JPS62270648A - Heat-resistant methacrylate resin composition - Google Patents
Heat-resistant methacrylate resin compositionInfo
- Publication number
- JPS62270648A JPS62270648A JP11421586A JP11421586A JPS62270648A JP S62270648 A JPS62270648 A JP S62270648A JP 11421586 A JP11421586 A JP 11421586A JP 11421586 A JP11421586 A JP 11421586A JP S62270648 A JPS62270648 A JP S62270648A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- parts
- weight
- methyl methacrylate
- resin
- 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.)
- Pending
Links
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 title abstract description 9
- 239000011342 resin composition Substances 0.000 title description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 45
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 22
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 14
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000113 methacrylic resin Substances 0.000 claims description 16
- -1 aromatic vinyl compound Chemical class 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 4
- 239000011347 resin Substances 0.000 abstract description 30
- 229920005989 resin Polymers 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract 4
- 238000006116 polymerization reaction Methods 0.000 description 23
- 238000000034 method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 16
- 230000003287 optical effect Effects 0.000 description 15
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000011324 bead Substances 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 5
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 2
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000005745 Captan Substances 0.000 description 2
- 235000009852 Cucurbita pepo Nutrition 0.000 description 2
- 241000219104 Cucurbitaceae Species 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- 235000001484 Trigonella foenum graecum Nutrition 0.000 description 2
- 244000250129 Trigonella foenum graecum Species 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229940117949 captan Drugs 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- LDVVMCZRFWMZSG-OLQVQODUSA-N (3ar,7as)-2-(trichloromethylsulfanyl)-3a,4,7,7a-tetrahydroisoindole-1,3-dione Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)Cl)C(=O)[C@H]21 LDVVMCZRFWMZSG-OLQVQODUSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- PSFDAYXWBWRTSM-UHFFFAOYSA-N 1-prop-2-enylpyrrole-2,5-dione Chemical compound C=CCN1C(=O)C=CC1=O PSFDAYXWBWRTSM-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 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
- ATZXURVLNCRXQJ-UHFFFAOYSA-N 2-sulfooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOS(O)(=O)=O ATZXURVLNCRXQJ-UHFFFAOYSA-N 0.000 description 1
- APMOEFCWQRJOPS-UHFFFAOYSA-N 5-ethenyl-1,5-dimethylcyclohexa-1,3-diene Chemical compound CC1=CC=CC(C)(C=C)C1 APMOEFCWQRJOPS-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GHXZTYHSJHQHIJ-UHFFFAOYSA-N Chlorhexidine Chemical compound C=1C=C(Cl)C=CC=1NC(N)=NC(N)=NCCCCCCN=C(N)N=C(N)NC1=CC=C(Cl)C=C1 GHXZTYHSJHQHIJ-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 241000276457 Gadidae Species 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GWFGDXZQZYMSMJ-UHFFFAOYSA-N Octadecansaeure-heptadecylester Natural products CCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC GWFGDXZQZYMSMJ-UHFFFAOYSA-N 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
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229960003260 chlorhexidine Drugs 0.000 description 1
- 125000006849 chlorophenylene group Chemical group 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
３発明の詳細な説明
〔産業上の利用分野〕
本発明は、透明な耐熱性メタクリアし樹脂組成物に関す
る。Detailed Description of the Invention 3 Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a transparent heat-resistant meth-clear resin composition.
メタクリル酸メチ〜を主成分とするメタクリル樹脂は光
学的性質および耐候性に極めて優れ、かつ機械的性質、
熱的性質ならびに成形加工性などに訃いても比較的バラ
ンスのとれた性能を有しているため、これらの特性を生
かして看板、照明用カバー、銘板、自動車部品、電気機
器部品、装飾用あるいは雑貨品など多くの分野で広く使
用されており、更に用途開発も進められている。Methyl methacrylate resin has excellent optical properties and weather resistance, as well as mechanical properties and
Even if it suffers from thermal properties and moldability, it has relatively well-balanced performance, so these characteristics can be used to create products such as signboards, lighting covers, nameplates, automobile parts, electrical equipment parts, decorations, etc. It is widely used in many fields such as miscellaneous goods, and further applications are being developed.
しかし、−面では熱変形温度が１００℃前後と、耐熱性
が充分でないために、その用途展間が制約されている分
野もかなりあり、耐熱性の向上に対する要求には根強い
ものがある。 −メタクリル樹脂の耐熱性を改善させる
方法についてはすでに多くの提案、例えばメタクリル酸
メチルトα−メチルスチレンを共重合させる方法、メタ
クリル酸メチル、α−メチルスチレンおよび無水マレイ
ン酸を共重合させる方法（特公昭４９−１０１５６号）
、メタクリル酸メチル、スチレンおよび無水マレイン酸
を共重合させる方法（特公昭５６−４３２４２号）、メ
タクリｌし酸メチμ、α−メチルスチレン、スチレンお
よび無水マレイン酸を共重合させる方法（特開昭５６−
８１３２２号）、ポリ−α−メチルスチレンをメタクリ
ル酸メチμに溶解シた後メタクリル酸メチルを重合させ
る方法（特公昭４３−１６１６号、特公昭４９−８７１
８号）、メタクリル酸メチルおよびＮ−アリルマレイン
酸イミドを共重合させる方法（特公昭４３−９７５５号
）、６メタクリル酸メチμ、α−メチルスチレンおよび
マレイミドを共重合させる方法（米国特許３６７６４０
４）、多官能単量体を用いた架橋ポリマーの存在下でメ
タクリル酸メチルを共重合させる方法、メタクリル酸メ
チルにメタクリル酸を共重合させた重合体、メタクリル
酸メチル、α−メチルスチレンおよびアクリロニトリル
を共重合させた重合体などがなされている。However, because the heat distortion temperature of the negative side is around 100° C. and the heat resistance is insufficient, there are many fields in which its application is restricted, and there is a deep-rooted demand for improved heat resistance. - Many proposals have already been made regarding methods for improving the heat resistance of methacrylic resins, such as a method of copolymerizing methyl methacrylate and α-methylstyrene, and a method of copolymerizing methyl methacrylate, α-methylstyrene, and maleic anhydride (especially Publication No. 49-10156)
, a method for copolymerizing methyl methacrylate, styrene, and maleic anhydride (Japanese Patent Publication No. 56-43242), a method for copolymerizing methyl methacrylic acid, α-methylstyrene, styrene, and maleic anhydride (Japanese Patent Publication No. 56-43242), 56-
81322), a method of dissolving poly-α-methylstyrene in methylene methacrylate and then polymerizing methyl methacrylate (Japanese Patent Publication No. 1616/1983, Japanese Patent Publication No. 49/871
8), a method for copolymerizing methyl methacrylate and N-allylmaleimide (Japanese Patent Publication No. 43-9755), a method for copolymerizing 6-methyl methacrylate, α-methylstyrene, and maleimide (US Pat. No. 367,640)
4), A method of copolymerizing methyl methacrylate in the presence of a crosslinked polymer using a polyfunctional monomer, a polymer obtained by copolymerizing methacrylic acid with methyl methacrylate, methyl methacrylate, α-methylstyrene, and acrylonitrile Polymers have been made by copolymerizing.
しかし上記提案の方法では重合速度が極めて小さいため
生産性が著しく低くて実用性がなかったシ、機械的性質
、耐候性および光学的性質が低下したり、また成形品が
著しく着色したり、あるいは成形領域が狭いために、成
形加工性が悪いなどいずれの場合も耐熱性はある程度改
善されるものの実用化にかいて多（の問題点が残されて
いる。However, in the above proposed method, the polymerization rate is extremely low, resulting in extremely low productivity and impractical properties.In addition, the mechanical properties, weather resistance, and optical properties may deteriorate, and the molded product may become significantly colored. Although the heat resistance is improved to some extent in both cases, there are still many problems with practical application, such as poor moldability due to the narrow molding area.
本発明はかかる現状に鑑み、メタクリル樹脂本来の優れ
た光学的性質、機械的性質、耐候性、成形加工性などの
特性を低下させることなく、かつ生産性にも優れた耐熱
性メタクリル樹脂を提供しようとするものである。In view of the current situation, the present invention provides a heat-resistant methacrylic resin that does not reduce the inherent excellent properties of methacrylic resin such as optical properties, mechanical properties, weather resistance, and moldability, and also has excellent productivity. This is what I am trying to do.
上記目的に沿って研究を行なった結果、特定の配合組成
を有するメタクリル酸メチル−Ｎ−シクロヘキシルマレ
イミド−芳香族ビニル化合物の共重合体構造を有する共
重合体とメタクリル酸メチルを７０重量％以上を有する
共重合体とからなるａ１指混合物が、その混合物の組成
と同じ組成をもつ単独共重合体よりも機械的性質にすぐ
れ、成形加工性も良く、生産性の点でも優れ、さらに共
重合体相互の屈折率が相異なるにもかかわらず透明性も
良いという全く予想外の効果があることが見出された。As a result of research conducted in line with the above objectives, we found that a copolymer having a copolymer structure of methyl methacrylate-N-cyclohexylmaleimide-aromatic vinyl compound with a specific composition and methyl methacrylate in an amount of 70% by weight or more. The a1-finger mixture consisting of a copolymer having the same composition as that of the mixture has superior mechanical properties, good molding processability, and superior productivity. It has been discovered that although the refractive indexes are different from each other, they have good transparency, which is a completely unexpected effect.
本発明の要旨とするところは、
囚メタクリル酸メチ／ｌ／４０〜９８重量％の）Ｎ−シ
クロヘキシルマンイミド１〜３０重量％及び
（Ｃ）芳香族ビニ／ｌ／化合物１〜３０重量％よ）なる
単量体混合物を重合して得られる共重合体（Ｉ）１〜９
９重量％とメタクリル酸メチルを７０重量％以上含有す
る重合体（■）１〜９９重量％からなる耐熱性メタクリ
ル樹脂組成物にある。The gist of the invention is that (C) 1 to 30% by weight of N-cyclohexylmanimide (methacrylic acid/methacrylate/l/40 to 98% by weight) and (C) 1 to 30% by weight of aromatic vinyl/l/compound. ) Copolymers (I) 1 to 9 obtained by polymerizing the monomer mixture
A heat-resistant methacrylic resin composition comprising 1 to 99% by weight of a polymer (■) containing 9% by weight and 70% by weight or more of methyl methacrylate.
本発明の最大の特徴は、上記の特定組成を有する耐熱性
の共重合体ＣＩ）とメタクリル酸メチルを主成分とする
樹脂をブレンドして均質分散させることによシ、前記特
公昭４３−９７５３号、米国特許３６７６４０４等に記
載される２元系、３元系の共重合体と比較して耐候性、
成型品の無色透明性に優れ、さらに耐熱性、成形加工性
においても極めてバランスのとれた組成物が意外にも得
られることにある。特に本発明の組成物の特徴は、熱変
形温度として１０５℃以上、好ましくは１１５℃以上の
ものが得られることを見出したことにある。The greatest feature of the present invention is that the heat-resistant copolymer CI) having the above-mentioned specific composition and a resin whose main component is methyl methacrylate are blended and homogeneously dispersed. weather resistance, compared to binary and ternary copolymers described in US Pat. No. 3,676,404, etc.
It is surprisingly possible to obtain a composition that is excellent in colorless transparency of the molded product and is also extremely well-balanced in terms of heat resistance and moldability. In particular, the composition of the present invention is characterized by the discovery that a heat distortion temperature of 105°C or higher, preferably 115°C or higher can be obtained.
本発明の組成物において共重合体（Ｉ）を構成するメタ
クリル酸メチ＃またはその部分重合体成分はメタクリル
樹脂本来の光学的性質、耐候性あるいは機械的性質を保
持し、共重合体（ＩＩ）との相溶性をよくするための成
分であり、共重合体（Ｉ）中４０〜９８重量％となる量
用いられる。４０重量％未満では上記の特性が失われ、
また９８重量％を超えると耐熱性の向上が望めなくなる
。In the composition of the present invention, the methyacrylate or its partial polymer component constituting the copolymer (I) retains the optical properties, weather resistance, or mechanical properties inherent to the methacrylic resin, and the copolymer (II) It is a component for improving compatibility with copolymer (I), and is used in an amount of 40 to 98% by weight in copolymer (I). If it is less than 40% by weight, the above properties will be lost,
Moreover, if it exceeds 98% by weight, no improvement in heat resistance can be expected.
また共重合体（Ｉ）の構成成分であるＮ−シクロヘキシ
ルマレイミドは耐熱性を向上させる成分であり、その量
は共重合体ＣＩ）中１〜３０重ｉ％、好ましくは３〜２
５重１チである。１重量％未満では耐熱性の点で劣シ、
３０重量％を超えると樹脂組成物が脆くなシやすく、重
合系が不安定になりやすいので生産性が低下する。Further, N-cyclohexylmaleimide, which is a constituent component of copolymer (I), is a component that improves heat resistance, and its amount is 1 to 30% by weight, preferably 3 to 2% by weight, in copolymer CI).
It is 5 layers and 1 inch. If it is less than 1% by weight, the heat resistance will be poor.
If it exceeds 30% by weight, the resin composition tends to become brittle and the polymerization system tends to become unstable, resulting in a decrease in productivity.
又、共重合体（Ｉ）の構成成分である芳香族ビニル化合
物は、例えばα−メチルスチレンを用いた場合には直接
的に耐熱性を向上させる相乗作用もあるが、むしろ、耐
熱性成分であるＮ−シクロヘキシルマレイミドの共重合
性度広を高めることにより間接的に耐熱性を向上させ、
生産性の改良に対して著しい効果をもたらす。さらに、
流動性の向上及び共重合体（ＩＩ）との相溶性の向上が
この成分によってもたらされるものである。In addition, the aromatic vinyl compound that is a component of copolymer (I) has a synergistic effect that directly improves heat resistance when α-methylstyrene is used, but it is rather a heat-resistant component. Indirectly improves heat resistance by increasing the degree of copolymerization of a certain N-cyclohexylmaleimide,
It has a significant effect on improving productivity. moreover,
This component brings about improved fluidity and improved compatibility with copolymer (II).
即ちメタクリル樹脂（ＩＩ）とメタクリル酸メチルとＮ
−シクロヘキシルマレイミドの２元共重合体との混合物
が透明性を保ち、機械的等の性質がメタク！Ｊ／Ｌ／樹
脂（ＩＩ）に近い特性を示すのはＮ−シクロヘキシルマ
レイミドの共重合割合がごく限られた少量のときだけで
あり、通常この混合物は相乗効果が認められないばかり
でなく、白濁やにごりが生じ光学的性質は劣るものしか
得られない。That is, methacrylic resin (II), methyl methacrylate and N
-The mixture of cyclohexylmaleimide and a binary copolymer maintains transparency and has excellent mechanical properties! J/L/Resin (II) exhibits properties similar to those of Resin (II) only when the copolymerization ratio of N-cyclohexylmaleimide is very limited and small; usually, this mixture not only has no synergistic effect but also becomes cloudy. Cloudiness occurs and only inferior optical properties can be obtained.
また、メタクリル酸メチルと芳香族ビニル化合物の共重
合体と共重合体（ＩＩ）との混合物は相溶性が悪く、一
般に不透明となることを考慮すると、本発明による方法
で物性の優れた、透明な樹脂が得られたのは驚くべき結
果であった。In addition, considering that a mixture of a copolymer of methyl methacrylate and an aromatic vinyl compound and copolymer (II) has poor compatibility and is generally opaque, the method of the present invention can be used to create a transparent material with excellent physical properties. It was a surprising result that a resin of this type was obtained.
本発明の芳香族ビニル化合物の例としては、スチレン、
Ｏ−９ｍ −ｗ ｐ−メチルスチレン、１．３−ジメチ
ルスチレン、２．４−ジメチルスチレン、ｐ−ｔ−ブチ
ルスチレン、α−メチルスチレン、α−メチルスチレン
、α−メチμｍｐ−メチμスチレンなどのモノビニリデ
ン芳香族炭化水素、’ −ｔ ｆｎ −＊ ｐ−クロ
ロスチレン、２．４−ジプロモスチレン、２−メチ＃−
４−クロロスチレンなどのアμハロモノビニリデン芳香
族炭化水素等が挙げられる。特にスチレン、ビニルトル
エン及びα−メチルスチレンからなる群から選ばれた少
なくとも１種が好ましく、さらに耐熱性向上の作用の大
きいα−メチルスチレンを含むことがよシ好ましい。Examples of the aromatic vinyl compound of the present invention include styrene,
O-9m -w p-methylstyrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, pt-butylstyrene, α-methylstyrene, α-methylstyrene, α-methyleneμmp-methyleneμstyrene, etc. monovinylidene aromatic hydrocarbon, ' -t fn -* p-chlorostyrene, 2,4-dipromostyrene, 2-methy#-
Examples include aμ halomonovinylidene aromatic hydrocarbons such as 4-chlorostyrene. Particularly preferred is at least one selected from the group consisting of styrene, vinyltoluene, and α-methylstyrene, and more preferably α-methylstyrene, which has a large effect of improving heat resistance.
前述の効果をあげるために共重合体（Ｉ）中に用いられ
る芳香族ビニル化合物の割合は１〜５０重量％の範囲で
あ）、好ましくは２〜２０重量％、より好ましくは２〜
１５重ｉｅｓの範囲である。The proportion of the aromatic vinyl compound used in the copolymer (I) in order to achieve the above-mentioned effects is in the range of 1 to 50% by weight), preferably 2 to 20% by weight, more preferably 2 to 50% by weight.
It is in the range of 15-fold ies.
１重に４未満では相乗効果が認められず、逆に３０重ｉ
ｓを超えると、共重合体（ＩＩ）との相溶性が低下し、
得られる樹脂組成物の透明性が低下する。No synergistic effect is observed with less than 4 in 1 layer, and conversely, with 30 i
If it exceeds s, the compatibility with copolymer (II) decreases,
The transparency of the resulting resin composition decreases.
本発明に於いては最終的に得られる樹脂組成物の耐熱性
、機械的性質、光学的性質あるいは成形加工性など樹脂
特性全般のパフンスを考慮すると、共重合体（Ｉ）はＮ
−シクロヘキシルマレイミドのモル数をα、芳香族ビニ
ル化合物のモル数をβとしたとき、両成分の配合比（β
／α）がα２〜５の範囲であることが必要であり、ＣＬ
５〜２の範囲が相乗効果の点で特に好ましい。In the present invention, considering the puffiness of the overall resin properties such as heat resistance, mechanical properties, optical properties, and moldability of the resin composition finally obtained, the copolymer (I) is
- When the number of moles of cyclohexylmaleimide is α and the number of moles of aromatic vinyl compound is β, the blending ratio of both components (β
/α) is required to be in the range of α2 to 5, and CL
The range of 5 to 2 is particularly preferable from the viewpoint of synergistic effects.
配合比がｒ：１．２未満あるいは５を超えると共重合体
（ＩＩ）との相溶性の低下が認められ、透明性が低下し
やすい傾向にある。When the blending ratio r is less than 1.2 or more than 5, compatibility with copolymer (II) is observed to decrease, and transparency tends to decrease.
本発明の組成物を構成する共重合体（ＩＩ）はメタクリ
ル樹脂本来の耐候性、機械的性質、光学的性質、成形加
工性を付与するだめのものでちる。共重合体（ＩＩ）中
の主成分であるメタクリル酸メチルはメタクリル樹脂本
来の耐候性、光学的性質、機械的性質を付与するための
ものでちシ、使用量が７０重量％未満であると前記物性
が低下する。より好ましくは８０重量％以上である。メ
タクリル酸メチルと共重合するのに使用される単量体と
してはアクリル酸メチル、アクリル酸エチルなどのアク
リル酸エステル１メタクリル酸エチル、メタクリル酸ブ
チルな、どのメタクリル酸エステル、スチレン、アクリ
ロニトリル、無水マレイン酸等が挙げられ、これらの単
量体は１種又は２種以上、３０重量−以下、好ましくは
２０重ｆｋ％以下の量で共重合される。The copolymer (II) constituting the composition of the present invention is a material that imparts the weather resistance, mechanical properties, optical properties, and moldability inherent to methacrylic resin. Methyl methacrylate, which is the main component in copolymer (II), is used to impart weather resistance, optical properties, and mechanical properties inherent to methacrylic resin, and if the amount used is less than 70% by weight. The physical properties are reduced. More preferably, it is 80% by weight or more. Monomers used for copolymerization with methyl methacrylate include acrylic esters such as methyl acrylate and ethyl acrylate; 1 methacrylic esters such as ethyl methacrylate and butyl methacrylate; styrene; acrylonitrile; and maleic anhydride. Examples include acids, and these monomers are copolymerized one or more in an amount of 30% by weight or less, preferably 20% by weight or less.
本発明の樹脂組成物を構成する共重合体（Ｉ）の使用量
は組成物中１〜９９重量％、好ましくは５〜９５重量％
であυ、１重量％未満であると耐熱性が劣り、９９重量
％を超えると機械的−性質、耐候性が劣る。The amount of copolymer (I) constituting the resin composition of the present invention is 1 to 99% by weight, preferably 5 to 95% by weight of the composition.
If it is less than 1% by weight, heat resistance will be poor, and if it exceeds 99% by weight, mechanical properties and weather resistance will be poor.
また共重合体（Ｉｔ）の使用量は１〜９９重量％、好ま
しくは５〜９５重量％である。より好ましくは１０〜９
０重量％である。１重量％未満では機械的性質、耐候性
が劣シ、９９重量％を超えると耐熱性の向上が望めない
。The amount of copolymer (It) used is 1 to 99% by weight, preferably 5 to 95% by weight. More preferably 10-9
It is 0% by weight. If it is less than 1% by weight, mechanical properties and weather resistance will be poor, and if it exceeds 99% by weight, no improvement in heat resistance can be expected.
本発明の組成物の用途の例としては、樹脂板としての使
用が１例として挙げられる。また成形材料としての使用
も他の好ましい例として挙げられる。特に、α５〜７５
のフローレート（ＦＲ）（ＡＳＴＭ Ｄ−１２５８に
準拠して２３０℃、１０ｋｇ／α２荷重下での１０分間
の押出量圀）を有する成形材料として特に有用なもので
ある。An example of the use of the composition of the present invention is use as a resin board. Another preferred example is use as a molding material. Especially α5~75
It is particularly useful as a molding material having a flow rate (FR) of (10 minute extrusion rate at 230 DEG C. and 10 kg/α2 load according to ASTM D-1258).
本発明の組成物を製造する方法は特に限定されず、例え
ば共電量体（Ｉ）を常法に従って塊状重合、懸濁重合な
どによシ製造し、得られた共重合体ＣＩ）と共重合体（
ｎ）とを混合後、２００〜３００℃の温度で溶融、混練
、押出を行なってブレンド樹脂を製造する方法、共重合
体（ｎ）を製造する単量体混合物に共重合体（Ｉ）を溶
解後、懸濁分散剤を含んだ水媒体中で懸濁重合あるいは
塊状重合する方法、また共重合体（ｎ）を共重合体（Ｉ
）を構成する単量体混合物に溶解後塊状重合する方法な
どが採用される。The method for producing the composition of the present invention is not particularly limited, and for example, the cocharger (I) is produced by bulk polymerization, suspension polymerization, etc. according to a conventional method, and copolymerized with the obtained copolymer CI). Combine (
n) and then melting, kneading, and extruding at a temperature of 200 to 300°C to produce a blend resin, a method in which copolymer (I) is added to a monomer mixture to produce copolymer (n). After dissolution, the copolymer (n) may be subjected to suspension polymerization or bulk polymerization in an aqueous medium containing a suspending dispersant.
) is dissolved in the monomer mixture constituting the compound, followed by bulk polymerization.
また本発明の組成物に於いては必要に応じて、紫外線吸
収剤、剥離剤、酸化防止剤、離型剤、染顔料などの添加
剤を添加してもよい。Additionally, additives such as ultraviolet absorbers, release agents, antioxidants, mold release agents, dyes and pigments may be added to the compositions of the present invention, if necessary.
以下、実施例により本発明をさらに詳しく説明するが、
実施例中の部は重量部を表す。Hereinafter, the present invention will be explained in more detail with reference to Examples.
Parts in the examples represent parts by weight.
なお、実施例中の樹脂組成物の物性評価は次の方法を用
いて行なった。The physical properties of the resin compositions in Examples were evaluated using the following method.
（１）引張強度、伸度
ＡＳＴＭ−Ｄ−６３８
（２） アイゾツト衝撃強度
ＡＳＴＭ、τ１Ｄ−２５６
（３）附熱変形性
熱変形温度（ＨＤＴ）Ｃ℃）
ＡＳＴＭ−Ｄ−６４８
（４）全光線透過率、曇価
ＡＳＴＭ−Ｄ−１００３
（５） メルトインデックス
ＡＥｉＴＭ−Ｄ−１２５８
２３０℃ 荷重１０に９
（６）射出成形板の色調及び透明性
目視
（７）耐光性
加速暴露試験 １１００時間、スガ（株）製耐候試験機
で温度６ｏ℃カーボンアーク灯、１時間当り１２分降雨
の条件で実施した。(1) Tensile strength, elongation ASTM-D-638 (2) Izot impact strength ASTM, τ1D-256 (3) Heat distortion temperature (HDT) Celsius) ASTM-D-648 (4) Total beam Transmittance, haze value ASTM-D-1003 (5) Melt index AEiTM-D-1258 230°C Load 10 to 9 (6) Color tone and transparency of injection molded plate Visual observation (7) Light resistance accelerated exposure test 1100 hours, Suga The test was carried out using a weather tester manufactured by Co., Ltd. under the conditions of a carbon arc lamp at a temperature of 6oC and rainfall of 12 minutes per hour.
（８）耐煮沸性
寸法２瓢×５０鱈Ｘ１［］０瓢の試験片を１００℃の純
水に４時間浸漬し白化の程度を目視判定した。(8) Boiling resistance Dimensions: A test piece of 2 gourds x 50 cods x 1 []0 gourds was immersed in pure water at 100°C for 4 hours, and the degree of whitening was visually determined.
（９）研削性
タクボ精機製ＨＤ−３０Ｗ手摺機を用い、寸法２ ＷＸ
１１０頑×１１０鱈の試験片を砥石面（ダイヤモンド
砥石、オーμメタｐポンド）へ圧着し研削する方法によ
シ評価した。(9) Grindability Using Takubo Seiki HD-30W handrail machine, dimension 2 WX
Evaluation was carried out by pressing a 110 x 110 cod test piece onto a grinding wheel surface (diamond grinding wheel, Ohmeta P-pond) and grinding it.
（イ） 曲げ試験（破壊強度、弾性係数）ＡＳＴＭ−Ｄ
−７９０−６３
（ロ）吸水率
ＡＳ’Ｉ’Ｍ−Ｄ−５７０−６３２４時間Ｑ２ Ｙ、
１．ｆｌｉ（イエローネスインデックス）ＡＳＴＭ−Ｄ
−１９２５（透過法）
実施例１．２及び比較例１は連続的樹脂板製造の実施態
様の説明であるが、その製造方法についてこ＼で補足説
明してお（：
重合原料を鋳型中で重合する方法において、鋳型がある
間隙をもって対向して走行する２個のエンドレスベルト
の対向面と２個のべ／Ｌ／）に挟まれた状態でべ／Ｌ／
トの走行に追随して走行するガスケットより形成され、
その鋳型の成形空間部にその上流端よシ重合原料を供給
し、これを該成形空間内部で連続的に重合率９日−以上
に重合せしめて下流端より樹脂板を連続的に取り出す方
式であり、例えば特願昭５９−７０２４号に記載されて
いる装置によシ製造できる。なお、本発明樹脂組成物は
このような製造方法によって得られる重合体に限定され
るものではない。(a) Bending test (fracture strength, elastic modulus) ASTM-D
-790-63 (b) Water absorption rate AS'I'M-D-570-6324 hours Q2 Y,
1. fli (yellowness index) ASTM-D
-1925 (Transmission method) Example 1.2 and Comparative Example 1 are explanations of embodiments of continuous resin plate production, but here is a supplementary explanation of the production method (: Polymerization raw material is placed in a mold. In the polymerization method, the mold is sandwiched between the opposing surfaces of two endless belts running opposite each other with a certain gap between them and the two belts (L/L/).
It is formed from a gasket that follows the movement of the vehicle.
In this method, a polymerization raw material is supplied into the molding space of the mold from the upstream end, and the material is continuously polymerized inside the molding space to a polymerization rate of 9 days or more, and the resin plate is continuously taken out from the downstream end. For example, it can be manufactured using the apparatus described in Japanese Patent Application No. 59-7024. Note that the resin composition of the present invention is not limited to the polymer obtained by such a manufacturing method.
実施例１
内容積５０Ｌの攪拌機付き耐圧重合釜を用い、２７に９
の脱イオン水、分散剤としてメタクリル酸メチ〃と２−
スルホキシエチルメタクリレートからなる共重合体３Ｉ
及び硫酸ナトリウム９０ｇを仕込み、メタクリル酸メチ
／Ｌ’７２部、Ｎ−シクロヘキシルマレイミド１７部、
α−メチμスチレン１０部、スチレン１部、ｎ−オクチ
ルメルカプタン（ＬＯ７部、アゾビスイソブチロニトリ
ルα５部からなる単量体混合物１８ｋｇを仕込み、２０
０ ｒｐｍで攪拌しながら窒素を１０ｔ／ｍｉｎの割合
で２０分間バブリングさせて系内の酸素を除き、８０℃
に４時間加熱して懸濁重合させ、さらに１２０℃に昇温
し、３０分間保持した後、冷却、水洗乾燥を行なって平
均粒径０．５ｍのビーズ状共重合体（Ｉ）を得た。Example 1 Using a pressure-resistant polymerization pot with an internal volume of 50 L and equipped with a stirrer, 27 to 9
deionized water, methacrylate as a dispersant and 2-
Copolymer 3I consisting of sulfoxyethyl methacrylate
and 90 g of sodium sulfate, 72 parts of methi methacrylate/L', 17 parts of N-cyclohexylmaleimide,
18 kg of a monomer mixture consisting of 10 parts of α-methylene μ styrene, 1 part of styrene, n-octyl mercaptan (7 parts of LO, and 5 parts of azobisisobutyronitrile α) was charged,
Bubble nitrogen at a rate of 10 t/min for 20 minutes while stirring at 0 rpm to remove oxygen from the system, and heat to 80°C.
The mixture was heated for 4 hours to carry out suspension polymerization, and the temperature was further raised to 120°C, held for 30 minutes, cooled, washed with water, and dried to obtain a bead-shaped copolymer (I) with an average particle size of 0.5 m. .
この共重合体（Ｉ） ５５部にメタクリル酸メチ°／Ｉ
／６５部、エアゾールＯＴ（アメリカンシアナミド社製
、剥離剤）０．０５部、紫外線吸収剤（ＬＯ５部、およ
びλ２′−アゾビスー２．４−ジメチμバレロニトリル
［１ＬＯＢ部を加え攪拌溶解せしめた。得られた重合原
料を減圧下において脱気させ、図面で示した連続装置に
連続的に供給し７５℃で１時間、次いで１３５℃で４分
間加熱重合せしめて板厚３■の樹脂板を得た。55 parts of this copolymer (I) and methyl methacrylate/I
/65 parts, 0.05 parts of Aerosol OT (manufactured by American Cyanamid, release agent), 5 parts of ultraviolet absorber (LO), and 1 LOB part of λ2'-azobis-2,4-dimethymuvaleronitrile were added and dissolved with stirring. The obtained polymerization raw material was degassed under reduced pressure and continuously fed to the continuous equipment shown in the drawing, and heated and polymerized at 75°C for 1 hour and then at 135°C for 4 minutes to obtain a resin plate with a thickness of 3 cm. Ta.
図面において１，１′はエンドレスベルト、２．２：４
３′は主プーリ−，４，４’、 ４６’はキャリヤロー
／Ｌ’、５．５’は第１重合区域、スフ′は温水スプレ
ー、八８′は第２重合区域、９，１０は冷却区域、１１
はキャリヤロー〃、１２．１２’はロール、１３はガス
ケット、１４は樹脂板、１５は重合原料注入装置である
。In the drawing, 1, 1' is an endless belt, 2.2:4
3' is the main pulley, 4, 4', 46' are the carrier row/L', 5.5' is the first polymerization zone, 88' is the hot water spray, 88' is the second polymerization zone, 9, 10 are the cooling area, 11
12 and 12' are rolls, 13 is a gasket, 14 is a resin plate, and 15 is a polymerization raw material injection device.
この樹脂板について物性を評価し、その結果を第１表に
示す。The physical properties of this resin plate were evaluated and the results are shown in Table 1.
実施例２
単量体混合物の組成を下記の通りとした以外は実施例１
と全く同様にして厚さ３■の樹脂板を得た。評価結果を
第１表に示す。Example 2 Example 1 except that the composition of the monomer mixture was as follows.
A resin plate with a thickness of 3 cm was obtained in exactly the same manner as above. The evaluation results are shown in Table 1.
メタクリル酸メチ／Ｌ’ ８５部Ｎ−シク
ロヘキシルマレイミド ９部α−メチμスチレン
６部
ｎ−オクチルメルカプタン １１．１５部アゾビ
スイソブチロニトリＡ／ ａ、ｓ部比較例１
メタクリル酸メチμ単量体のみを加熱用ジャケット、冷
却用ジャケット、コンデンサー及ヒ攪拌機を備えた５ｏ
ｏｏｔの円筒縦型反応槽に１０００を仕込み加熱した。Methyl methacrylate/L' 85 parts N-cyclohexylmaleimide 9 parts α-methylene μ styrene 6 parts n-octyl mercaptan 11.15 parts Azobisisobutyronitrile A/a, s parts Comparative example 1 Methyl μ methacrylate monomer amount Only the body is equipped with a heating jacket, a cooling jacket, a condenser and a stirrer.
1000 was charged into a cylindrical vertical reaction tank and heated.
該単量体が８０℃に昇温したとき、重合開始剤として２
．２′−アゾビス−２，４−ジメチルバレロニトリルを
単量体に対して（ＬＯ６５％加えて攪拌した。該単量体
は重合反応を開始し、重合熱により飽和温度に達し、コ
ンデンサーよシ還流を始め、重合開始剤を添加した時点
より８分を経過した後、急速に冷却を行なって、２０℃
での粘度が１８００ ｃｐ。When the monomer was heated to 80°C, 2
．． 2'-azobis-2,4-dimethylvaleronitrile was added to the monomer (LO65%) and stirred. The monomer started a polymerization reaction, reached a saturation temperature due to the heat of polymerization, and was refluxed from the condenser. After 8 minutes from the time when the polymerization initiator was added, the temperature was rapidly cooled to 20°C.
Viscosity at 1800 cp.
重合転化率が２２チのシラツブ状部分電合物を得た。A siliculate partially charged product with a polymerization conversion of 22 was obtained.
上記の如くして調製した７ラップ状部分重合物１００部
にエアシー／ｕＯＴα０５部、紫外線吸収剤１０５部及
び２２′−アゾビス−２，４−ジメチルバレロニトリル
０．０８部を加えて攪拌溶解させ重合原料を得た。この
重合原料を用いて実施例１と全く同じ方法で厚さ３餌の
樹脂板を得た。05 parts of Air Sea/uOTα, 105 parts of ultraviolet absorber, and 0.08 parts of 22'-azobis-2,4-dimethylvaleronitrile were added to 100 parts of the 7-wrap partial polymer prepared as above, and the mixture was stirred and dissolved to polymerize. I got the raw material. Using this polymerization raw material, a resin plate having a thickness of 3 layers was obtained in exactly the same manner as in Example 1.
この樹脂板を評価し第１表に示す結果を得た。This resin plate was evaluated and the results shown in Table 1 were obtained.
第 １ 表
実施例１ ２ 比較例１
表面外観
外観（目視判定） 無色透明 無色透明 無
色透明光沢度（チ） １０６ １０９
１１０全透（％ ） ９１．２ ９１
． ｑ ９五〇ｍ （ｉｔｔｉｉ）
ｚ２１．４ ０．９曲げ強度（ゆ／α２）
１０２８ １１０４ １０９４曲げ弾性係数
（〃） 五０Ｘ１０’ 五０Ｘ１０’ 五
０Ｘ１０４耐熱性（ＨＤＴ、’Ｃ） １０７
１０５ １００吸水率（２４時間、チ） α５
ｒＸ５ ０．３耐 煮 沸 性
変化なし 変化なし 表面白化対 光
性 変化なし 変化なし 変化なし第１
表の結果で明らかな様に、比較例１のメタクリル樹脂板
と比較し、本発明品は表面外観、機械的性質、吸水性、
耐煮沸性及び耐候性において、遜色なく、しかも耐熱性
は大幅に向上しており、メタクリル樹脂板として有用な
ものである。Table 1 Example 1 2 Comparative Example 1 Surface appearance (visual judgment) Colorless and transparent Colorless and transparent Colorless and transparent Glossiness (chi) 106 109
110 complete transparency (%) 91.2 91
．． q 950m (ittii)
z21.4 0.9 bending strength (yu/α2)
1028 1104 1094 Flexural modulus (〃) 50X10'50X10' 50X104 Heat resistance (HDT, 'C) 107
105 100 water absorption rate (24 hours, chi) α5
rX5 0.3 boiling resistance
No change No change Surface whitening vs. light
Gender No change No change No change 1st
As is clear from the results in the table, compared to the methacrylic resin board of Comparative Example 1, the product of the present invention has improved surface appearance, mechanical properties, water absorption,
It has comparable boiling resistance and weather resistance, and has significantly improved heat resistance, making it useful as a methacrylic resin board.
実施例３〜４、比較例２．３
実施例１と同じ内容積ＳＱＬの耐圧重合釜を用い、単量
体混合物の組成をメタクリル酸メチｆｉ／７０部、Ｎ−
シクロヘキシルマレイミド１８部、α−メチルスチレン
１２部、ｎ−オクチルメ〜カプタンｎ、ｏｓ部、アゾビ
スイソブチロニトリ／Ｌ’α５部、ステアリン酸モノグ
リセフィト（ＬＯ５部、紫外線吸収剤０．１部とする以
外は実施例１と同様に操作して共重合体（Ｉ）のビーズ
を得た。Examples 3 to 4, Comparative Example 2.3 Using a pressure-resistant polymerization pot with the same internal volume SQL as in Example 1, the composition of the monomer mixture was changed to methacrylic acid methifi/70 parts, N-
Cyclohexylmaleimide 18 parts, α-methylstyrene 12 parts, n-octyl me-captan n, os parts, azobisisobutyronitrile/L'α 5 parts, stearic acid monoglycephyte (LO 5 parts, ultraviolet absorber 0.1 parts) Beads of copolymer (I) were obtained in the same manner as in Example 1 except for the following.
また同じ重合釜を用いて、単量体混合物の組成をメタク
リル酸メチ／Ｉ／９７部、アクリμ酸メチＡ／３部、ｎ
−オクチｐメ〃カプタン０．２２部、アゾビスイソブチ
ロニトリｉｖα１部、ステアリルステアレート００５部
、紫外線吸収剤１１部とし、重合時間を２時間とする以
外は実施例１と全く同様にしてメタクリル樹脂共重合体
（ＩＩ）のビーズを得た。Further, using the same polymerization pot, the composition of the monomer mixture was changed to 97 parts of methi methacrylate/I, 3 parts of methyl acrylate A, n
- 0.22 parts of octypmethcaptan, 1 part of azobisisobutyronitrile ivα, 0.05 parts of stearyl stearate, and 11 parts of ultraviolet absorber were used, and the polymerization time was 2 hours. Beads of methacrylic resin copolymer (II) were obtained.
これらを第２表に示す割合でヘンシェルミキサーでブレ
ンドした後、２ペント付小型２軸押出機で２５０℃の温
度でベレットに賦形した。These were blended using a Henschel mixer in the proportions shown in Table 2, and then shaped into pellets at a temperature of 250°C using a small twin-screw extruder with two pens.
このペレットを下記の条件で射出成形し、得られた試験
片（１１０■Ｘ１１０ｍＸ２ｓａ＋厚）から第３表の評
価結果を得た。This pellet was injection molded under the following conditions, and the evaluation results shown in Table 3 were obtained from the resulting test piece (110 mm x 110 m x 2 sa + thickness).
射出成形機：（株）日本製鋼新製Ｖ−１７−６５型スク
リュ一式自動射出成形機
射出成形条件ニジリンダ一温度２５５℃射出成形圧 ７
００ ｋｇ７ｃｍｚ
金型温度 ６０℃
比較例４
単量体混合物の組成をメタクリル酸メチル７６．９部、
アクリル酸メチ１２．１部、Ｎ−シクロヘキシルマンイ
ミド１２．６ 部、α−メチルスｆＶンａ４部、ｎ−オ
クチルメルカプタンα０５部、アゾビスイソブチロニト
リル０．５部、ステアリン酸モノグリセライドＱ、０５
部、紫外線吸収剤０．１部とする以外は実施例１と全く
同様に操作して共重合体（Ｉ）のビーズを得た。Injection molding machine: Nippon Steel Corporation V-17-65 screw set automatic injection molding machine Injection molding conditions Niji cylinder temperature 255℃ Injection molding pressure 7
00 kg7cmz Mold temperature 60℃ Comparative Example 4 The composition of the monomer mixture was 76.9 parts of methyl methacrylate,
Methyl acrylate 12.1 parts, N-cyclohexylmanimide 12.6 parts, α-methyls fVn a 4 parts, n-octyl mercaptan α 05 parts, azobisisobutyronitrile 0.5 parts, stearic acid monoglyceride Q, 05
Beads of copolymer (I) were obtained in the same manner as in Example 1 except that the amount of UV absorbent was 0.1 part.
このビーズを比較例２と全く同様に押出し、射出成形し
て第３表の結果を得た。These beads were extruded and injection molded in exactly the same manner as in Comparative Example 2 to obtain the results shown in Table 3.
第 ２ 表
■
ト
第３表から明白な様に、本発明品は耐熱性に優れ、光学
的、機械的性質あるいは耐光性もメタクリル樹脂（比較
例３）と比較して遜色ないものである。なお、本発明以
外の方法でも耐熱性を向上させることができ、その方法
は特願昭５９−２６２８６８号として提案されているが
、本発明の組成物はその提案の共重合体よりも、全体と
しての組成が同じであっても、優れた物性を示すことが
判明した。As is clear from Tables 2 and 3, the products of the present invention have excellent heat resistance, and are comparable in optical, mechanical properties, and light resistance to methacrylic resins (Comparative Example 3). Note that heat resistance can be improved by methods other than the present invention, and this method has been proposed in Japanese Patent Application No. 59-262868, but the composition of the present invention has a higher overall heat resistance than the proposed copolymer. It has been found that even if the composition is the same, they exhibit excellent physical properties.
比較例５．６
単量体混合物の組成をメタクリμ酸メチμ７０部、Ｎ−
シフ冒ヘキＶ）ｖマレイミド３１］部、Ｎ−オクチμメ
ルカプタン１２部、アゾビスイソブチロニトリｆｉ／１
１部、ステアリン酸モノグリセライドＣＬＯ５部、紫外
線吸収剤Ｑ、１部とし、重合時間を９０分とする以外は
実施例１と全く同じに操作してビーズ状２元共重合体を
得た。Comparative Example 5.6 The composition of the monomer mixture was changed to 70 parts of methacrylic acid, N-
31 parts of Schiff's maleimide, 12 parts of N-octymu mercaptan, azobisisobutyronitrifi/1
A bead-shaped binary copolymer was obtained by carrying out the same procedure as in Example 1, except that the polymerization time was 90 minutes, and the polymerization time was 90 minutes.
このビーズは未反応単量体が多く含まれていたのでメタ
ノールで洗浄し、乾燥した後、実施例３．４と全く同様
にメタクリル共重合体（ＩＩ）と第４表に示す割合でブ
レンドし、押出し賦形した後、射出成形し、評価を実施
した。Since these beads contained a large amount of unreacted monomer, they were washed with methanol, dried, and then blended with methacrylic copolymer (II) in the proportions shown in Table 4 in exactly the same manner as in Example 3.4. After extrusion shaping, injection molding was performed and evaluation was performed.
第 ４ 表
比較例５及び６の射出成形試片は黄色に着色し、半透明
であシ、かつ重合体の相溶性が悪く濃淡の斑が認められ
た。従って、これらの試片は実施例３．４と比較して、
大幅に光学性能の劣ったものであった。The injection molded specimens of Comparative Examples 5 and 6 in Table 4 were colored yellow, translucent and opaque, and had poor compatibility with the polymer, with uneven shading observed. Therefore, these specimens compared with Example 3.4,
The optical performance was significantly inferior.
実施例５．６
メタクリ／Ｌ’酸メチ／Ｉ／ａａａｇ、α−メチルスチ
レンｓａｇ、ｐ−メチルスチレン４０ｇ、Ｎ−シクロヘ
キシルマレイミド１１０ｇ、ｔ−ドデシルメルカプタン
１．５９ 、アゾビスイソブチロニトリ／１１０−ａｌ
ｌ、エアシー／Ｌ’−ＯＴα１９及び紫外線吸収剤０−
５９からなる単量体混合物を溶解後ガスケットを介して
３■の間隔とした２枚のガラスからなるセルに流し込み
、６５℃の温水中で重合硬化させた。そして温水中に浸
漬してから内温がピークに達するまでの時間をモル中に
セットした熱電対で確認し、１時間を経過後温水中から
七μを取出し、１３０℃の空気加熱炉中で２時間処理し
た。冷却後ガラス板をはずし、板厚約３ｆＩ１１の樹脂
板を得た。この板をクリーンボックス中で粉砕し、３〜
４ｆｆｉ１１程度のベレット状とした。このベレットと
三菱レイヨン（株）製メタクリ〃樹脂３アクリベットＶ
Ｈ”を第５表に示す割合で、タンブラ−でブレンド後、
実施例３と全く同様に押出し賦形後、射出成形し、第５
表の結果を得た。Example 5.6 Methacrylate/L' acid methyl/I/aaag, α-methylstyrene sag, p-methylstyrene 40g, N-cyclohexylmaleimide 110g, t-dodecylmercaptan 1.59, azobisisobutyronitrile/110 -al
l, air sea/L'-OTα19 and ultraviolet absorber 0-
After melting, the monomer mixture consisting of 59 was poured into a cell consisting of two glass sheets separated by 3 squares through a gasket, and polymerized and hardened in warm water at 65°C. Then, the time from immersion in hot water until the internal temperature reaches its peak was confirmed using a thermocouple set in the mold. After 1 hour, the 7μ sample was taken out of the hot water and placed in an air heating oven at 130℃. It was treated for 2 hours. After cooling, the glass plate was removed to obtain a resin plate with a thickness of about 3 fI11. This board is crushed in a clean box, and
It was made into a pellet shape of about 4ffi11. This beret and Mitsubishi Rayon Co., Ltd.'s Methacrylic Resin 3 Acrybet V
H" in the proportions shown in Table 5, after blending in a tumbler,
After extrusion shaping and injection molding in exactly the same manner as in Example 3, the fifth
Obtained the results in the table.
実施例７
メタクリル酸メチル７９部、Ｎ−シクロヘキシフレマレ
イミド１２部、α−メチルスチレン８部、アクリル酸エ
チ／Ｌ／１部、ｎ−オクチμメμカプタンα１２部、ア
ゾビスイソブチロニトリμｍ３５部からなる単量体混合
物を用いる以外は実施例１と同様にしてビーズ状共重合
体ＣＩ）ヲ得り。このビーズとアクリベットＶＨ（前述
）とを等量の割合でへンシエルミキサーでブレンドした
後実施例３と全く同様に押出し賦形した。Example 7 Methyl methacrylate 79 parts, N-cyclohexyfremaleimide 12 parts, α-methylstyrene 8 parts, ethyl acrylate/L/1 part, n-octyme μcaptan α 12 parts, azobisisobutyronitrium μm 35 A bead-like copolymer CI) was obtained in the same manner as in Example 1, except that a monomer mixture consisting of These beads and Acryvet VH (described above) were blended in equal amounts using a Henschel mixer, and then extruded and shaped in exactly the same manner as in Example 3.
得られたベレットを用い中心肉厚３１１１１のレンズを
成形した。透明で着色は認められず、また光学的歪もほ
とんどなかった。型の転写性も良好で、１００℃での使
用に耐えるものであった。A lens having a center wall thickness of 31,111 mm was molded using the obtained pellet. It was transparent with no coloration and almost no optical distortion. The mold had good transferability and could withstand use at 100°C.
レンズの周辺部の研削性を評価した結果、ポリマーの付
着は認められず良好であった。As a result of evaluating the grindability of the peripheral area of the lens, it was found to be good with no polymer adhesion observed.
なお、実施例３と同様に射出成形品の評価を行った結果
、このメタクリル樹脂組成物の耐熱性は１１１℃で、全
光線透過率は９２．８％、曇価は［１８であった。In addition, as a result of evaluating the injection molded product in the same manner as in Example 3, the heat resistance of this methacrylic resin composition was 111° C., the total light transmittance was 92.8%, and the haze value was [18].
実施例８
メタクリル酸メチｆｉ／７７０ｇ、スチレン１２０１１
無水マＶイン酸１００ｇ、アクリル酸メチ１Ｖ１０ｆｉ
、ラウロイルパーオキサイド五５ｇ、ｎ−オクチμメμ
カプタン２．２ｇ、剥離剤ＪＰ−５０４（城北化学（株
）製）α４ｇ、紫外線吸収剤ａ、ｓｇからなる単量体混
合物を７６℃の温水中で重合硬化させる以外は実施例５
と全く同様に操作して共重合体（■）のベレットを得た
。Example 8 Methyfi methacrylate/770g, styrene 12011
100g of anhydrous mavic acid, 1V10fi of acrylic acid
, lauroyl peroxide 5g, n-octium μm
Example 5 except that a monomer mixture consisting of 2.2 g of captan, release agent JP-504 (manufactured by Johoku Kagaku Co., Ltd.) α4g, ultraviolet absorbers a and sg was polymerized and cured in hot water at 76°C.
A pellet of copolymer (■) was obtained in exactly the same manner as above.
実施例５で用いた共重合体ＣＩ）と共重合体（Ｉｔ）を
等量の割合でヘンシェルミキサーでブレンドし、実施例
３と全く同様にして評価を行ない下記の結果を得た。Copolymer CI) and copolymer (It) used in Example 5 were blended in equal amounts using a Henschel mixer, and evaluated in exactly the same manner as in Example 3 to obtain the following results.
熱変形温度（６） １１７全光線透過率（
（５） ９２．２曇 価 （釣
１．６引張強度（ｋｇ／ｃｍ” ）
ｙ ｏ ｓアイゾツト衝撃強度（ゆ・α／
ｚ） １．２射出成形板の色調（目視）
淡黄色透明実施例９
メタクリル酸メチ／Ｌ’６５部、メタクリル樹脂（アク
リベットＶＨ） ２０部、α−メチｐスチレン６部、Ｎ
−７クロヘキＶ／Ｉ／マレイミド９部ラウロイルパーオ
キサイド１２部、エアゾールＯＴα０１部を混合溶解し
、後は実施例５と全く同様に操作し、板厚約３１１１１
１の樹脂板を得た。Heat distortion temperature (6) 117 Total light transmittance (
(5) 92.2 cloud price (fishing)
1.6 tensile strength (kg/cm”)
y o s Izot impact strength (yu・α/
z) 1.2 Color tone of injection molded plate (visual observation)
Light yellow transparent Example 9 Methyl methacrylate/L' 65 parts, methacrylic resin (Acrivet VH) 20 parts, α-methyp-styrene 6 parts, N
-7 Chlorohex V/I/maleimide 9 parts lauroyl peroxide 12 parts and aerosol OTα 01 part were mixed and dissolved, and the rest was operated in exactly the same manner as in Example 5, and the plate thickness was approximately 31111.
A resin plate of No. 1 was obtained.
この樹脂板の物性を測定し第６表の結果を得た比較例７
α−メチルスチレンとＮ−シクロヘキＶＩＩ／−ＱＶイ
ミドの代りにメタクリル酸メチμを用い２以外は全〈実
施例９と同様に操作し、第６表Ｃ結果を得た。The physical properties of this resin plate were measured and the results shown in Table 6 were obtained. Comparative Example 7 Methyl methacrylate μ was used in place of α-methylstyrene and N-cyclohex VII/-QV imide. The same procedure was carried out to obtain the results shown in Table 6, C.
比較例８
Ｎ−シクロヘギＶ／Ｌ／マレイミドの代すにＮ−（０−
クロロフエニ／Ｉ／）マレイミドヲ用いるね外は実施例
９と全く同様に操作し、第６表の着果を得た。Comparative Example 8 N-(0-
The procedure was carried out in exactly the same manner as in Example 9 except that chlorophenylene/I/) maleimide was used, and the results shown in Table 6 were obtained.
比較例９
（アクリベットＶＨ）２０部、Ｎ−シクロヘキシルマレ
イミド１０部、ラウロイμパーオキサイドＱ、２部、エ
アシー／ｌ１０Ｔ１０１部を混合溶・ 解し、後は実施
例９と全く同様に操作し、第６□ 表の結果を得た。Comparative Example 9 20 parts of (Acrivet VH), 10 parts of N-cyclohexylmaleimide, 2 parts of Lauroy μ Peroxide Q, and 101 parts of Air Sea/l10T were mixed and dissolved, and the rest was operated in exactly the same manner as in Example 9. 6□ Obtained the results shown in the table.
第６表
・ｌ
「
、−（−
あ
：［
し
！ 本発明によるもの（実施例９）はメタクリル１
樹脂単独（比較例７）に比較し、光学的性質が同等
で耐熱性にすぐれ、他のマレイミド系化合物を用いたも
の（比較例８）より着色が少な−くもの（比較例９）よ
り耐熱性、光学特性いずれもすぐれたものであることが
わかる。Table 6・l " , -(- A: [ Shi! The product according to the present invention (Example 9) is methacryl 1
Compared to the resin alone (Comparative Example 7), it has the same optical properties and excellent heat resistance, and has less coloring than the resin using other maleimide compounds (Comparative Example 8), but has better heat resistance than the resin (Comparative Example 9). It can be seen that both the properties and optical properties are excellent.
本発明の樹脂は、ポリメチルメタクリレートにほぼ匹敵
するすぐれた機械的性質、耐候性および成形加工性を保
持し、且つ優れた耐熱性を有する。The resin of the present invention maintains excellent mechanical properties, weather resistance, and moldability almost comparable to polymethyl methacrylate, and has excellent heat resistance.
本発明の樹脂は上述のような特性をもつため次の用途に
有用である。Since the resin of the present invention has the above-mentioned properties, it is useful for the following uses.
看板、照明用カバー、銘板、自動車用部品、電気機器部
品、装飾用あるいは雑貨品など、アクリμ系樹脂の使用
されている分野での応用ができる。特に高い耐熱性を要
求される分野に対応できる。It can be applied in fields where acrylic μ-based resins are used, such as signboards, lighting covers, nameplates, automobile parts, electrical equipment parts, decorations, and miscellaneous goods. It can be used in fields that require particularly high heat resistance.
また光学用素子としての分野、特にレンズ用として、屈
折率が高く、耐熱性が高く、低吸湿性でちゃ、レンズ用
として必要な表面性、加工性に秀れているため形態安定
性も良く、使用雰囲気がアクリル樹脂よシも広く有利に
使用できる（例として、ピックアップレンズ、めがね用
レンズ、カメラ用レンズ、プロジェクタ−用フレネルレ
ンズ等が挙げられる）。また、光デイスク用の基板や光
伝送性繊維の芯またはさや材としても用いられる。In addition, it is suitable for use in the field of optical elements, especially for lenses, as it has a high refractive index, high heat resistance, low moisture absorption, and has excellent surface properties and processability necessary for lenses, so it has good morphological stability. It can also be used advantageously in a wide range of environments other than acrylic resin (eg, pickup lenses, glasses lenses, camera lenses, Fresnel lenses for projectors, etc.). It is also used as a substrate for optical disks and as a core or sheath material for optically transmitting fibers.
第１図は、実施例１及び２の樹脂板を製造するために用
いられる連続重合装置の正面説明図である。図面中の主
要な符号は次の通りである：１．１′・・・エンドレス
ベルト
２、 ２’、 ３． ３’・・・主プーリ５．５′・
・−第１重合区域
７．７′・・・温水スプレー
８．８′・・・第２重合区域
９．１０・・・冷却区域
１３・・・ガスケット
１４・・・樹脂板
１５・・・原料注入装置FIG. 1 is an explanatory front view of a continuous polymerization apparatus used for manufacturing the resin plates of Examples 1 and 2. The main symbols in the drawings are as follows: 1.1'...endless belt 2, 2', 3. 3'...Main pulley 5.5'.
-First polymerization zone 7.7'...Hot water spray 8.8'...Second polymerization zone 9.10...Cooling zone 13...Gasket 14...Resin plate 15...Raw material injection device
Claims (1)
ロヘキシルマレイミド１〜３０重量％及び芳香族ビニル
化合物１〜３０重量％からなる単量体混合物の共重合体
（ I ）１〜９９重量％とメタクリル酸メチルを７０重
量％以上含有する重合体（II）９９〜１重量％とからな
る耐熱性メタクリル樹脂組成物。 ２、芳香族ビニル化合物が、スチレン、α−メチルスチ
レン、ビニルトルエンよりなる群より選ばれた少なくと
も１種である特許請求範囲第１項記載の耐熱性メタクリ
ル樹脂組成物。 ３、共重合体（ I ）が、Ｎ−シクロヘキシルマレイミ
ドのモル数をα、芳香族ビニル化合物のモル数をβとし
たとき両成分の配合比（β／α）が０．５〜２となる量
的関係で構成されたものであることを特徴とする特許請
求範囲第１項記載の耐熱性メタクリル樹脂組成物。[Scope of Claims] 1. Copolymer (I) of a monomer mixture consisting of 98-40% by weight of methyl methacrylate, 1-30% by weight of N-cyclohexylmaleimide and 1-30% by weight of an aromatic vinyl compound (I) 1- A heat-resistant methacrylic resin composition comprising 99% by weight of a polymer (II) containing 70% by weight or more of methyl methacrylate. 2. The heat-resistant methacrylic resin composition according to claim 1, wherein the aromatic vinyl compound is at least one selected from the group consisting of styrene, α-methylstyrene, and vinyltoluene. 3. In the copolymer (I), when the number of moles of N-cyclohexylmaleimide is α and the number of moles of the aromatic vinyl compound is β, the blending ratio of both components (β/α) is 0.5 to 2. The heat-resistant methacrylic resin composition according to claim 1, characterized in that it is composed of quantitative relationships.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11421586A JPS62270648A (en) | 1986-05-19 | 1986-05-19 | Heat-resistant methacrylate resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11421586A JPS62270648A (en) | 1986-05-19 | 1986-05-19 | Heat-resistant methacrylate resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62270648A true JPS62270648A (en) | 1987-11-25 |
Family
ID=14632098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11421586A Pending JPS62270648A (en) | 1986-05-19 | 1986-05-19 | Heat-resistant methacrylate resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62270648A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0333378A2 (en) * | 1988-03-15 | 1989-09-20 | Mitsubishi Denki Kabushiki Kaisha | Magnetic tape recording and playback device |
| US5430115A (en) * | 1988-08-15 | 1995-07-04 | Mitsubishi Rayon Co., Ltd. | Maleimide copolymer and a process for producing the same |
| JP2006117942A (en) * | 2005-10-20 | 2006-05-11 | Hitachi Chem Co Ltd | Pseudo-crosslinked resin composition and molded item, sheet, film and optical part obtained from it |
| WO2013005634A1 (en) | 2011-07-01 | 2013-01-10 | 旭化成ケミカルズ株式会社 | Acrylic thermoplastic resin composition and molded article thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61162509A (en) * | 1985-01-10 | 1986-07-23 | Nippon Shokubai Kagaku Kogyo Co Ltd | Thermoplastic resin and thermoplastic resin composition containing the same |
| JPH0240260A (en) * | 1988-07-29 | 1990-02-09 | Nittetsu Boshoku Kk | Thick film painting method by fluiridized bed coating process |
-
1986
- 1986-05-19 JP JP11421586A patent/JPS62270648A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61162509A (en) * | 1985-01-10 | 1986-07-23 | Nippon Shokubai Kagaku Kogyo Co Ltd | Thermoplastic resin and thermoplastic resin composition containing the same |
| JPH0240260A (en) * | 1988-07-29 | 1990-02-09 | Nittetsu Boshoku Kk | Thick film painting method by fluiridized bed coating process |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0333378A2 (en) * | 1988-03-15 | 1989-09-20 | Mitsubishi Denki Kabushiki Kaisha | Magnetic tape recording and playback device |
| US5430115A (en) * | 1988-08-15 | 1995-07-04 | Mitsubishi Rayon Co., Ltd. | Maleimide copolymer and a process for producing the same |
| JP2006117942A (en) * | 2005-10-20 | 2006-05-11 | Hitachi Chem Co Ltd | Pseudo-crosslinked resin composition and molded item, sheet, film and optical part obtained from it |
| WO2013005634A1 (en) | 2011-07-01 | 2013-01-10 | 旭化成ケミカルズ株式会社 | Acrylic thermoplastic resin composition and molded article thereof |
| JP5190564B2 (en) * | 2011-07-01 | 2013-04-24 | 旭化成ケミカルズ株式会社 | Acrylic thermoplastic resin composition and molded article thereof |
| TWI468456B (en) * | 2011-07-01 | 2015-01-11 | Asahi Kasei Chemicals Corp | Acrylic thermal plastic resin composition and the compact thereof |
| US10030134B2 (en) | 2011-07-01 | 2018-07-24 | Asahi Kasei Kabushiki Kaisha | Acrylic thermoplastic resin composition and molded article thereof |
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