JP7359194B2 - Resin compositions, molded bodies, and vehicle parts - Google Patents
Resin compositions, molded bodies, and vehicle parts Download PDFInfo
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- JP7359194B2 JP7359194B2 JP2021115771A JP2021115771A JP7359194B2 JP 7359194 B2 JP7359194 B2 JP 7359194B2 JP 2021115771 A JP2021115771 A JP 2021115771A JP 2021115771 A JP2021115771 A JP 2021115771A JP 7359194 B2 JP7359194 B2 JP 7359194B2
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- 239000011342 resin composition Substances 0.000 title claims description 59
- -1 molded bodies Substances 0.000 title description 9
- 229920001577 copolymer Polymers 0.000 claims description 84
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 69
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 43
- 238000000465 moulding Methods 0.000 claims description 35
- 239000006082 mold release agent Substances 0.000 claims description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 125000000524 functional group Chemical group 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 16
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical group O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 claims description 3
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 claims description 3
- BYNVYIUJKRRNNC-UHFFFAOYSA-N docosanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCCCCCCCCCCCCCCCC(O)=O BYNVYIUJKRRNNC-UHFFFAOYSA-N 0.000 claims description 3
- GHBFNMLVSPCDGN-UHFFFAOYSA-N rac-1-monooctanoylglycerol Chemical compound CCCCCCCC(=O)OCC(O)CO GHBFNMLVSPCDGN-UHFFFAOYSA-N 0.000 claims description 3
- IYVVKFYDGRJWTR-UHFFFAOYSA-N 2-decanoylglycerol Chemical compound CCCCCCCCCC(=O)OC(CO)CO IYVVKFYDGRJWTR-UHFFFAOYSA-N 0.000 claims description 2
- UWLPCYBIJSLGQO-UHFFFAOYSA-N dodecanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCCCCCC(O)=O UWLPCYBIJSLGQO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000004925 Acrylic resin Substances 0.000 description 9
- 229920000178 Acrylic resin Polymers 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 238000004898 kneading Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 230000001771 impaired effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 238000005482 strain hardening Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000004035 construction material Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- SKKHNUKNMQLBTJ-UHFFFAOYSA-N 3-bicyclo[2.2.1]heptanyl 2-methylprop-2-enoate Chemical compound C1CC2C(OC(=O)C(=C)C)CC1C2 SKKHNUKNMQLBTJ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 235000021189 garnishes Nutrition 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- ARIWANIATODDMH-AWEZNQCLSA-N 1-lauroyl-sn-glycerol Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)CO ARIWANIATODDMH-AWEZNQCLSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- QJKFETKWAWVFBY-UHFFFAOYSA-N 5-(benzylamino)-5-oxopentanoic acid Chemical compound OC(=O)CCCC(=O)NCC1=CC=CC=C1 QJKFETKWAWVFBY-UHFFFAOYSA-N 0.000 description 1
- ARIWANIATODDMH-UHFFFAOYSA-N Lauric acid monoglyceride Natural products CCCCCCCCCCCC(=O)OCC(O)CO ARIWANIATODDMH-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- AVTLBBWTUPQRAY-BUHFOSPRSA-N V-59 Substances CCC(C)(C#N)\N=N\C(C)(CC)C#N AVTLBBWTUPQRAY-BUHFOSPRSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- DEWNCLAWVNEDHG-UHFFFAOYSA-M sodium;2-(2-methylprop-2-enoyloxy)ethanesulfonate Chemical compound [Na+].CC(=C)C(=O)OCCS([O-])(=O)=O DEWNCLAWVNEDHG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、樹脂組成物、成形体及び車両用部品に関する。 The present invention relates to a resin composition , a molded article, and a vehicle part.
ポリメチルメタクリレートやポリカーボネートは、優れた透明性や寸法安定性から、光学材料、車両用部品、照明用材料、建築用材料等、様々な分野で幅広く用いられている。近年、ポリメチルメタクリレートやポリカーボネートの成形体は、部品の薄肉化や細密化に伴い、より高性能化が求められている。その性能の１つとして、耐熱性が挙げられる。特に、テールランプやヘッドランプ等の車両用部品は、自動車等の車両が高温多湿下でも用いられるため、より優れた耐熱性が求められている。 Polymethyl methacrylate and polycarbonate are widely used in various fields such as optical materials, vehicle parts, lighting materials, and construction materials due to their excellent transparency and dimensional stability. In recent years, molded bodies of polymethyl methacrylate and polycarbonate are required to have higher performance as parts become thinner and more detailed. One of its properties is heat resistance. In particular, vehicle parts such as tail lamps and head lamps are required to have better heat resistance because vehicles such as automobiles are used even under high temperature and humidity.
しかしながら、ポリメチルメタクリレートは、優れた透明性や耐候性を有するものの、耐熱性が十分ではなかった。また、ポリカーボネートは、優れた耐熱性や耐衝撃性を有するものの、光学的歪みである複屈折率が大きく成形体に光学的異方性が生じる、また、成形加工性や耐傷性や耐油性に著しく劣る。 However, although polymethyl methacrylate has excellent transparency and weather resistance, it does not have sufficient heat resistance. In addition, although polycarbonate has excellent heat resistance and impact resistance, it has a large birefringence, which is an optical distortion, and optical anisotropy occurs in molded products, and it also has poor moldability, scratch resistance, and oil resistance. Significantly inferior.
そのため、ポリメチルメタクリレートに代表されるアクリル樹脂の耐熱性を改善する検討が行われている。例えば、特許文献１には、メチルメタクリレート単位とメタクリル酸単位とグルタル酸無水物単位を有する共重合体が提案されている。 Therefore, studies are being conducted to improve the heat resistance of acrylic resins such as polymethyl methacrylate. For example, Patent Document 1 proposes a copolymer having methyl methacrylate units, methacrylic acid units, and glutaric anhydride units.
しかしながら、特許文献１で提案されている共重合体は、グルタル酸無水物単位（無水グルタル酸単位）が過剰であるため、外観、低吸水性、成形性に劣る。 However, the copolymer proposed in Patent Document 1 has an excess of glutaric anhydride units (glutaric anhydride units), and therefore is inferior in appearance, low water absorption, and moldability.
そこで、本発明の目的は、耐熱性、流動性、機械特性、外観、低吸水性、成形性に優れた共重合体を提供することにある。また、本発明の目的は、得られる共重合体の耐熱性、流動性、機械特性、外観、低吸水性、成形性に優れる共重合体の製造方法を提供することにある。 Therefore, an object of the present invention is to provide a copolymer that is excellent in heat resistance, fluidity, mechanical properties, appearance, low water absorption, and moldability. Another object of the present invention is to provide a method for producing a copolymer that has excellent heat resistance, fluidity, mechanical properties, appearance, low water absorption, and moldability.
（１）メチル（メタ）アクリレート単位（Ａ１）及び（メタ）アクリル酸単位（Ａ２）を含む共重合体（Ａ）と、少なくとも２つの官能基を有する有機物である離型剤（Ｂ）とを含有し、下記式（１’）で示す（メタ）アクリル酸単位（Ａ２）の残存率が、５０％以上である、樹脂組成物。
（メタ）アクリル酸単位（Ａ２）の残存率（％）＝｛［共重合体中の（メタ）アクリル酸単位（Ａ２）の割合（ｍｏｌ％）］／（［共重合体中の（メタ）アクリル酸単位（Ａ２）の割合（ｍｏｌ％）］＋［共重合体中の無水グルタル酸単位（Ａ３）の割合（ｍｏｌ％）］）｝×１００・・・（１’）
（２）前記式（１’）で示す（メタ）アクリル酸単位（Ａ２）の残存率が、９０％以上である、前記の樹脂組成物。
（３）メチル（メタ）アクリレート単位（Ａ１）及び（メタ）アクリル酸単位（Ａ２）を含む共重合体（Ａ）を含有し、下記条件（２’）を満たす前記の樹脂組成物。
１０≧樹脂組成物の積分分子量分布より求めた２５０℃、２０分加熱後のｌｏｇ［２Ｍｗ］以上の割合％／樹脂組成物の積分分子量分布より求めた加熱前のｌｏｇ［２Ｍｗ］以上の割合％≧１．５・・・（２’）
（４）離型剤（Ｂ）の有機物は少なくとも２つの官能基を有する前記の樹脂組成物。
（５）離型剤（Ｂ）の有機物が有する官能基が、ヒドロキシル基、カルボキシル基、アミノ基、アミド基からなる群より選ばれる少なくとも１種である、前記の樹脂組成物。
（６）少なくとも２つの官能基を有する有機物である離型剤（Ｂ）の分子量が、１００～５００である、前記の樹脂組成物。
（７）少なくとも２つの官能基を有する有機物である離型剤（Ｂ）が、グリセリンモノステアレート、グリセリンモノベヘネート、グリセリンモノ１，２－ヒドロキシステアレート、グリセリンモノオレート、グリセリンモノカプリレート、グリセリンモノカプレート及びグリセリンモノラウレートからなる群より選ばれる少なくとも１種である、前記の樹脂組成物。
（８）少なくとも２つの官能基を有する有機物である離型剤（Ｂ）の含有量が、共重合体（Ａ）１００質量部に対して、０．０１質量部～１質量部である、前記の樹脂組成物。
（９）共重合体（Ａ）が、更に、無水グルタル酸単位（Ａ３）を含む、前記の樹脂組成物。
（１０）共重合体（Ａ）を構成する単量体単位において、メチル（メタ）アクリレート単位（Ａ１）が８０ｍｏｌ％以上、（メタ）アクリル酸由来の繰り返し単位（Ａ２）が１ｍｏｌ％～１５ｍｏｌ％、及び無水グルタル酸単位（Ａ３）が５ｍｏｌ％以下である、前記の樹脂組成物。
(1) A copolymer (A) containing methyl (meth)acrylate units (A1) and (meth)acrylic acid units (A2) and a mold release agent (B) which is an organic substance having at least two functional groups. A resin composition containing 50% or more of (meth)acrylic acid units (A2) represented by the following formula (1').
Remaining rate (%) of (meth)acrylic acid units (A2) = {[ratio (mol%) of (meth)acrylic acid units (A2) in the copolymer]/([(meth)acrylic acid units (A2) in the copolymer Proportion of acrylic acid units (A2) (mol%) + [proportion of glutaric anhydride units (A3) in copolymer (mol%)]) x 100... (1')
(2) The resin composition described above, wherein the residual rate of the (meth)acrylic acid unit (A2) represented by the formula (1') is 90% or more.
(3) The resin composition described above, which contains a copolymer (A) containing methyl (meth)acrylate units (A1) and (meth)acrylic acid units (A2), and satisfies the following condition (2').
10≧Proportion% of log[2Mw] or more after heating at 250°C for 20 minutes determined from the integral molecular weight distribution of the resin composition/Proportion% of log[2Mw] or more before heating determined from the integral molecular weight distribution of the resin composition ≧1.5...(2')
(4) The resin composition described above, in which the organic substance of the mold release agent (B) has at least two functional groups.
(5) The resin composition described above, wherein the organic substance of the mold release agent (B) has at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and an amide group.
(6) The resin composition described above, wherein the mold release agent (B), which is an organic substance having at least two functional groups, has a molecular weight of 100 to 500.
(7) The mold release agent (B) which is an organic substance having at least two functional groups is glycerin monostearate, glycerin monobehenate, glycerin mono-1,2-hydroxystearate, glycerin monooleate, glycerin monocaprylate, The above resin composition is at least one member selected from the group consisting of glycerin monocaprate and glycerin monolaurate.
(8) The content of the mold release agent (B), which is an organic substance having at least two functional groups, is 0.01 part by mass to 1 part by mass with respect to 100 parts by mass of the copolymer (A). resin composition.
(9) The above resin composition, wherein the copolymer (A) further contains a glutaric anhydride unit (A3).
(10) In the monomer units constituting the copolymer (A), 80 mol% or more of methyl (meth)acrylate units (A1) and 1 mol% to 15 mol% of repeating units (A2) derived from (meth)acrylic acid , and the resin composition described above, wherein the glutaric anhydride unit (A3) is 5 mol% or less.
（１１）メチル（メタ）アクリレート（ａ１）及び（メタ）アクリル酸（ａ２）を含む単量体を重合して前駆体を得て、得られた前駆体と少なくとも２つの官能基を有する有機物である離型剤（Ｂ）とを溶融混練し、前記式（１’）で示す（メタ）アクリル酸単位（ａ２）の残存率を５０％以上とする、樹脂組成物の製造方法。
（１２）重合方法が、懸濁重合である、前記の樹脂組成物の製造方法。
（１３）少なくとも２つの官能基を有する有機物である離型剤（Ｂ）の含有量が、前駆体１００質量部に対して、０．０１～１質量部である、前記の樹脂組成物の製造方法。
（１４）溶融混練温度が、１５０℃～２７０℃である、前記の樹脂組成物の製造方法。
(11) A precursor is obtained by polymerizing a monomer containing methyl (meth)acrylate (a1) and (meth)acrylic acid (a2), and the obtained precursor is combined with an organic substance having at least two functional groups. A method for producing a resin composition, which comprises melt-kneading a certain mold release agent (B) so that the residual rate of (meth)acrylic acid units (a2) represented by the formula (1') is 50% or more.
(12) The method for producing the resin composition described above, wherein the polymerization method is suspension polymerization.
(13) Production of the resin composition described above, wherein the content of the mold release agent (B), which is an organic substance having at least two functional groups, is 0.01 to 1 part by mass based on 100 parts by mass of the precursor. Method.
(14) The method for producing the resin composition described above, wherein the melt-kneading temperature is 150°C to 270°C.
（１５）前記の樹脂組成物を成形した成形体。
（１６）前記の成形体を含む車両用部品。
(15) A molded article obtained by molding the resin composition described above.
(16) A vehicle part including the molded article.
本発明の樹脂組成物は、耐熱性、流動性、機械特性、外観、低吸水性、成形性に優れる。
また、本発明の樹脂組成物の製造方法は、得られる樹脂組成物の耐熱性、流動性、機械特性、外観、低吸水性、成形性に優れる。
更に、本発明の成形体は、耐熱性、流動性、機械特性、外観、低吸水性、成形性に優れる。
The resin composition of the present invention has excellent heat resistance, fluidity, mechanical properties, appearance, low water absorption, and moldability.
Furthermore, the method for producing a resin composition of the present invention provides a resin composition that is excellent in heat resistance, fluidity, mechanical properties, appearance, low water absorption, and moldability.
Furthermore, the molded article of the present invention has excellent heat resistance, fluidity, mechanical properties, appearance, low water absorption, and moldability.
本発明の樹脂組成物において共重合体（Ａ）は、メチル（メタ）アクリレート単位（Ａ１）及び（メタ）アクリル酸単位（Ａ２）（以下、単に「単位（Ａ１）」、「単位（Ａ２）」ということがある。）を含む。 In the resin composition of the present invention, the copolymer (A) includes methyl (meth)acrylate units (A1) and (meth)acrylic acid units (A2) (hereinafter simply referred to as "units (A1)" and "units (A2)"). ).
単位（Ａ１）及び単位（Ａ２）を含む共重合体中の単位（Ａ１）の含有率は、共重合体１００ｍｏｌ％中、８０ｍｏｌ％以上９９ｍｏｌ％以下がより好ましく、９０ｍｏｌ％以上９８ｍｏｌ％以下が更に好ましい。単位（Ａ１）の含有率が８０ｍｏｌ％以上であると、特に、外観、低吸水性、成形性の観点で、アクリル樹脂本来の性能を損なわない。また、単位（Ａ１）の含有率が９９ｍｏｌ％以下であると、共重合体の耐熱性、機械特性に優れる。
尚、本明細書において、共重合体中の各単位の含有率は、１Ｈ－ＮＭＲ測定から算出した値とする。
The content of the unit (A1) in the copolymer containing the unit (A1) and the unit (A2) is more preferably 80 mol% or more and 99 mol% or less, more preferably 90 mol% or more and 98 mol% or less, based on 100 mol% of the copolymer. preferable. When the content of the unit (A1) is 80 mol% or more, the inherent performance of the acrylic resin is not impaired, particularly in terms of appearance, low water absorption, and moldability. Moreover, when the content of the unit (A1) is 99 mol% or less, the copolymer has excellent heat resistance and mechanical properties.
In this specification, the content of each unit in the copolymer is a value calculated from 1 H-NMR measurement.
単位（Ａ１）及び単位（Ａ２）を含む共重合体中の単位（Ａ２）の含有率は、共重合体１００ｍｏｌ％中、０．４５ｍｏｌ％以上７ｍｏｌ％以下が好ましく、０．５ｍｏｌ％以上６ｍｏｌ％以下がより好ましい。単位（Ａ２）の含有率が０．４５ｍｏｌ％以上であると、共重合体の耐熱性、機械特性に優れる。また、単位（Ａ２）の含有率が７ｍｏｌ％以下であると、特に、外観、低吸水性、成形性の観点で、アクリル樹脂本来の性能を損なわない。 The content of the unit (A2) in the copolymer containing the unit (A1) and the unit (A2) is preferably 0.45 mol% or more and 7 mol% or less, and 0.5 mol% or more and 6 mol% or less, based on 100 mol% of the copolymer. The following are more preferable. When the content of the unit (A2) is 0.45 mol% or more, the copolymer has excellent heat resistance and mechanical properties. Moreover, when the content of the unit (A2) is 7 mol % or less, the inherent performance of the acrylic resin is not impaired, especially in terms of appearance, low water absorption, and moldability.
単位（Ａ１）及び単位（Ａ２）を含む共重合体中の（メタ）アクリル酸単位（Ａ２）の残存率が、５０％以上が好ましく、９０％以上がより好ましい。また、単位（Ａ１）及び単位（Ａ２）を含む共重合体中の（メタ）アクリル酸単位（Ａ２）の残存率は９９．９％以下が好ましく、９９．７％以下がより好ましい。５０％以上であると、外観の観点で、アクリル樹脂本来の性能を損なわないだけでなく、（メタ）アクリル酸のヒドロキシル基と離型剤（Ｂ）との架橋反応による高分子量化が起こり、成形安定性に優れる。また、９９．９％以下であると、共重合体の耐熱性に優れる。アクリル酸単位（Ａ２）の残存率は下記式（１’）より算出した。
なお、ここでいう成形安定性とは、伸長流動特性が影響する成形方法であり、発泡成形、ブロー成形、フィルム成形などが挙げられる。これらの成形方法においては加熱成形時（伸長）時の歪硬化性が重要となる。歪硬化性を有することで、成形品の偏肉や吹き破れの防止できることで成形が安定し、成形中に成形品が切れるなどのトラブルが発生しにくく、生産性も向上する。歪硬化性を発現させるために、一般には高分子量物や長鎖分岐構造物を添加するが、本発明では離型剤（Ｂ）の添加により、一部が高分子量化するために、歪硬化性を発現することが期待できるため非常に効率的である。
（メタ）アクリル酸単位（Ａ２）の残存率（％）＝｛［共重合体中の（メタ）アクリル酸単位（Ａ２）の割合（ｍｏｌ％）］／（［共重合体中の（メタ）アクリル酸単位（Ａ２）の割合（ｍｏｌ％）］＋［共重合体中の無水グルタル酸単位（Ａ３）の割合（ｍｏｌ％）］）｝×１００・・・（１’）
The residual rate of the (meth)acrylic acid unit (A2) in the copolymer containing the unit (A1) and the unit (A2) is preferably 50% or more, more preferably 90% or more. Further, the residual rate of the (meth)acrylic acid unit (A2) in the copolymer containing the unit (A1) and the unit (A2) is preferably 99.9% or less, more preferably 99.7% or less. If it is 50% or more, not only will the original performance of the acrylic resin not be impaired in terms of appearance, but also the crosslinking reaction between the hydroxyl groups of (meth)acrylic acid and the mold release agent (B) will cause the polymer to have a high molecular weight. Excellent molding stability. Moreover, when it is 99.9% or less, the copolymer has excellent heat resistance. The residual rate of acrylic acid units (A2) was calculated from the following formula (1').
In addition, the molding stability here refers to a molding method that is influenced by elongational flow characteristics, and includes foam molding, blow molding, film molding, and the like. In these forming methods, strain hardening during heat forming (elongation) is important. By having strain hardening properties, it is possible to prevent uneven thickness and blow-out of the molded product, thereby stabilizing the molding, making it difficult for problems such as the molded product to break during molding, and improving productivity. In order to develop strain hardening properties, high molecular weight substances or long chain branched structures are generally added, but in the present invention, by adding the mold release agent (B), the molecular weight is partially increased, so strain hardening is not achieved. It is very efficient because it can be expected to express sexual characteristics.
Remaining rate (%) of (meth)acrylic acid units (A2) = {[ratio (mol%) of (meth)acrylic acid units (A2) in the copolymer]/([(meth)acrylic acid units (A2) in the copolymer Proportion of acrylic acid units (A2) (mol%) + [proportion of glutaric anhydride units (A3) in copolymer (mol%)]) x 100... (1')
本発明に記載の離型剤（Ｂ）とは、金型成形後に金型から剥離しやすくする目的と一部高分子量化のための部分架橋効果を目的として添加する成分である。
離型剤（Ｂ）の有機物は官能基が２つ以上であり、中でも２つが好ましい。官能基が２つ以上であると、溶融混練や溶融成形の際に共重合体（Ａ）の（メタ）アクリル酸のヒドロキシル基との架橋反応による高分子量化が起こり、成形安定性に優れる。また官能基が少ないほど、樹脂組成物から得られる成形品の表面にくもりが発生し難い傾向がある。ここで言う官能基としては特に限定されないが、カルボニル基、ヒドロキシル基、カルボキシル基、アミノ基、アミド基などが挙げられる。
The mold release agent (B) according to the present invention is a component added for the purpose of facilitating peeling from the mold after molding and for the purpose of partial crosslinking effect for increasing the molecular weight.
The organic substance of the mold release agent (B) has two or more functional groups, and preferably two functional groups. When the number of functional groups is two or more, a high molecular weight occurs due to a crosslinking reaction with the hydroxyl group of (meth)acrylic acid in the copolymer (A) during melt-kneading or melt-molding, resulting in excellent molding stability. Furthermore, the fewer functional groups there are, the less likely clouding will occur on the surface of a molded article obtained from the resin composition. The functional groups mentioned here are not particularly limited, but include carbonyl groups, hydroxyl groups, carboxyl groups, amino groups, amide groups, and the like.
離型剤（Ｂ）の分子量は１００～５００が好ましく、２００～４００がより好ましい。分子量が１００より大きいと揮発性が低いため、金型クモリに対して十分な効果が得られる。一方、分子量が５００より小さいとメタクリル樹脂との相溶性が高いため、離型時に金型への残存が少なく、金型汚れ、成形品のクモリが発生しにくい。 The molecular weight of the mold release agent (B) is preferably 100 to 500, more preferably 200 to 400. When the molecular weight is greater than 100, the volatility is low and a sufficient effect against mold cloudiness can be obtained. On the other hand, when the molecular weight is less than 500, the compatibility with the methacrylic resin is high, so there is little remaining in the mold upon demolding, and mold stains and cloudiness of the molded product are less likely to occur.
少なくとも２つの官能基を有する有機物である離型剤（Ｂ）としては例えば、グリセリンモノステアレート、グリセリンモノベヘネート、グリセリンモノ１，２－ヒドロキシステアレート、グリセリンモノオレート、グリセリンモノカプリレート、グリセリンモノカプレート及びグリセリンモノラウレートが挙げられる。また、これらを組み合わせて使用してもよく、１つ以下の官能基を有する有機物である離型剤と併用して使用してもよい。 Examples of the mold release agent (B) which is an organic substance having at least two functional groups include glycerin monostearate, glycerin monobehenate, glycerin mono-1,2-hydroxystearate, glycerin monooleate, glycerin monocaprylate, and glycerin Mention may be made of monocaprate and glycerol monolaurate. Moreover, these may be used in combination, and may be used in combination with a mold release agent which is an organic substance having one or less functional group.
離型剤（Ｂ）の含有量は、共重合体（Ａ）１００質量部に対して、０．０１～１質量部が好ましく、０．１～０．３質量部がより好ましい。含有量が０．０１質量部より多いと離型性が向上し、１質量部より少ないと添加剤のブリードによる金型汚染の影響が少ない。 The content of the mold release agent (B) is preferably 0.01 to 1 part by weight, more preferably 0.1 to 0.3 parts by weight, based on 100 parts by weight of the copolymer (A). When the content is more than 0.01 parts by mass, mold release properties are improved, and when the content is less than 1 part by mass, mold contamination due to additive bleeding is less affected.
樹脂組成物の積分分子量分布より求めた２５０℃、２０分加熱後のｌｏｇ［２Ｍｗ］以上の割合％／樹脂組成物の積分分子量分布より求めた加熱前のｌｏｇ［２Ｍｗ］以上の割合％（２’）は１．５以上１０以下が好ましく、２以上７以下がより好ましい。樹脂組成物の積分分子量分布より求めた２５０℃、２０分加熱後のｌｏｇ［２Ｍｗ］以上の割合が、１．５以上であると成形安定性に優れ、１０以下であると流動性に優れる。 Percentage % of log[2Mw] or higher after heating at 250°C for 20 minutes, determined from the integral molecular weight distribution of the resin composition/Ratio% of log[2Mw] or higher before heating, determined from the integral molecular weight distribution of the resin composition (2 ') is preferably 1.5 or more and 10 or less, more preferably 2 or more and 7 or less. When the ratio of log [2Mw] or more after heating at 250° C. for 20 minutes, determined from the integral molecular weight distribution of the resin composition, is 1.5 or more, the molding stability is excellent, and when it is 10 or less, the molding stability is excellent.
単位（Ａ１）、単位（Ａ２）及び無水グルタル酸単位（Ａ３）（以下、単に「単位（Ａ３）」ということがある。）を含む共重合体中の単位（Ａ３）の含有率は、共重合体１００ｍｏｌ％中、０．００１ｍｏｌ％以上０．２５ｍｏｌ％以下が好ましく、０．００１ｍｏｌ％以上０．１５ｍｏｌ％以下がより好ましい。単位（Ａ３）の含有率が０．００１ｍｏｌ％以上であると、共重合体の耐熱性、機械特性に優れる。また、単位（Ａ３）の含有率が０．２５ｍｏｌ％以下であると、特に、外観、低吸水性、成形性の観点で、アクリル樹脂本来の性能を損なわない。 The content of units (A3) in a copolymer containing units (A1), units (A2), and glutaric anhydride units (A3) (hereinafter sometimes simply referred to as "units (A3)") is In 100 mol% of the polymer, 0.001 mol% or more and 0.25 mol% or less are preferable, and 0.001 mol% or more and 0.15 mol% or less are more preferable. When the content of the unit (A3) is 0.001 mol% or more, the copolymer has excellent heat resistance and mechanical properties. Moreover, when the content of the unit (A3) is 0.25 mol % or less, the inherent performance of the acrylic resin is not impaired, especially in terms of appearance, low water absorption, and moldability.
単位（Ａ１）８０ｍｏｌ％以上、単位（Ａ２）０．４５ｍｏｌ％以上７ｍｏｌ％以下及び単位（Ａ３）０．００１ｍｏｌ％以上０．２５ｍｏｌ％以下を含む共重合体を得るには、メチル（メタ）アクリレート（ａ１）８０ｍｏｌ％以上及び（メタ）アクリル酸（ａ２）０．７ｍｏｌ％以上７ｍｏｌ％以下を含む単量体混合物を重合して前駆体を得て、得られた前駆体を押出機等により加熱溶融混練し、前駆体中の単位（Ａ１）と単位（Ａ２）を反応させ、単位（Ａ３）を形成させればよい。 To obtain a copolymer containing units (A1) of 80 mol% or more, units (A2) of 0.45 mol% or more and 7 mol% or less, and units (A3) of 0.001 mol% or more and 0.25 mol% or less, methyl (meth)acrylate A monomer mixture containing (a1) 80 mol% or more and (meth)acrylic acid (a2) 0.7 mol% or more and 7 mol% or less is polymerized to obtain a precursor, and the obtained precursor is heated with an extruder etc. What is necessary is to melt-knead and react the units (A1) and the units (A2) in the precursor to form the units (A3).
加熱温度は、２００℃以上２７０℃以下が好ましく、２１０℃以上２６０℃以下がより好ましい。加熱温度が２００℃以上であると、共重合体の流動性に優れ、共重合体や樹脂組成物の生産性に優れる。また、加熱温度が２７０℃以下であると、共重合体の熱劣化を抑制することができる。 The heating temperature is preferably 200°C or more and 270°C or less, more preferably 210°C or more and 260°C or less. When the heating temperature is 200° C. or higher, the copolymer has excellent fluidity and productivity of the copolymer and resin composition. Further, when the heating temperature is 270° C. or lower, thermal deterioration of the copolymer can be suppressed.
加熱時間は、１秒以上２４００秒以下が好ましく、５秒以上１８００秒以下がより好ましく、１０秒以上１２００秒以下が更に好ましい。加熱時間が１秒以上であると、共重合体や樹脂組成物を十分混合することができる。また、加熱時間が２４００秒以下であると、共重合体の熱劣化を抑制することができる。 The heating time is preferably 1 second or more and 2400 seconds or less, more preferably 5 seconds or more and 1800 seconds or less, and even more preferably 10 seconds or more and 1200 seconds or less. When the heating time is 1 second or more, the copolymer and the resin composition can be sufficiently mixed. Further, when the heating time is 2400 seconds or less, thermal deterioration of the copolymer can be suppressed.
本発明の共重合体は、単位（Ａ１）、単位（Ａ２）、単位（Ａ３）以外にも、他の単量体単位（Ａ４）（以下、単に「単位（Ａ４）」ということがある。）を含んでもよい。 In addition to the unit (A1), the unit (A2), and the unit (A3), the copolymer of the present invention has another monomer unit (A4) (hereinafter sometimes simply referred to as "unit (A4)"). ) may also be included.
単位（Ａ４）の含有率は、樹脂組成物がアクリル樹脂本来の性能を損なわないことから、共重合体１００ｍｏｌ％中、１５ｍｏｌ％以下が好ましく、５ｍｏｌ％以下がより好ましい。 The content of the unit (A4) is preferably 15 mol% or less, more preferably 5 mol% or less, based on 100 mol% of the copolymer, since the resin composition does not impair the inherent performance of the acrylic resin.
単位（Ａ４）を構成する単量体としては、例えば、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、グリシジル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、テトラシクロドデカニル（メタ）アクリレート、シクロヘキサンジメタノールモノ（メタ）アクリレート等の（メタ）アクリレート類；スチレン、α－メチルスチレン等の芳香族ビニル単量体等が挙げられる。 Examples of the monomer constituting the unit (A4) include ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec. -Butyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate , tridecyl (meth)acrylate, stearyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate acrylate, norbornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tetracyclododecanyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, etc. (Meth)acrylates; aromatic vinyl monomers such as styrene and α-methylstyrene; and the like.
メチル（メタ）アクリレートは、メチルメタクリレート及びメチルアクリレートの内の少なくとも一方をいう。
メチル（メタ）アクリレート（ａ１）の中でも、共重合体の外観、機械特性に優れることから、メチルメタクリレートが主成分であることが好ましい。また、共重合体の耐熱分解性を向上させる観点で、メチルアクリレートをメチルメタクリレートと共に用いることがより好ましい。
単位（Ａ１）も同様に、共重合体の外観、機械特性に優れることから、メチルメタクリレート単位が主成分であることが好ましい。また、共重合体の耐熱分解性を向上させる観点で、メチルアクリレート単位がメチルメタクリレート単位と共に含まれることがより好ましい。
Methyl (meth)acrylate refers to at least one of methyl methacrylate and methyl acrylate.
Among methyl (meth)acrylate (a1), it is preferable that methyl methacrylate is the main component because the copolymer has excellent appearance and mechanical properties. Further, from the viewpoint of improving the heat decomposition resistance of the copolymer, it is more preferable to use methyl acrylate together with methyl methacrylate.
Similarly, the unit (A1) preferably has a methyl methacrylate unit as a main component since the copolymer has excellent appearance and mechanical properties. Moreover, from the viewpoint of improving the heat decomposition resistance of the copolymer, it is more preferable that methyl acrylate units are included together with methyl methacrylate units.
（メタ）アクリル酸は、アクリル酸及びメタクリル酸の内の少なくとも一方をいう。
（メタ）アクリル酸（ａ２）の中でも、共重合体の耐熱性に優れることから、メタクリル酸が好ましい。
単位（Ａ２）も同様に、共重合体の耐熱性に優れることから、メタクリル酸単位が好ましい。
(Meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.
Among (meth)acrylic acids (a2), methacrylic acid is preferred because the copolymer has excellent heat resistance.
Similarly, the unit (A2) is preferably a methacrylic acid unit because the copolymer has excellent heat resistance.
メチル（メタ）アクリレート（ａ１）及び（メタ）アクリル酸（ａ２）を含む単量体混合物中のメチル（メタ）アクリレート（ａ１）の含有率は、単量体混合物１００ｍｏｌ％中、８０ｍｏｌ％以上が好ましく、また９９．５ｍｏｌ％以下が好ましい。前記含有率は、９０ｍｏｌ％以上９９ｍｏｌ％以下がより好ましい。メチル（メタ）アクリレート（ａ１）の含有率が８０ｍｏｌ％以上であると、特に、外観、低吸水性、成形性の観点で、アクリル樹脂本来の性能を損なわない。また、メチル（メタ）アクリレート（ａ１）の含有率が９９．５ｍｏｌ％以下であると、共重合体の耐熱性、機械特性に優れる。 The content of methyl (meth)acrylate (a1) in the monomer mixture containing methyl (meth)acrylate (a1) and (meth)acrylic acid (a2) is 80 mol% or more in 100 mol% of the monomer mixture. It is preferably 99.5 mol% or less. The content is more preferably 90 mol% or more and 99 mol% or less. When the content of methyl (meth)acrylate (a1) is 80 mol% or more, the inherent performance of the acrylic resin is not impaired, particularly in terms of appearance, low water absorption, and moldability. Moreover, when the content of methyl (meth)acrylate (a1) is 99.5 mol% or less, the copolymer has excellent heat resistance and mechanical properties.
メチル（メタ）アクリレート（ａ１）及び（メタ）アクリル酸（ａ２）を含む単量体混合物中の（メタ）アクリル酸（ａ２）の含有率は、単量体混合物１００ｍｏｌ％中、０．７ｍｏｌ％以上７ｍｏｌ％以下が好ましく、１ｍｏｌ％以上６ｍｏｌ％以下がより好ましい。（メタ）アクリル酸（ａ２）の含有率が０．７ｍｏｌ％以上であると、共重合体の耐熱性、機械特性に優れる。また、（メタ）アクリル酸（ａ２）の含有率が７ｍｏｌ％以下であると、特に、外観、低吸水性、成形性の観点で、アクリル樹脂本来の性能を損なわない。 The content of (meth)acrylic acid (a2) in the monomer mixture containing methyl (meth)acrylate (a1) and (meth)acrylic acid (a2) is 0.7 mol% in 100 mol% of the monomer mixture. It is preferably 7 mol% or less, more preferably 1 mol% or more and 6 mol% or less. When the content of (meth)acrylic acid (a2) is 0.7 mol% or more, the copolymer has excellent heat resistance and mechanical properties. Moreover, when the content of (meth)acrylic acid (a2) is 7 mol % or less, the inherent performance of the acrylic resin is not impaired, especially in terms of appearance, low water absorption, and moldability.
単量体混合物は、メチル（メタ）アクリレート（ａ１）、（メタ）アクリル酸（ａ２）以外にも、他の単量体（ａ４）を含んでもよい。
他の単量体（ａ４）は、メチル（メタ）アクリレート（ａ１）、（メタ）アクリル酸（ａ２）と共重合が可能なものであればよい。
The monomer mixture may contain other monomers (a4) in addition to methyl (meth)acrylate (a1) and (meth)acrylic acid (a2).
The other monomer (a4) may be any monomer that can be copolymerized with methyl (meth)acrylate (a1) and (meth)acrylic acid (a2).
他の単量体（ａ４）の含有率は、樹脂組成物がアクリル樹脂本来の性能を損なわないことから、単量体混合物１００ｍｏｌ％中、１５ｍｏｌ％以下が好ましく、５ｍｏｌ％以下がより好ましい。 The content of the other monomer (a4) is preferably 15 mol% or less, more preferably 5 mol% or less, based on 100 mol% of the monomer mixture, since the resin composition does not impair the inherent performance of the acrylic resin.
他の単量体（ａ４）としては、例えば、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、グリシジル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、テトラシクロドデカニル（メタ）アクリレート、シクロヘキサンジメタノールモノ（メタ）アクリレート等の（メタ）アクリレート類；スチレン、α－メチルスチレン等の芳香族ビニル単量体等が挙げられる。 Other monomers (a4) include, for example, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, Norbornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tetracyclododecanyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, etc. ) Acrylates; examples include aromatic vinyl monomers such as styrene and α-methylstyrene.
単量体混合物の重合方法としては、例えば、塊状重合、溶液重合、懸濁重合、乳化重合等が挙げられる。これらの単量体混合物の重合方法の中でも、単量体混合物の反応効率に優れることから、塊状重合、溶液重合、懸濁重合が好ましい。 Examples of methods for polymerizing the monomer mixture include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Among these methods for polymerizing monomer mixtures, bulk polymerization, solution polymerization, and suspension polymerization are preferred because they are excellent in reaction efficiency of monomer mixtures.
単量体混合物の重合において、重合温度、重合開始剤種類、重合開始剤量等は、重合方法や得ようとする共重合体に応じて、適宜設定すればよい。 In the polymerization of the monomer mixture, the polymerization temperature, type of polymerization initiator, amount of polymerization initiator, etc. may be appropriately set depending on the polymerization method and the copolymer to be obtained.
共重合体（Ａ）の質量平均分子量は、５０，０００以上１５０，０００以下であり、７０，０００以上１３０，０００以下が好ましい。共重合体の質量平均分子量が５０，０００以上であると、共重合体の機械特性に優れる。また、共重合体の質量平均分子量が１５０，０００以下であると、共重合体の流動性に優れる。
尚、本明細書において、質量平均分子量は、標準試料として標準ポリスチレンを用い、ゲルパーミエーションクロマトグラフィーを用いて測定した値とする。
The mass average molecular weight of the copolymer (A) is 50,000 or more and 150,000 or less, preferably 70,000 or more and 130,000 or less. When the mass average molecular weight of the copolymer is 50,000 or more, the copolymer has excellent mechanical properties. Further, when the mass average molecular weight of the copolymer is 150,000 or less, the copolymer has excellent fluidity.
In this specification, the mass average molecular weight is a value measured using gel permeation chromatography using standard polystyrene as a standard sample.
前記共重合体の質量平均分子量を制御するためには、単量体混合物の重合において連鎖移動剤の量を調整することが好ましい。
単量体混合物の重合における連鎖移動剤の含有量は、所望の共重合体の質量平均分子量とすることができることから、単量体混合物１００質量部に対して、０．１質量部以上０．５質量部以下が好ましく、０．１５質量部以上０．４質量部以下がより好ましい。
In order to control the weight average molecular weight of the copolymer, it is preferable to adjust the amount of chain transfer agent in the polymerization of the monomer mixture.
The content of the chain transfer agent in the polymerization of the monomer mixture can be set to the weight average molecular weight of the desired copolymer, and therefore, the content of the chain transfer agent in the polymerization of the monomer mixture is 0.1 parts by mass or more and 0.1 parts by mass or more based on 100 parts by mass of the monomer mixture. It is preferably 5 parts by mass or less, and more preferably 0.15 parts by mass or more and 0.4 parts by mass or less.
前記共重合体のビカット軟化温度は、１１５℃以上が好ましく、また１２５℃以下が好ましい。共重合体のビカット軟化温度が１１５℃以上であると、共重合体の耐熱性に優れる。また、共重合体のビカット軟化温度が１２５℃以下であると、共重合体の流動性に優れる。
尚、本明細書において、ビカット軟化温度は、ＩＳＯ３０６のＡ５０法に準拠して測定した値とする。
The Vicat softening temperature of the copolymer is preferably 115°C or higher, and preferably 125°C or lower. When the Vicat softening temperature of the copolymer is 115° C. or higher, the copolymer has excellent heat resistance. Further, when the Vicat softening temperature of the copolymer is 125° C. or less, the copolymer has excellent fluidity.
In this specification, the Vicat softening temperature is a value measured in accordance with the A50 method of ISO306.
本発明の樹脂組成物は、前記共重合体を含む。 The resin composition of the present invention contains the copolymer.
本発明の樹脂組成物は、前記の共重合体以外に、他の添加剤を含んでもよい。
他の添加剤としては、例えば、紫外線吸収剤、酸化防止剤、可塑剤、光拡散剤、艶消剤、滑剤、帯電防止剤、顔料等の着色剤等が挙げられる。これらの他の添加剤は、１種を単独で用いてもよく、２種以上を併用してもよい。
日光等の紫外線による共重合体の劣化を抑制することから、樹脂組成物中に紫外線吸収剤を含むことが好ましい。
溶融混練や溶融成形の際に共重合体の熱劣化を抑制することから、樹脂組成物中に酸化防止剤を含むことが好ましい。
The resin composition of the present invention may contain other additives in addition to the above copolymer.
Examples of other additives include ultraviolet absorbers, antioxidants, plasticizers, light diffusing agents, matting agents, lubricants, antistatic agents, and colorants such as pigments. These other additives may be used alone or in combination of two or more.
In order to suppress deterioration of the copolymer due to ultraviolet rays such as sunlight, it is preferable to include an ultraviolet absorber in the resin composition.
In order to suppress thermal deterioration of the copolymer during melt-kneading and melt-molding, it is preferable to include an antioxidant in the resin composition.
前記共重合体と他の添加剤とを混合する方法としては、例えば、二軸押出機等の装置を用いて溶融混練する方法等が挙げられる。また、前駆体と他の添加剤とを加熱溶融混練し、単位（Ａ３）を形成させて共重合体を得ると共に、他の添加剤と混合してもよい。 Examples of the method for mixing the copolymer and other additives include a method of melt-kneading using a device such as a twin-screw extruder. Alternatively, the precursor and other additives may be heat-melted and kneaded to form units (A3) to obtain a copolymer, and the copolymer may be mixed with other additives.
本発明の成形体は、本発明の樹脂組成物を成形して得られる。 The molded article of the present invention is obtained by molding the resin composition of the present invention.
成形体を得るための成形方法としては、例えば、射出成形、押出成形、加圧成形、ブロー成形、フィルム成型等が挙げられる。また、得られた成形体を、更に圧空成形や真空成形等の二次成形してもよい。 Examples of the molding method for obtaining the molded body include injection molding, extrusion molding, pressure molding, blow molding, and film molding. Further, the obtained molded product may be further subjected to secondary molding such as pressure forming or vacuum forming.
成形温度は、２００℃以上２７０℃以下が好ましく、２１０℃以上２６０℃以下がより好ましい。成形温度が２００℃以上であると、樹脂組成物の流動性に優れ、成形体の外観に優れる。また、成形温度が２７０℃以下であると、共重合体の熱劣化を抑制することができる。 The molding temperature is preferably 200°C or more and 270°C or less, more preferably 210°C or more and 260°C or less. When the molding temperature is 200° C. or higher, the resin composition has excellent fluidity and the molded product has excellent appearance. Further, when the molding temperature is 270°C or less, thermal deterioration of the copolymer can be suppressed.
成形時間は、３０秒以上１２００秒以下が好ましく、４５秒以上９００秒以下がより好ましく、６０秒以上６００秒以下が更に好ましい。成形時間が３０秒以上であると、樹脂組成物の流動性に優れ、成形体の外観に優れる。また、成形時間が１２００秒以下であると、共重合体の熱劣化を抑制することができる。 The molding time is preferably 30 seconds or more and 1200 seconds or less, more preferably 45 seconds or more and 900 seconds or less, and even more preferably 60 seconds or more and 600 seconds or less. When the molding time is 30 seconds or more, the resin composition has excellent fluidity and the molded product has excellent appearance. Further, when the molding time is 1200 seconds or less, thermal deterioration of the copolymer can be suppressed.
本発明の成形体は、耐熱性、機械特性、外観、成形性に優れることから、光学材料、車両用部品、照明用材料、建築用材料等に用いることができ、特に、自動車等の車両用部品に好適である。
自動車等の車両用部品としては、例えば、リアランプアウターカバー、リアランプ内部の光学部材、ヘッドライト用のインナーレンズ（プロジェクターレンズやＰＥＳレンズと称される場合がある）、メーターカバー、ドアミラーハウジング、ピラーカバー（サッシュカバー）、ライセンスガーニッシュ、フロントグリル、フォグガーニッシュ、エンブレム等が挙げられる。
Since the molded article of the present invention has excellent heat resistance, mechanical properties, appearance, and moldability, it can be used for optical materials, vehicle parts, lighting materials, construction materials, etc., and especially for vehicles such as automobiles. Suitable for parts.
Examples of vehicle parts for automobiles include rear lamp outer covers, optical members inside rear lamps, inner lenses for headlights (sometimes referred to as projector lenses or PES lenses), meter covers, door mirror housings, and pillar covers. (sash cover), license garnish, front grill, fog garnish, emblem, etc.
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.
（共重合体中の各単位の含有率）
実施例・比較例で得られた共重合体及び重ジメチルスルホキシドを、撹拌子を備えた２０ｍｌのシュレンク管に供給し、撹拌しながら８０℃に加熱し、共重合体を溶解させた。その後、２３℃まで冷却し、ベンジルアミンをシュレンク管に供給し、撹拌しながら８０℃に加熱した。１時間反応させた後、反応溶液を抜き取り、核磁気共鳴装置（ｖａｒｉａｎ社製、２７０ＭＨｚ）を用い、測定温度８０℃、積算回数３２回の条件で、１Ｈ－ＮＭＲ測定を行った。
得られた１Ｈ－ＮＭＲ測定結果から、３．７ｐｐｍ付近に存在するシングレットピークの未反応ベンジルアミンのベンジルプロトンの積分値と、４．２ｐｐｍ付近に存在するシングレットピークのグルタル酸ベンジルアミドのベンジルプロトンの積分値との比から、共重合体中の単位（Ａ３）の含有率を算出した。また、３．５ｐｐｍ付近に存在するシングレットピークの単位（Ａ１）由来のプロトンの積分値、０．５ｐｐｍ以上２．５ｐｐｍ以下付近に存在する単位（Ａ１）と単位（Ａ２）由来のプロトンの積分値をそれぞれ、３．７ｐｐｍ付近に存在するシングレットピークの未反応ベンジルアミンのベンジルプロトンの積分値と比をとることで、共重合体中の単位（Ａ１）及び単位（Ａ２）の含有率を算出した。
(Content of each unit in copolymer)
The copolymers and heavy dimethyl sulfoxide obtained in Examples and Comparative Examples were supplied to a 20 ml Schlenk tube equipped with a stirrer, and heated to 80° C. while stirring to dissolve the copolymers. Thereafter, the mixture was cooled to 23°C, and benzylamine was fed into a Schlenk tube, and heated to 80°C with stirring. After reacting for 1 hour, the reaction solution was extracted and 1 H-NMR measurement was performed using a nuclear magnetic resonance apparatus (manufactured by Varian, 270 MHz) at a measurement temperature of 80° C. and a total number of 32 times.
From the obtained 1 H-NMR measurement results, the integrated value of the benzyl proton of unreacted benzylamine with a singlet peak existing around 3.7 ppm, and the benzyl proton of glutaric acid benzylamide with a singlet peak around 4.2 ppm. The content of the unit (A3) in the copolymer was calculated from the ratio with the integral value of . In addition, the integral value of protons derived from the singlet peak unit (A1) existing around 3.5 ppm, the integral value of protons derived from the unit (A1) and unit (A2) existing around 0.5 ppm to 2.5 ppm, The content of unit (A1) and unit (A2) in the copolymer was calculated by taking the ratio of the integral value of the benzyl proton of unreacted benzylamine of the singlet peak existing around 3.7 ppm, respectively. .
（質量平均分子量）
実施例・比較例で得られた共重合体２０ｍｇを、１０ｍｌのテトラヒドロフランに溶解し、０．２μｍメンブレンフィルターで濾過して、試料溶液を得た。得られた試料溶液について、ゲルパーミエーションクロマトグラフィー（機種名「ＨＬＣ－８３２０ ＧＰＣ Ｅｃｏ ＳＥＣ」、東ソー（株）製）を用い、質量平均分子量を測定した。分離カラムとして「ＴＳＫｇｅｌ ＳｕｐｅｒＨＭ－Ｈ」（商品名、東ソー（株）製、内径６．０ｍｍ×長さ１５ｃｍ）を２本直列にしたもの、溶媒としてテトラヒドロフラン、検出器として示差屈折計、標準試料として標準ポリスチレンを用い、流量０．６ｍｌ／分、測定温度４０℃、注入量０．０１ｍｌの条件とした。
(mass average molecular weight)
20 mg of the copolymer obtained in Examples and Comparative Examples was dissolved in 10 ml of tetrahydrofuran and filtered through a 0.2 μm membrane filter to obtain a sample solution. The mass average molecular weight of the obtained sample solution was measured using gel permeation chromatography (model name: "HLC-8320 GPC Eco SEC", manufactured by Tosoh Corporation). Two "TSKgel SuperHM-H" (trade name, manufactured by Tosoh Corporation, inner diameter 6.0 mm x length 15 cm) were connected in series as a separation column, tetrahydrofuran was used as a solvent, a differential refractometer was used as a detector, and a standard sample was used. Using standard polystyrene, the conditions were a flow rate of 0.6 ml/min, a measurement temperature of 40° C., and an injection amount of 0.01 ml.
（樹脂組成物の加熱による分子量変化）
実施例・比較例で得られた樹脂組成物について、その質量平均分子量（Ｍｗ）および積分分子量分布を、ゲルパーミエーションクロマトグラフィーを用い、測定した。次に、実施例・比較例で得られた樹脂組成物を、２５０℃に加熱した乾燥機（機種名「ＤＲＶ３２０ＤＡ」、アドバンテック東洋（株）製）中で２０分加熱した後、ゲルパーミエーションクロマトグラフィーを用い、積分分子量分布を測定した。測定条件は前記（共重合体中の各単位の含有率）の項に記載している条件と同条件とした。下記式（２’）の条件を満たす樹脂組成物は共重合体と離型剤による部分架橋反応が進行し、高分子量化するため、成形安定性が向上することになる。そのため、下記式（２’）の条件を満たす樹脂組成物の成形安定性を「○」、（２’）の条件を満たさない樹脂組成物のそれを「×」とした。
１０≧樹脂組成物の積分分子量分布より求めた加熱後のｌｏｇ［２Ｍｗ］以上の割合％／樹脂組成物の積分分子量分布より求めた加熱前のｌｏｇ［２Ｍｗ］以上の割合％≧１．５・・・（２’）
(Molecular weight change due to heating of resin composition)
The mass average molecular weight (Mw) and integral molecular weight distribution of the resin compositions obtained in Examples and Comparative Examples were measured using gel permeation chromatography. Next, the resin compositions obtained in Examples and Comparative Examples were heated for 20 minutes in a dryer (model name "DRV320DA", manufactured by Advantech Toyo Co., Ltd.) heated to 250°C, and then subjected to gel permeation chromatography. The integral molecular weight distribution was measured using graphography. The measurement conditions were the same as those described in the section (Content of each unit in copolymer) above. In a resin composition that satisfies the conditions of the following formula (2'), a partial crosslinking reaction between the copolymer and the mold release agent proceeds and the molecular weight is increased, so that molding stability is improved. Therefore, the molding stability of the resin composition satisfying the condition of formula (2') below was rated as "○", and that of the resin composition that did not satisfy the condition of formula (2') was rated as "x".
10≧Proportion% of log[2Mw] or more after heating determined from the integral molecular weight distribution of the resin composition/Proportion% of more than log[2Mw] before heating determined from the integral molecular weight distribution of the resin composition≧1.5. ...(2')
（耐熱性評価）
実施例・比較例で得られた樹脂組成物を、射出成形機（機種名「ＩＳ－１００」、東芝機械（株）製）を用い、成形温度２５０℃、成形時間３６０秒の条件で射出成形し、８０ｍｍ×８ｍｍ×４ｍｍの成形体を得た。得られた８０ｍｍ×８ｍｍ×４ｍｍの成形体を切断し、４０ｍｍ×８ｍｍ×４ｍｍの成形体を得た後、８０℃で１６時間アニールを行い、得られた成形体を耐熱性評価の試験片として用いた。
耐熱性評価として、ＨＤＴ／ＶＩＣＡＴ試験機（機種名「Ｎｏ．１４８－ＨＡＤ ヒートデストーションテスター」、（株）安田精機製作所製）を用い、ＩＳＯ３０６のＡ５０法に準拠し、ビカット軟化温度試験を行い、ビカット軟化温度を測定した。
尚、各共重合体３回ビカット軟化温度試験を行い、その平均値をビカット軟化温度とした。
(Heat resistance evaluation)
The resin compositions obtained in Examples and Comparative Examples were injection molded using an injection molding machine (model name "IS-100", manufactured by Toshiba Machinery Co., Ltd.) at a molding temperature of 250°C and a molding time of 360 seconds. A molded article measuring 80 mm x 8 mm x 4 mm was obtained. The resulting 80 mm x 8 mm x 4 mm molded body was cut to obtain a 40 mm x 8 mm x 4 mm molded body, and then annealed at 80°C for 16 hours, and the resulting molded body was used as a test piece for heat resistance evaluation. Using.
As a heat resistance evaluation, a Vicat softening temperature test was conducted using an HDT/VICAT tester (model name "No. 148-HAD Heat Distortion Tester", manufactured by Yasuda Seiki Seisakusho Co., Ltd.) in accordance with ISO306 A50 method. , the Vicat softening temperature was measured.
Each copolymer was subjected to the Vicat softening temperature test three times, and the average value was taken as the Vicat softening temperature.
（離型性評価）
実施例・比較例で得られた樹脂組成物を射出成形機（機種名「ＩＳ－１００」、東芝機械（株）製）を用い、成形温度２５０℃、成形時間３６０秒の条件で射出成形し、１００ｍｍ×５０ｍｍ×２ｍｍの成形体を得た。
いずれも安定的に剥離したものを「○」、剥離し難いものがあったものを「×」と評価した。
(Mold releasability evaluation)
The resin compositions obtained in Examples and Comparative Examples were injection molded using an injection molding machine (model name "IS-100", manufactured by Toshiba Machinery Co., Ltd.) at a molding temperature of 250°C and a molding time of 360 seconds. A molded article of 100 mm x 50 mm x 2 mm was obtained.
In both cases, those that were stably peeled off were evaluated as "○", and those that were difficult to peel off were evaluated as "x".
［製造例０］
脱イオン水９００質量部、メタクリル酸２－スルホエチルナトリウム６０質量部、メタクリル酸カリウム１０質量部及びメチルメタクリレート１２質量部を、撹拌機、温度計及び冷却管を備えたフラスコに供給し、窒素を放流しながら、フラスコの内温が５０℃になるよう加熱した。その後、２，２’－アゾビス（２－メチルプロピオンアミジン）二塩酸塩０．０８質量部を供給し、フラスコの内温が６０℃になるよう加熱した。その後、滴下ポンプを用いて、メチルメタクリレートを０．２４質量部／分の速度で７５分間滴下した。その後、６時間保持し、分散剤（固形分１０質量％）を得た。
[Manufacture example 0]
900 parts by weight of deionized water, 60 parts by weight of sodium 2-sulfoethyl methacrylate, 10 parts by weight of potassium methacrylate and 12 parts by weight of methyl methacrylate were fed into a flask equipped with a stirrer, a thermometer and a condenser, and nitrogen was added. While discharging water, the flask was heated to an internal temperature of 50°C. Thereafter, 0.08 parts by mass of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was supplied, and the flask was heated so that the internal temperature reached 60°C. Thereafter, using a dropping pump, methyl methacrylate was added dropwise at a rate of 0.24 parts by mass/min for 75 minutes. Thereafter, the mixture was held for 6 hours to obtain a dispersant (solid content: 10% by mass).
［製造例１］
脱イオン水２０００質量部及び硫酸ナトリウム４．２質量部を、攪拌機、温度計、冷却管及び窒素ガス導入管を備えたセパラブルフラスコに供給し、３２０ｒｐｍの撹拌速度で１５分間撹拌した。その後、メチルメタクリレート（９５ｍｏｌ％）（商品名「アクリエステルＭ」、三菱レイヨン（株）製）１３３９．４質量部、メタクリル酸（５ｍｏｌ％）６０．６質量部、２，２’－アゾビス－２－メチルブチロニトリル（重合開始剤、商品名「Ｖ－５９」、和光純薬工業（株）製）２．８質量部、ｎ－オクチルメルカプタン（連鎖移動剤、東京化成工業（株）製）４．２質量部（単量体合計１００質量部に対する含有量が０．３質量部）及びリケマールＳ－１００Ａ（離型剤、理研ビタミン（株）製）２．８質量部（単量体合計１００質量部に対する含有量が０．２質量部）をセパラブルフラスコに供給し、５分間撹拌した。その後、製造例０で製造した分散剤６．７２質量部をセパラブルフラスコに供給し、撹拌し、セパラブルフラスコ中の単量体混合物を水中に分散させた。その後、窒素ガスを１５分間放流した。
その後、セパラブルフラスコの内温が７５℃になるよう加熱し、重合発熱ピークが観測されるまでその温度を保持した。重合発熱ピークが観測された後、セパラブルフラスコの内温が９０℃になるよう加熱し、６０分間保持し、重合を完了させた。その後、セパラブルフラスコ内の混合物を濾過し、濾過物を脱イオン水で洗浄し、８０℃で１６時間乾燥し、ビーズ状の前駆体（１）を得た。
[Manufacture example 1]
2000 parts by mass of deionized water and 4.2 parts by mass of sodium sulfate were supplied to a separable flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introduction tube, and stirred for 15 minutes at a stirring speed of 320 rpm. Thereafter, 1339.4 parts by mass of methyl methacrylate (95 mol%) (trade name "Acryester M", manufactured by Mitsubishi Rayon Co., Ltd.), 60.6 parts by mass of methacrylic acid (5 mol%), 2,2'-azobis-2 - 2.8 parts by mass of methylbutyronitrile (polymerization initiator, trade name "V-59", manufactured by Wako Pure Chemical Industries, Ltd.), n-octyl mercaptan (chain transfer agent, manufactured by Tokyo Chemical Industry Co., Ltd.) 4.2 parts by mass (content is 0.3 parts by mass based on 100 parts by mass of monomers in total) and Rikemar S-100A (mold release agent, manufactured by Riken Vitamin Co., Ltd.) 2.8 parts by mass (total monomers) 0.2 parts by mass per 100 parts by mass) was supplied to a separable flask and stirred for 5 minutes. Thereafter, 6.72 parts by mass of the dispersant produced in Production Example 0 was supplied to the separable flask and stirred to disperse the monomer mixture in the separable flask in water. Thereafter, nitrogen gas was released for 15 minutes.
Thereafter, the separable flask was heated to an internal temperature of 75° C., and the temperature was maintained until an exothermic peak of polymerization was observed. After the exothermic peak of polymerization was observed, the separable flask was heated to an internal temperature of 90° C. and maintained for 60 minutes to complete polymerization. Thereafter, the mixture in the separable flask was filtered, and the filtered product was washed with deionized water and dried at 80° C. for 16 hours to obtain a bead-shaped precursor (1).
［製造例２～４］
単量体混合物中のメチル（メタ）アクリレート（ａ１）、（メタ）アクリル酸（ａ２）の含有率及び離型剤の種類・含有量を表１のように変更したこと以外は製造例１と同様の操作を行い、ビーズ状の前駆体（２）～（４）を得た。
[Production Examples 2 to 4]
Same as Production Example 1 except that the content of methyl (meth)acrylate (a1) and (meth)acrylic acid (a2) in the monomer mixture and the type and content of the mold release agent were changed as shown in Table 1. A similar operation was performed to obtain bead-shaped precursors (2) to (4).
［実施例１］
得られたビーズ状の前駆体（１）を、二軸混練押出機（Ｗｅｒｎｅｒ＆Ｐｆｌｅｉｄｅｒｅｒ社製、３０ｍｍφ）を用い、混練温度２５０℃、混練時間６０秒で溶融混練し、グルタル酸無水物単位（Ａ３）を形成させ、ペレット状の樹脂組成物を得た。
[Example 1]
The obtained bead-like precursor (1) was melt-kneaded using a twin-screw kneading extruder (manufactured by Werner & Pfleiderer, 30 mmφ) at a kneading temperature of 250°C and a kneading time of 60 seconds to form glutaric anhydride units (A3). was formed to obtain a pellet-shaped resin composition.
［比較例１～３］
用いる前駆体を前駆体（２）～（４）とすること以外は実施例１と同様の操作を行い、ペレット状の樹脂組成物を得た。
得られた樹脂組成物の評価結果を、表２に示す。
[Comparative Examples 1 to 3]
A pellet-shaped resin composition was obtained by carrying out the same operation as in Example 1 except that the precursors used were precursors (2) to (4).
Table 2 shows the evaluation results of the obtained resin composition.
実施例１で得られた樹脂組成物は、耐熱性、離型性、成形安定性に優れた。
一方、比較例１で得られた樹脂組成物は、離型性と成形安定性に劣り、比較例２で得られた樹脂組成物は、成形安定性に劣った。また、比較例３で得られた樹脂組成物は、耐熱性と成形安定性に劣った。
The resin composition obtained in Example 1 had excellent heat resistance, mold releasability, and molding stability.
On the other hand, the resin composition obtained in Comparative Example 1 had poor mold releasability and molding stability, and the resin composition obtained in Comparative Example 2 had poor molding stability. Further, the resin composition obtained in Comparative Example 3 was inferior in heat resistance and molding stability.
本発明の成形体は、耐熱性、離型性、流動性、機械特性、外観、低吸水性、成形性に優れることから、光学材料、車両用部品、照明用材料、建築用材料等に用いることができ、特に、自動車の車両用部品に好適である。 The molded article of the present invention has excellent heat resistance, mold releasability, fluidity, mechanical properties, appearance, low water absorption, and moldability, and is therefore used for optical materials, vehicle parts, lighting materials, construction materials, etc. It is particularly suitable for automobile parts.
Claims (5)
共重合体（Ａ）１００ｍｏｌ％中、メチル（メタ）アクリレート単位（Ａ１）が８０ｍｏｌ％以上、（メタ）アクリル酸単位（Ａ２）が０．４５ｍｏｌ％以上７ｍｏｌ％以下、及び無水グルタル酸単位（Ａ３）が０．００１ｍｏｌ％以上０．２５ｍｏｌ％以下であり、
少なくとも２つの官能基を有する有機物である離型剤（Ｂ）が、グリセリンモノステアレート、グリセリンモノベヘネート、グリセリンモノ１，２－ヒドロキシステアレート、グリセリンモノオレート、グリセリンモノカプリレート、グリセリンモノカプレート及びグリセリンモノラウレートからなる群より選ばれる少なくとも１種であり、
離型剤（Ｂ）の含有量が、共重合体（Ａ）１００質量部に対して、０．０１～１質量部である、樹脂組成物（但し、流動性ポリオルガノシロキサンを含まない。）。
（メタ）アクリル酸単位（Ａ２）の残存率（％）＝｛［共重合体（Ａ）中の（メタ）アクリル酸単位（Ａ２）の割合（ｍｏｌ％）］／（［共重合体（Ａ）中の（メタ）アクリル酸単位（Ａ２）の割合（ｍｏｌ％）］＋［共重合体（Ａ）中の無水グルタル酸単位（Ａ３）の割合（ｍｏｌ％）］）｝×１００・・・（１’） A copolymer (A) containing methyl (meth)acrylate units (A1), (meth)acrylic acid units (A2) and glutaric anhydride units (A3), and a mold release agent that is an organic substance having at least two functional groups. (B) and the residual rate of the (meth)acrylic acid unit (A2) represented by the following formula (1') is 90% or more,
In 100 mol% of copolymer (A), methyl (meth)acrylate unit (A1) is 80 mol% or more, (meth)acrylic acid unit (A2) is 0.45 mol% or more and 7 mol% or less, and glutaric anhydride unit (A3) ) is 0.001 mol% or more and 0.25 mol% or less,
The mold release agent (B) which is an organic substance having at least two functional groups is glycerin monostearate, glycerin monobehenate, glycerin mono-1,2-hydroxystearate, glycerin monooleate, glycerin monocaprylate, glycerin monocaprate. and at least one member selected from the group consisting of glycerin monolaurate,
A resin composition in which the content of the mold release agent (B) is 0.01 to 1 part by mass based on 100 parts by mass of the copolymer (A) (however, it does not contain a fluid polyorganosiloxane). .
Remaining rate (%) of (meth)acrylic acid units (A2) = {[Ratio (mol%) of (meth)acrylic acid units (A2) in copolymer (A)]/([Copolymer (A) ) in (mol%) of (meth)acrylic acid units (A2)] + [proportion of glutaric anhydride units (A3) in copolymer (A) (mol%)])}×100... (1')
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