JP2021165406A - Resin composition, molded body and component for vehicle - Google Patents
Resin composition, molded body and component for vehicle Download PDFInfo
- Publication number
- JP2021165406A JP2021165406A JP2021115771A JP2021115771A JP2021165406A JP 2021165406 A JP2021165406 A JP 2021165406A JP 2021115771 A JP2021115771 A JP 2021115771A JP 2021115771 A JP2021115771 A JP 2021115771A JP 2021165406 A JP2021165406 A JP 2021165406A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- resin composition
- copolymer
- unit
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 77
- 229920001577 copolymer Polymers 0.000 claims abstract description 91
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 79
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 52
- 125000000524 functional group Chemical group 0.000 claims abstract description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical group O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 125000003368 amide group Chemical group 0.000 claims abstract description 4
- 125000003277 amino group Chemical group 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 238000000465 moulding Methods 0.000 claims description 38
- 239000000178 monomer Substances 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 235000011187 glycerol Nutrition 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 11
- 238000004898 kneading Methods 0.000 claims description 9
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 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 5
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 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 4
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 238000010521 absorption reaction Methods 0.000 abstract description 13
- 239000006082 mold release agent Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 16
- 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
- 239000004925 Acrylic resin Substances 0.000 description 9
- 229920000178 Acrylic resin Polymers 0.000 description 9
- -1 n-octyl Chemical group 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
- 238000004132 cross linking Methods 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 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
- 238000003756 stirring Methods 0.000 description 3
- 238000005482 strain hardening 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-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
- 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
- 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
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 238000001816 cooling Methods 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
- 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
- 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
- 241000239290 Araneae Species 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- VTWUAZLFPRUHDB-UHFFFAOYSA-N S(=O)(=O)(O)CC[Na].C(C(=C)C)(=O)O Chemical compound S(=O)(=O)(O)CC[Na].C(C(=C)C)(=O)O VTWUAZLFPRUHDB-UHFFFAOYSA-N 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
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000011109 contamination 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
- 239000000706 filtrate Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 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
- 229920000642 polymer Polymers 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
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 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
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、樹脂組成物、樹脂組成物の製造方法、成形体及び車両用部品に関する。 The present invention relates to a resin composition, a method for producing a resin composition, a molded product, and vehicle parts.
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。 Polymethylmethacrylate and polycarbonate are widely used in various fields such as optical materials, vehicle parts, lighting materials, and building materials because of their excellent transparency and dimensional stability. In recent years, molded products of polymethylmethacrylate and polycarbonate are required to have higher performance as parts become thinner and finer. One of its performances is heat resistance. In particular, vehicle parts such as tail lamps and headlamps are required to have better heat resistance because vehicles such as automobiles are used even in high temperature and high 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 polymethylmethacrylate has excellent transparency and weather resistance, its heat resistance is not sufficient. In addition, although polycarbonate has excellent heat resistance and impact resistance, it has a large birefringence, which is an optical strain, and causes optical anisotropy in the molded body, and also has excellent molding processability, scratch resistance, and oil resistance. Remarkably 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 typified by polymethylmethacrylate. For example, Patent Document 1 proposes a copolymer having a methyl methacrylate unit, a methacrylic acid unit, and a glutaric anhydride unit.
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 is inferior in appearance, low water absorption, and moldability because the glutaric acid anhydride unit (glutaric acid anhydride unit) is excessive.
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 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 excellent in heat resistance, fluidity, mechanical properties, appearance, low water absorption and moldability of the obtained copolymer.
（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 a methyl (meth) acrylate unit (A1) and a (meth) acrylic acid unit (A2), and a release agent (B) which is an organic substance having at least two functional groups. A resin composition containing 50% or more of the (meth) acrylic acid unit (A2) represented by the following formula (1').
Residual rate (%) of (meth) acrylic acid unit (A2) = {[ratio of (meth) acrylic acid unit (A2) in copolymer (mol%)] / ([(meth) in copolymer Acrylic acid unit (A2) ratio (mol%)] + [ratio of anhydrous glutaric acid unit (A3) in copolymer (mol%)])} x 100 ... (1')
(2) The resin composition having a residual ratio of the (meth) acrylic acid unit (A2) represented by the formula (1') of 90% or more.
(3) The above-mentioned resin composition containing a copolymer (A) containing a methyl (meth) acrylate unit (A1) and a (meth) acrylic acid unit (A2) and satisfying the following condition (2').
10 ≧ Ratio% of log [2Mw] or more after heating at 250 ° C. for 20 minutes obtained from the integrated molecular weight distribution of the resin composition / Percentage% of log [2Mw] or more before heating obtained from the integrated molecular weight distribution of the resin composition ≧ 1.5 ・ ・ ・ (2')
(4) The above-mentioned resin composition having at least two functional groups as the organic substance of the release agent (B).
(5) The above-mentioned resin composition, wherein the functional group contained in the organic substance of the release agent (B) is at least one 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 release agent (B), which is an organic substance having at least two functional groups, has a molecular weight of 100 to 500.
(7) The release agent (B), which is an organic substance having at least two functional groups, is glycerin monostearate, glycerin monobehenate, glycerin mono1,2-hydroxystearate, glycerin monooleate, glycerin monocaprilate, The above-mentioned resin composition, which is at least one selected from the group consisting of a glycerin monoca plate and a glycerin monolaurate.
(8) The content of the 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-mentioned resin composition, wherein the copolymer (A) further contains a glutaric anhydride unit (A3).
(10) Among the monomer units constituting the copolymer (A), the methyl (meth) acrylate unit (A1) is 80 mol% or more, and the repeating unit (A2) derived from (meth) acrylic acid is 1 mol% to 15 mol%. , And the above-mentioned resin composition having a glutaric anhydride unit (A3) of 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 monomer containing methyl (meth) acrylate (a1) and (meth) acrylic acid (a2) was polymerized to obtain a precursor, and the obtained precursor and an organic substance having at least two functional groups were used. A method for producing a resin composition, wherein a certain release agent (B) is melt-kneaded and the residual ratio of the (meth) acrylic acid unit (a2) represented by the above formula (1') is 50% or more.
(12) The method for producing the above-mentioned resin composition, wherein the polymerization method is suspension polymerization.
(13) Production of the above-mentioned resin composition, wherein the content of the release agent (B), which is an organic substance having at least two functional groups, is 0.01 to 1 part by mass with respect to 100 parts by mass of the precursor. Method.
(14) The method for producing a resin composition, 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 product obtained by molding the above resin composition.
(16) Vehicle parts including the molded body.
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 is excellent in heat resistance, fluidity, mechanical properties, appearance, low water absorption, and moldability.
In addition, the method for producing a resin composition of the present invention is excellent in heat resistance, fluidity, mechanical properties, appearance, low water absorption, and moldability of the obtained resin composition.
Further, the molded product of the present invention is excellent in 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) is a methyl (meth) acrylate unit (A1) and a (meth) acrylic acid unit (A2) (hereinafter, simply "unit (A1)", "unit (A2)). ”) Is included.
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, and further preferably 90 mol% or more and 98 mol% or less in 100 mol% of the copolymer. preferable. When the content of the unit (A1) is 80 mol% or more, the original performance of the acrylic resin is not impaired, particularly from the viewpoint of appearance, low water absorption, and moldability. Further, when the content of the unit (A1) is 99 mol% or less, the heat resistance and mechanical properties of the copolymer are excellent.
In the present specification, the content of each unit in the copolymer is a value calculated from 1 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% in 100 mol% of the copolymer. The following is more preferable. When the content of the unit (A2) is 0.45 mol% or more, the heat resistance and mechanical properties of the copolymer are excellent. Further, when the content of the unit (A2) is 7 mol% or less, the original performance of the acrylic resin is not impaired, particularly from the viewpoint 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 ratio 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. The residual ratio 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 the original performance of the acrylic resin is not impaired from the viewpoint of appearance, but also the molecular weight is increased by the cross-linking reaction between the hydroxyl group of (meth) acrylic acid and the release agent (B). Excellent molding stability. Further, when it is 99.9% or less, the heat resistance of the copolymer is excellent. The residual rate of the acrylic acid unit (A2) was calculated from the following formula (1').
The molding stability referred to here is a molding method in which the elongation flow property affects, and examples thereof include foam molding, blow molding, and film molding. In these molding methods, strain curability during heat molding (elongation) is important. By having the strain hardening property, it is possible to prevent uneven thickness and blow-by of the molded product, so that the molding is stable, troubles such as the molded product being cut during molding are less likely to occur, and the productivity is also improved. Generally, a high molecular weight substance or a long-chain branched structure is added in order to develop strain hardening property, but in the present invention, the addition of the release agent (B) causes a part of the molecular weight to be increased, so that the strain hardening is performed. It is very efficient because it can be expected to express sex.
Residual rate (%) of (meth) acrylic acid unit (A2) = {[ratio of (meth) acrylic acid unit (A2) in copolymer (mol%)] / ([(meth) in copolymer Acrylic acid unit (A2) ratio (mol%)] + [ratio of anhydrous glutaric acid unit (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) described in the present invention is a component added for the purpose of facilitating peeling from the mold after mold molding and for the purpose of partial cross-linking effect for partially increasing the molecular weight.
The organic substance of the release agent (B) has two or more functional groups, and two or more are preferable. When the number of functional groups is two or more, the copolymer (A) has a high molecular weight due to a cross-linking reaction with the hydroxyl group of (meth) acrylic acid during melt-kneading or melt-molding, and the molding stability is excellent. Further, the smaller the number of functional groups, the less likely it is that the surface of the molded product obtained from the resin composition will become cloudy. The functional group referred to here is not particularly limited, and examples thereof include a carbonyl group, a hydroxyl group, a carboxyl group, an amino group, and an amide group.
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 release agent (B) is preferably 100 to 500, more preferably 200 to 400. When the molecular weight is larger than 100, the volatility is low, so that a sufficient effect can be obtained on the mold spider. On the other hand, when the molecular weight is smaller than 500, the compatibility with the methacrylic resin is high, so that the residue on the mold is small at the time of mold release, and the mold is less likely to be soiled and the molded product is less likely to become cloudy.
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 release agent (B), which is an organic substance having at least two functional groups, include glycerin monostearate, glycerin monobehenate, glycerin mono1,2-hydroxystearate, glycerin monooleate, glycerin monocaprilate, and glycerin. Examples include monocaplate and glycerin monolaurate. Further, these may be used in combination, or may be used in combination with a mold release agent which is an organic substance having one or less functional groups.
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 release agent (B) is preferably 0.01 to 1 part by mass, more preferably 0.1 to 0.3 parts by mass with respect to 100 parts by mass of the copolymer (A). If the content is more than 0.01 part by mass, the releasability is improved, and if it is less than 1 part by mass, the influence of mold contamination due to the bleeding of the additive is small.
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 more after heating at 250 ° C. for 20 minutes obtained from the integrated molecular weight distribution of the resin composition / Percentage% of log [2Mw] or more before heating determined from the integrated molecular weight distribution of the resin composition (2) ') Is preferably 1.5 or more and 10 or less, and 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 integrated 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 fluidity 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 the unit (A3) in the copolymer including the unit (A1), the unit (A2) and the glutaric anhydride unit (A3) (hereinafter, may be simply referred to as "unit (A3)") is the same. Of the 100 mol% of the polymer, 0.001 mol% or more and 0.25 mol% or less is preferable, and 0.001 mol% or more and 0.15 mol% or less is more preferable. When the content of the unit (A3) is 0.001 mol% or more, the heat resistance and mechanical properties of the copolymer are excellent. Further, when the content of the unit (A3) is 0.25 mol% or less, the original performance of the acrylic resin is not impaired, particularly from the viewpoint 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 80 mol% or more of the unit (A1), 0.45 mol% or more and 7 mol% or less of the unit (A2), and 0.001 mol% or more and 0.25 mol% or less of the unit (A3), 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 by an extruder or the like. The unit (A1) and the unit (A2) in the precursor may be reacted by melt-kneading to form the unit (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 higher and 270 ° C. or lower, and more preferably 210 ° C. or higher and 260 ° C. or lower. When the heating temperature is 200 ° C. or higher, the fluidity of the copolymer is excellent, and the productivity of the copolymer and the resin composition is excellent. 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 further 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, the 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 may be referred to as another monomer unit (A4) (hereinafter, simply "unit (A4)". ) May 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, because the resin composition does not impair the original 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, and 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. (Meta) Acrylates; Examples thereof include aromatic vinyl monomers such as styrene and α-methylstyrene.
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 the methyl (meth) acrylates (a1), it is preferable that methyl methacrylate is the main component because the copolymer is excellent in appearance and mechanical properties. Further, from the viewpoint of improving the thermostable decomposition property of the copolymer, it is more preferable to use methyl acrylate together with methyl methacrylate.
Similarly, the unit (A1) is preferably a methyl methacrylate unit as a main component because it is excellent in appearance and mechanical properties of the copolymer. Further, from the viewpoint of improving the thermostable decomposition property of the copolymer, it is more preferable that the methyl acrylate unit is contained together with the methyl methacrylate unit.
（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。
(Meta) acrylic acid refers to at least one of acrylic acid and methacrylic acid.
Among the (meth) acrylic acids (a2), methacrylic acid is preferable because the copolymer has excellent heat resistance.
Similarly, the unit (A2) is preferably a methacrylic acid unit because it is excellent in heat resistance of the copolymer.
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 preferable, and 99.5 mol% or less is preferable. The content is more preferably 90 mol% or more and 99 mol% or less. When the content of the methyl (meth) acrylate (a1) is 80 mol% or more, the original performance of the acrylic resin is not impaired, particularly from the viewpoint of appearance, low water absorption and moldability. Further, when the content of methyl (meth) acrylate (a1) is 99.5 mol% or less, the heat resistance and mechanical properties of the copolymer are excellent.
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) was 0.7 mol% in 100 mol% of the monomer mixture. More than 7 mol% is preferable, and 1 mol% or more and 6 mol% or less is more preferable. When the content of (meth) acrylic acid (a2) is 0.7 mol% or more, the heat resistance and mechanical properties of the copolymer are excellent. Further, when the content of (meth) acrylic acid (a2) is 7 mol% or less, the original performance of the acrylic resin is not impaired, particularly from the viewpoint 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 one capable of copolymerizing 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, because the resin composition does not impair the original 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。 Examples of the other monomer (a4) include ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and sec-butyl. (Meta) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (Meta) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (Meta) such as 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 the polymerization method of the monomer mixture include bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like. Among these polymerization methods of the monomer mixture, bulk polymerization, solution polymerization and suspension polymerization are preferable because the reaction efficiency of the monomer mixture is excellent.
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, the type of the polymerization initiator, the amount of the polymerization initiator and the like may be appropriately set according to 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 mechanical properties of the copolymer are excellent. Further, when the mass average molecular weight of the copolymer is 150,000 or less, the fluidity of the copolymer is excellent.
In the present specification, the mass average molecular weight is a value measured by using standard polystyrene as a standard sample and using gel permeation chromatography.
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 mass average molecular weight of the copolymer, it is preferable to adjust the amount of the chain transfer agent in the polymerization of the monomer mixture.
Since the content of the chain transfer agent in the polymerization of the monomer mixture can be set to the mass average molecular weight of the desired copolymer, 0.1 parts by mass or more and 0 parts by mass or more with respect to 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 heat resistance of the copolymer is excellent. Further, when the Vicat softening temperature of the copolymer is 125 ° C. or lower, the fluidity of the copolymer is excellent.
In this specification, the Vicat softening temperature is a value measured according to 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 above-mentioned 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-mentioned copolymer.
Examples of other additives include ultraviolet absorbers, antioxidants, plasticizers, light diffusing agents, matting agents, lubricants, antistatic agents, colorants such as pigments, and the like. These other additives may be used alone or in combination of two or more.
It is preferable to include an ultraviolet absorber in the resin composition because it suppresses deterioration of the copolymer due to ultraviolet rays such as sunlight.
It is preferable to include an antioxidant in the resin composition because it suppresses thermal deterioration of the copolymer during melt kneading and melt molding.
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 of mixing the copolymer with other additives include a method of melt-kneading using an apparatus such as a twin-screw extruder. Further, the precursor and other additives may be heat-melted and kneaded to form a unit (A3) to obtain a copolymer, and 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 product 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 a molded body include injection molding, extrusion molding, pressure molding, blow molding, film molding and the like. Further, the obtained molded product may be further subjected to secondary molding such as compressed air molding 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 higher and 270 ° C. or lower, and more preferably 210 ° C. or higher and 260 ° C. or lower. When the molding temperature is 200 ° C. or higher, the fluidity of the resin composition is excellent and the appearance of the molded product is excellent. Further, when the molding temperature is 270 ° C. or lower, 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 further preferably 60 seconds or more and 600 seconds or less. When the molding time is 30 seconds or more, the fluidity of the resin composition is excellent and the appearance of the molded body is excellent. Further, when the molding time is 1200 seconds or less, the 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 body of the present invention is excellent in heat resistance, mechanical properties, appearance, and moldability, it can be used for optical materials, vehicle parts, lighting materials, building materials, etc., and in particular, for vehicles such as automobiles. Suitable for parts.
Examples of vehicle parts such as automobiles include a rear lamp outer cover, an optical member inside the rear lamp, an inner lens for headlights (sometimes referred to as a projector lens or a PES lens), a meter cover, a door mirror housing, and a pillar cover. (Sash cover), licensed 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。 Hereinafter, the present invention will be specifically described 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 rate of each unit in the copolymer)
The copolymer and deuterated dimethylsulfoxide obtained in Examples and Comparative Examples were supplied to a 20 ml Schlenk tube equipped with a stirrer and heated to 80 ° C. with stirring to dissolve the copolymer. Then, the temperature was cooled to 23 ° C., benzylamine was supplied to the Schlenk tube, and the mixture was heated to 80 ° C. with stirring. After reacting for 1 hour, the reaction solution was withdrawn, and 1 H-NMR measurement was carried out using a nuclear magnetic resonance apparatus (manufactured by Varian, 270 MHz) under the conditions of a measurement temperature of 80 ° C. and an integration frequency of 32 times.
From the obtained 1 H-NMR measurement result, the integral value of the benzyl proton of the unreacted benzylamine of the singlet peak present at around 3.7 ppm and the benzyl proton of the glutaric benzylamide of the singlet peak present at the vicinity of 4.2 ppm. The content of the unit (A3) in the copolymer was calculated from the ratio with the integrated value of. Further, the integrated value of the proton derived from the unit (A1) of the singlet peak existing near 3.5 ppm, and the integrated value of the protons derived from the unit (A1) and the unit (A2) existing near 0.5 ppm or more and 2.5 ppm or less. The content of the unit (A1) and the unit (A2) in the copolymer was calculated by taking the ratio with the integral value of the benzyl proton of the unreacted benzylamine of the singlet peak existing in the vicinity of 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) in series as a separation column, tetrahydrofuran as a solvent, differential refractometer as a detector, and a standard sample. Using standard polystyrene, the conditions were a flow rate of 0.6 ml / min, a measurement temperature of 40 ° C., and an injection volume 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’）
(Change in molecular weight due to heating of resin composition)
The mass average molecular weight (Mw) and the integrated 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 in a dryer (model name "DRV320DA", manufactured by Advantech Toyo Co., Ltd.) heated to 250 ° C. for 20 minutes, and then gel permeation chromatography was performed. The integrated molecular weight distribution was measured using chromatography. The measurement conditions were the same as those described in the above section (content of each unit in the copolymer). In the resin composition satisfying the condition of the following formula (2'), the partial cross-linking reaction by the copolymer and the release agent proceeds to increase the molecular weight, so that the molding stability is improved. Therefore, the molding stability of the resin composition satisfying the condition of the following formula (2') was designated as "○", and that of the resin composition not satisfying the condition of (2') was designated as "x".
10 ≧ Ratio% of log [2Mw] or more after heating obtained from the integrated molecular weight distribution of the resin composition / Ratio% of log [2Mw] or more after heating obtained from the integrated 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 composition obtained in Examples and Comparative Examples is injection-molded using an injection molding machine (model name "IS-100", manufactured by Toshiba Machine Co., Ltd.) under the conditions of a molding temperature of 250 ° C. and a molding time of 360 seconds. Then, a molded product having a size of 80 mm × 8 mm × 4 mm was obtained. The obtained 80 mm × 8 mm × 4 mm molded product was cut to obtain a 40 mm × 8 mm × 4 mm molded product, which was then annealed at 80 ° C. for 16 hours, and the obtained molded product was used as a test piece for heat resistance evaluation. Using.
As a heat resistance evaluation, an HDT / VICAT tester (model name "No. 148-HAD heat distortion tester", manufactured by Yasuda Seiki Seisakusho Co., Ltd.) was used to perform a Vicut softening temperature test in accordance with the A50 method of ISO306. , The Vicat softening temperature was measured.
The Vicat softening temperature test was performed three times for each copolymer, 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。
(Evaluation of releasability)
The resin composition obtained in Examples and Comparative Examples was injection-molded using an injection molding machine (model name "IS-100", manufactured by Toshiba Machine Co., Ltd.) under the conditions of a molding temperature of 250 ° C. and a molding time of 360 seconds. , A molded product having a size of 100 mm × 50 mm × 2 mm was obtained.
In each case, 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。
[Manufacturing Example 0]
900 parts by mass of deionized water, 60 parts by mass of 2-sulfoethyl sodium methacrylate, 10 parts by mass of potassium methacrylate and 12 parts by mass of methyl methacrylate were supplied to a flask equipped with a stirrer, a thermometer and a cooling tube to add nitrogen. While discharging, the flask was heated so that the internal temperature of the flask was 50 ° C. Then, 0.08 parts by mass of 2,2'-azobis (2-methylpropionamidine) dihydrochloride was supplied, and the flask was heated so that the internal temperature of the flask was 60 ° C. Then, using a dropping pump, methyl methacrylate was added dropwise at a rate of 0.24 parts by mass / min for 75 minutes. Then, it 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。
[Manufacturing 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 at a stirring rate of 320 rpm for 15 minutes. After that, methyl methacrylate (95 mol%) (trade name "Acryester M", manufactured by Mitsubishi Rayon Co., Ltd.) 1339.4 parts by mass, methacrylic acid (5 mol%) 60.6 parts by mass, 2,2'-azobis-2. -Methylbutyronitrile (polymerization initiator, trade name "V-59", manufactured by Wako Pure Chemical Industries, Ltd.) 2.8 parts by mass, n-octyl mercaptan (chain transfer agent, manufactured by Tokyo Kasei Kogyo Co., Ltd.) 4.2 parts by mass (content is 0.3 parts by mass with respect to 100 parts by mass of total monomer) and Rikemar S-100A (molder, manufactured by RIKEN Vitamin Co., Ltd.) 2.8 parts by mass (total monomer) The content was 0.2 parts by mass with respect to 100 parts by mass) was supplied to the separable flask, and the mixture was stirred for 5 minutes. Then, 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. Then, nitrogen gas was discharged for 15 minutes.
Then, the temperature of the separable flask was heated to 75 ° C., and the temperature was maintained until the peak of heat generation of polymerization was observed. After the polymerization exothermic peak was observed, the flask was heated so that the internal temperature of the separable flask was 90 ° C. and held for 60 minutes to complete the polymerization. Then, the mixture in the separable flask was filtered, the filtrate was washed with deionized water, and dried at 80 ° C. for 16 hours to obtain a beaded 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。
[Manufacturing Examples 2 to 4]
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 release agent were changed as shown in Table 1. The same operation was carried out 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-shaped precursor (1) was melt-kneaded using a twin-screw kneading extruder (manufactured by Werner & Pfreederer, 30 mmφ) at a kneading temperature of 250 ° C. and a kneading time of 60 seconds, and glutaric acid anhydride unit (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]
The same operation as in Example 1 was carried out except that the precursors used were the precursors (2) to (4), to obtain a pellet-shaped resin composition.
The evaluation results of the obtained resin composition are shown in Table 2.
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 was excellent in heat resistance, mold releasability, and molding stability.
On the other hand, the resin composition obtained in Comparative Example 1 was inferior in mold releasability and molding stability, and the resin composition obtained in Comparative Example 2 was inferior in 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。 Since the molded body of the present invention is excellent in heat resistance, mold releasability, fluidity, mechanical properties, appearance, low water absorption, and moldability, it is used for optical materials, vehicle parts, lighting materials, building materials, and the like. It can be made and is particularly suitable for vehicle parts of automobiles.
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 is a resin composition, a formed configuration and vehicle parts.
Claims (15)
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、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’） It contains a copolymer (A) containing a methyl (meth) acrylate unit (A1) and a (meth) acrylic acid unit (A2), and a release agent (B) which is an organic substance having at least two functional groups. The residual rate of the (meth) acrylic acid unit (A2) represented by the following formula (1') is 90% or more.
The release agent (B), which is an organic substance having at least two functional groups, is glycerin monostearate, glycerin monobehenate, glycerin mono1,2-hydroxystearate, glycerin monooleate, glycerin monocaprilate, glycerin monocaplate. And at least one resin composition selected from the group consisting of glycerin monolaurate (however, it does not contain fluid polyorganosiloxane).
Residual rate (%) of (meth) acrylic acid unit (A2) = {[ratio of (meth) acrylic acid unit (A2) in copolymer (mol%)] / ([(meth) in copolymer Acrylic acid unit (A2) ratio (mol%)] + [ratio of anhydrous glutaric acid unit (A3) in copolymer (mol%)])} x 100 ... (1')
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’） The resin composition according to claim 1, which contains a copolymer (A) containing a methyl (meth) acrylate unit (A1) and a (meth) acrylic acid unit (A2) and satisfies the following condition (2').
10 ≧ Ratio% of log [2Mw] or more after heating at 250 ° C. for 20 minutes obtained from the integrated molecular weight distribution of the resin composition / Percentage% of log [2Mw] or more before heating obtained from the integrated molecular weight distribution of the resin composition ≧ 1.5 ・ ・ ・ (2')
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種とする、樹脂組成物の製造方法。
（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’） A monomer containing methyl (meth) acrylate (a1) and (meth) acrylic acid (a2) is polymerized to obtain a precursor, which is an organic substance having at least two functional groups with the obtained precursor. The agent (B) is melt-kneaded to make the residual ratio of the (meth) acrylic acid unit (a2) represented by the following formula (1') 90% or more.
The release agent (B), which is an organic substance having at least two functional groups, is glycerin monostearate, glycerin monobehenate, glycerin mono1,2-hydroxystearate, glycerin monooleate, glycerin monocaprilate, glycerin monocaplate. A method for producing a resin composition, which comprises at least one selected from the group consisting of glycerin monolaurate and glycerin monolaurate.
Residual rate (%) of (meth) acrylic acid unit (A2) = {[ratio of (meth) acrylic acid unit (A2) in copolymer (mol%)] / ([(meth) in copolymer Acrylic acid unit (A2) ratio (mol%)] + [ratio of anhydrous glutaric acid unit (A3) in copolymer (mol%)])} x 100 ... (1')
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021115771A JP7359194B2 (en) | 2017-03-27 | 2021-07-13 | Resin compositions, molded bodies, and vehicle parts |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017061077A JP2018162405A (en) | 2017-03-27 | 2017-03-27 | Resin composition, method for producing resin composition, molded body and component for vehicle |
| JP2021115771A JP7359194B2 (en) | 2017-03-27 | 2021-07-13 | Resin compositions, molded bodies, and vehicle parts |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017061077A Division JP2018162405A (en) | 2017-03-27 | 2017-03-27 | Resin composition, method for producing resin composition, molded body and component for vehicle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2021165406A true JP2021165406A (en) | 2021-10-14 |
| JP7359194B2 JP7359194B2 (en) | 2023-10-11 |
Family
ID=63859735
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017061077A Pending JP2018162405A (en) | 2017-03-27 | 2017-03-27 | Resin composition, method for producing resin composition, molded body and component for vehicle |
| JP2021115771A Active JP7359194B2 (en) | 2017-03-27 | 2021-07-13 | Resin compositions, molded bodies, and vehicle parts |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017061077A Pending JP2018162405A (en) | 2017-03-27 | 2017-03-27 | Resin composition, method for producing resin composition, molded body and component for vehicle |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JP2018162405A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04335051A (en) * | 1991-05-13 | 1992-11-24 | Asahi Chem Ind Co Ltd | Transparent heat-resistant resin composition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130141466A (en) * | 2010-08-31 | 2013-12-26 | 가부시키가이샤 구라레 | Polymer composition and molded product |
-
2017
- 2017-03-27 JP JP2017061077A patent/JP2018162405A/en active Pending
-
2021
- 2021-07-13 JP JP2021115771A patent/JP7359194B2/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04335051A (en) * | 1991-05-13 | 1992-11-24 | Asahi Chem Ind Co Ltd | Transparent heat-resistant resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018162405A (en) | 2018-10-18 |
| JP7359194B2 (en) | 2023-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6733548B2 (en) | Copolymer, method for producing copolymer, resin composition, molded article and vehicle | |
| JP5138220B2 (en) | Resin composition and polymer containing polymer particles | |
| JP5357019B2 (en) | Fluidity improver for aromatic polycarbonate resin and method for producing the same, aromatic polycarbonate resin composition, and molded article | |
| JP6932965B2 (en) | Resin composition, manufacturing method of resin composition, molded body and vehicle parts | |
| JP6204649B2 (en) | Vehicle member cover containing methacrylic resin | |
| JP6911921B2 (en) | Thermoplastic composition, molded parts, and vehicle parts | |
| JP2022059643A (en) | Transparent thermoplastic resin composition, method for producing the same, molded article obtained by molding transparent thermoplastic resin composition, and method for manufacturing molded article | |
| JP2009215476A (en) | Styrenic resin composition for light diffusing plate and process for producing the same | |
| JP2022059643A5 (en) | ||
| JP2009256406A (en) | Acrylic resin | |
| JP5247314B2 (en) | Methacrylic resin composition | |
| JP2021165406A (en) | Resin composition, molded body and component for vehicle | |
| KR20100002408A (en) | Thermoplastic resin | |
| JP5008155B2 (en) | Acrylic resin production method, acrylic resin, and molded article | |
| JP7010710B2 (en) | Resin molded products for automobiles | |
| JP2007091810A (en) | Extrusion molded article | |
| JP5621836B2 (en) | Methacrylic resin composition | |
| JP6801223B2 (en) | A method for producing a macromonomer copolymer and a method for producing a molded product using the same. | |
| JP5672321B2 (en) | Methacrylic resin composition | |
| JP2020147715A (en) | Polymer for melt molding, resin composition for melt molding, resin molded product, and method for producing polymer for melt molding and resin molded product | |
| JP2016169365A (en) | Methacrylic resin composition, method for producing the same, and molded body | |
| JP2018162403A (en) | Resin composition, method for producing resin composition, molded body and component for vehicle | |
| JP2018162404A (en) | Resin composition, method for producing resin composition, molded body and component for vehicle | |
| JPH11140265A (en) | Methacrylic resin composition | |
| JP2019104944A (en) | Resin material, surface hardness improver, polycarbonate resin composition, and molded body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20210811 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20210811 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20220519 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220531 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20220725 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220928 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20230117 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230414 |
|
| C60 | Trial request (containing other claim documents, opposition documents) |
Free format text: JAPANESE INTERMEDIATE CODE: C60 Effective date: 20230414 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20230421 |
|
| C21 | Notice of transfer of a case for reconsideration by examiners before appeal proceedings |
Free format text: JAPANESE INTERMEDIATE CODE: C21 Effective date: 20230425 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230606 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230802 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20230829 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20230911 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 7359194 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |