えば、コンピューター、ノートブック型パソコン、タブレット端末、スマートフォン、携帯電話等の情報・モバイル機器やプリンター、複写機等のＯＡ機器等の電子部品等が挙げられる。
前記電子機器としては、例えば、コンピューター、ノートブック型パソコン、タブレット端末、スマートフォン、携帯電話等の情報・モバイル機器やプリンター、複写機等のＯＡ機器、テレビ、冷蔵庫、掃除機等の家庭電化製品等が挙げられる。
Examples of the electronic parts include electronic parts of information/mobile devices such as computers, notebook personal computers, tablet terminals, smartphones, and mobile phones, and office automation devices such as printers and copiers.
Examples of the electronic device include information/mobile devices such as computers, notebook computers, tablet terminals, smartphones, and mobile phones, office automation equipment such as printers and copiers, and home appliances such as televisions, refrigerators, and vacuum cleaners.
なお、本発明は下記（１）に記載の樹脂組成物に係るものであるが、下記（２）～（９）を発明の実施形態として含む。
（１）ＰＣ樹脂、ＰＳ樹脂、ＡＢＳ樹脂、およびリン系化合物を含有する樹脂組成物であって、
前記ＰＣ樹脂を、樹脂合計１００質量部に対して４５質量部以上７０質量部未満含有し、
前記ＰＣ樹脂とＡＢＳ樹脂とを合計で、樹脂合計１００質量部に対し７０質量部以上８５質量部以下含有し、
前記ＰＳ樹脂を、樹脂合計１００質量部に対し１５質量部以上３０質量部以下含有し、
前記リン系化合物は、そのうち少なくとも一種がホスファゼン系化合物であり、
前記ホスファゼン系化合物を樹脂合計１００質量部に対し０．１質量部以上４．０質量部以下含有する樹脂組成物。
（２）前記ホスファゼン系化合物を含む前記リン系化合物の総含有量が樹脂合計１００質量部に対し１６質量部未満である、上記（１）に記載の樹脂組成物。
（３）前記ＰＣ樹脂を樹脂合計１００質量部に対し６０質量部以上７０質量部未満含有する、上記（１）または（２）に記載の樹脂組成物。
（４）前記リン系化合物が、ホスファゼン系化合物と、ホスファゼン系化合物以外のリン系化合物を含有し、前記ホスファゼン系化合物以外のリン系化合物が、赤燐および／またはリン酸エステルである、上記（１）乃至（３）のいずれか１項に記載の樹脂組成物。
（５）２３℃におけるシャルピー衝撃強度が４．０ｋＪ／ｍ２以上である、上記（１）乃至（４）のいずれか１項に記載の樹脂組成物。
（６）２３℃における引張強度が４０ＭＰａ以上である、上記（１）乃至（５）のいずれか１項に記載の樹脂組成物。
（７）上記（１）乃至（６）のいずれか１項に記載の樹脂組成物から成ることを特徴とする成形体。
（８）上記（７）に記載の成形体を有することを特徴とする電子部品。
（９）上記（７）に記載の成形体を有することを特徴とする電子機器。
The present invention relates to the resin composition described in (1) below, but also includes the following (2) to (9) as embodiments of the invention.
(1) A resin composition containing a PC resin, a PS resin, an ABS resin, and a phosphorus-based compound,
The PC resin is contained in an amount of 45 parts by mass or more and less than 70 parts by mass per 100 parts by mass of the total resin,
The PC resin and the ABS resin are contained in a total amount of 70 parts by mass or more and 85 parts by mass or less per 100 parts by mass of the total resin,
The PS resin is contained in an amount of 15 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the total resin,
At least one of the phosphorus-based compounds is a phosphazene-based compound,
The resin composition contains the phosphazene compound in an amount of 0.1 parts by mass or more and 4.0 parts by mass or less per 100 parts by mass of the total resin.
(2) The resin composition according to (1) above, wherein the total content of the phosphorus-based compounds including the phosphazene-based compound is less than 16 parts by mass per 100 parts by mass of the total resin.
(3) The resin composition according to (1) or (2) above, containing the PC resin in an amount of 60 parts by mass or more and less than 70 parts by mass per 100 parts by mass of the total resin.
(4) The resin composition according to any one of (1) to (3), wherein the phosphorus-based compound contains a phosphazene-based compound and a phosphorus-based compound other than the phosphazene-based compound, and the phosphorus-based compound other than the phosphazene-based compound is red phosphorus and/or a phosphoric acid ester.
(5) The resin composition according to any one of (1) to (4), having a Charpy impact strength at 23°C of 4.0 kJ / m2 or more.
(6) The resin composition according to any one of (1) to (5) above, having a tensile strength at 23° C. of 40 MPa or more.
(7) A molded article comprising the resin composition according to any one of (1) to (6) above.
(8) An electronic component comprising the molded article according to (7) above.
(9) An electronic device comprising the molded article according to (7) above.
以下に実施例に基づいて本発明をより詳細に説明するが、本発明の技術的範囲は下記実施例に何ら限定されるものではない。 The present invention will be described in more detail below with reference to examples, but the technical scope of the present invention is not limited to the following examples.
（実施例１～１５、比較例１～６）
表１～表３に示す組成（質量部）で原料を配合し、原材料をスクリュー径２５ｍｍ、スクリュー有効長Ｌ／Ｄ＝２６の二軸溶融混練押出機（テクノベル製）を用いて、シリンダ温度２３０℃で混練して樹脂組成物を得た。
次に得られた樹脂組成物を用いて、設定温度２４０℃で溶融し、射出成形して評価片を得た。
(Examples 1 to 15, Comparative Examples 1 to 6)
The raw materials were blended according to the compositions (parts by mass) shown in Tables 1 to 3, and the raw materials were kneaded at a cylinder temperature of 230°C using a twin-screw melt kneading extruder (manufactured by Technovel) with a screw diameter of 25 mm and an effective screw length L/D = 26 to obtain resin compositions.
Next, the obtained resin composition was melted at a set temperature of 240° C. and injection molded to obtain an evaluation piece.
表１～表３に記載の原材料は以下の通りである。
尚、表１～表３においては、「部数」の欄は、配合した原料の質量部数を、「比率」の欄は、樹脂合計１００質量部に対する質量部数を示す。
［原材料］
（樹脂）
ＰＣ樹脂：Ｈ－３０００ＶＲ（三菱エンジニアリングプラスチックス社製）
ＰＳ樹脂：Ｈ６５０（東洋スチレン社製）
ＡＢＳ樹脂：２５０－Ｘ１０（東レ社製）
（リン系化合物）
ホスファゼン系化合物：ＳＰＳ１００
（大塚化学社製、主成分として、６員環の環状構造を有し、その６個
の側鎖全てがフェノキシ基である芳香族ホスファゼン化合物）
リン酸エステル：ＰＸ－２００
（大八化学社製、芳香族縮合リン酸エステル、融点９２℃以上）、
赤燐：高純度赤燐（日本化学工業社製）
The raw materials listed in Tables 1 to 3 are as follows.
In Tables 1 to 3, the "Parts" column indicates the parts by mass of the blended raw materials, and the "Ratio" column indicates the parts by mass relative to 100 parts by mass of the total resin.
[raw materials]
(resin)
PC resin: H-3000VR (manufactured by Mitsubishi Engineering Plastics Corporation)
PS resin: H650 (manufactured by Toyo Styrene Co., Ltd.)
ABS resin: 250-X10 (manufactured by Toray Industries, Inc.)
(Phosphorus compounds)
Phosphazene compound: SPS100
(Otsuka Chemical Co., Ltd., mainly contains a six-membered ring structure,
(Aromatic phosphazene compound in which all side chains are phenoxy groups)
Phosphate ester: PX-200
(manufactured by Daihachi Chemical Industry Co., Ltd., aromatic condensed phosphate ester, melting point 92°C or higher),
Red phosphorus: High-purity red phosphorus (manufactured by Nippon Chemical Industry Co., Ltd.)
［評価試験方法］
得られた評価片を用いて、以下の評価を行った。
（シャルピー衝撃強度）
ＩＳＯ１７９－１に準拠して、シャルピー衝撃試験機を用いて、２３℃において、衝撃試験を行った。なお、試験片にはノッチ（切れ目）を付けた。測定値（ｋＪ／ｍ2）が高い値であるほど、耐衝撃性に優れていると評価した。
［評価基準］
ランク 測定値（ｋＪ／ｍ2）
◎ ： ６．０以上
〇 ： ５．０以上６．０未満
△ ： ４．０以上５．０未満
× ： ４未満
[Evaluation test method]
The obtained evaluation pieces were used to carry out the following evaluations.
(Charpy impact strength)
An impact test was carried out at 23° C. using a Charpy impact tester in accordance with ISO 179-1. The test specimens were notched. The higher the measured value (kJ/m 2 ), the more excellent the impact resistance was evaluated to be.
[Evaluation criteria]
Rank Measured value (kJ/ m2 )
◎: 6.0 or more 〇: 5.0 or more and less than 6.0 △: 4.0 or more and less than 5.0 ×: Less than 4
（引張強度）
ＩＳＯ５２７－２に準拠して、２３℃において、引張試験を行った。測定値（ＭＰａ）が高い値であるほど、剛性（引張強度）に優れていると評価した。
［評価基準］
ランク 測定値（ＭＰａ）
◎ ： ５０以上
〇 ： ４５以上５０未満
△ ： ４０以上４５未満
× ： ４０未満
(Tensile strength)
A tensile test was carried out in accordance with ISO 527-2 at 23° C. The higher the measured value (MPa), the more excellent the rigidity (tensile strength) was evaluated to be.
[Evaluation criteria]
Rank Measured value (MPa)
◎: 50 or more 〇: 45 or more but less than 50 △: 40 or more but less than 45 ×: Less than 40
（難燃性）
米国アンダーライターズ・ラボラトリーズ（ＵＬ）が定めるＵＬ９４試験（機器の部品用プラスチック材料の燃焼試験）に準拠して、難燃試験を行なった。試験片の厚みｔは１．５ｍｍとした。
まずＵＬ９４Ｖ試験を行い、「Ｖ－０」、「Ｖ－１」、「Ｖ－２」の判定を行った。
次に、前記ＵＬ９４Ｖ試験において、「Ｖ－０」、または「Ｖ－１」ランクに適合した材料について、ＵＬ９４－５Ｖ試験を行い、「５Ｖ－Ａ」、「５Ｖ－Ｂ」の判定を行った。
前記ＵＬ９４－５Ｖ試験において「５Ｖ－Ａ」、「５Ｖ－Ｂ」のいずれの基準も満たすことができなかった場合、表１において、ＵＬ９４－５Ｖ試験の結果を「－」と示した。
前記ＵＬ９４－５Ｖ試験において「５Ｖ－Ａ」、「５Ｖ－Ｂ」である場合が合格であり、ＵＬ９４Ｖ試験の結果が「Ｖ－０」、「Ｖ－１」であっても、ＵＬ９４－５Ｖ試験において「５Ｖ－Ａ」、「５Ｖ－Ｂ」のいずれの基準も満たすことができなかった場合は、不合格とした。
(Flame retardance)
A flame retardancy test was carried out in accordance with the UL94 test (combustion test for plastic materials for device parts) specified by Underwriters Laboratories (UL) in the U.S. The thickness t of the test piece was 1.5 mm.
First, a UL94V test was carried out and the samples were rated as "V-0", "V-1" or "V-2".
Next, the materials that met the "V-0" or "V-1" rank in the UL94V test were subjected to a UL94-5V test and were judged as "5V-A" or "5V-B".
In the UL94-5V test, if the criteria for either "5V-A" or "5V-B" were not met, the result of the UL94-5V test in Table 1 was indicated as "-".
The UL94-5V test was passed if it was "5V-A" or "5V-B", and was failed if it did not meet either of the criteria of "5V-A" or "5V-B" in the UL94-5V test, even if the result of the UL94V test was "V-0" or "V-1".
（成形性）
上記評価片の外観を観察し、表面に現れたブツの数により成形性を評価した。
◎ ：ブツ無し
〇 ：ブツ３個未満
△ ：ブツ３個以上５個未満
× ：ブツ５個以上
(Moldability)
The appearance of the evaluation piece was observed, and the moldability was evaluated based on the number of bumps that appeared on the surface.
◎: No lumps 〇: Less than 3 lumps △: 3 to less than 5 lumps ×: 5 or more lumps
（ＰＳ樹脂比率）
ＰＳ樹脂の比率の数値により、コストについて評価した。
［評価基準］
ランク 配合比率（樹脂１００質量部に対する配合質量部数）
◎ ：２２以上
〇 ：１８以上２２未満
△ ：１５以上１８未満
× ：１５未満
(PS resin ratio)
The cost was evaluated based on the ratio of PS resin.
[Evaluation criteria]
Rank Mixing ratio (number of parts by mass per 100 parts by mass of resin)
◎: 22 or more 〇: 18 or more and less than 22 △: 15 or more and less than 18 ×: Less than 15
表１～表３に実施例及び比較例の樹脂組成物についての樹脂組成、シャルピー衝撃強度、引張強度、難燃性、成形性及びＰＳ樹脂比率についての数値を示す。
また、表４に実施例及び比較例の樹脂組成物について評価結果を示す。
Tables 1 to 3 show the resin composition, Charpy impact strength, tensile strength, flame retardancy, moldability and PS resin ratio for the resin compositions of the examples and comparative examples.
Table 4 shows the evaluation results for the resin compositions of the examples and comparative examples.
Claims (9)
前記ＰＣ樹脂を、樹脂合計１００質量部に対して４５質量部以上７０質量部未満含有し、
前記ＡＢＳ樹脂を、樹脂合計１００質量部に対して１５質量部以上４０質量部以下含有し、
前記ＰＣ樹脂とＡＢＳ樹脂とを合計で、樹脂合計１００質量部に対して７０質量部以上８５質量部以下含有し、
前記ＰＳ樹脂を、樹脂合計１００質量部に対して１５質量部以上３０質量部以下含有し、
前記ＰＣ樹脂が芳香族ポリカーボネート樹脂であり、
前記リン系化合物は、そのうち少なくとも一種がホスファゼン系化合物であり、
前記ホスファゼン系化合物を樹脂合計１００質量部に対し０．１質量部以上４．０質量部以下含有する樹脂組成物。 A resin composition containing a PC resin, a PS resin, an ABS resin, and a phosphorus-based compound,
The PC resin is contained in an amount of 45 parts by mass or more and less than 70 parts by mass per 100 parts by mass of the total resin,
The ABS resin is contained in an amount of 15 parts by mass or more and 40 parts by mass or less per 100 parts by mass of the total resin,
The PC resin and the ABS resin are contained in a total amount of 70 parts by mass or more and 85 parts by mass or less per 100 parts by mass of the total resin,
The PS resin is contained in an amount of 15 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the total resin,
The PC resin is an aromatic polycarbonate resin,
At least one of the phosphorus-based compounds is a phosphazene-based compound,
The resin composition contains the phosphazene compound in an amount of 0.1 parts by mass or more and 4.0 parts by mass or less per 100 parts by mass of the total resin.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001123058A (en) | 1999-10-23 | 2001-05-08 | Cheil Industries Inc | Thermoplastic resin composition having flame retardance |
| JP2009137942A (en) | 2007-12-10 | 2009-06-25 | Cheil Industries Inc | Sterically hindered phenyl-containing phosphonate compound, method for producing the same, and flame-retardant polycarbonate resin composition containing the same |
| JP2016003290A (en) | 2014-06-17 | 2016-01-12 | 明文産業株式会社 | Flame-retardant resin composition, molded body and method for producing flame-retardant resin composition |
| JP2019119887A (en) | 2017-12-29 | 2019-07-22 | ロッテ アドバンスト マテリアルズ カンパニー リミテッド | Thermoplastic resin composition and molded article molded therefrom |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001123058A (en) | 1999-10-23 | 2001-05-08 | Cheil Industries Inc | Thermoplastic resin composition having flame retardance |
| JP2009137942A (en) | 2007-12-10 | 2009-06-25 | Cheil Industries Inc | Sterically hindered phenyl-containing phosphonate compound, method for producing the same, and flame-retardant polycarbonate resin composition containing the same |
| JP2016003290A (en) | 2014-06-17 | 2016-01-12 | 明文産業株式会社 | Flame-retardant resin composition, molded body and method for producing flame-retardant resin composition |
| JP2019119887A (en) | 2017-12-29 | 2019-07-22 | ロッテ アドバンスト マテリアルズ カンパニー リミテッド | Thermoplastic resin composition and molded article molded therefrom |
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