JPS63215705A - New methyl methacrylate copolymer and heat-resistant resin composition containing the same - Google Patents
New methyl methacrylate copolymer and heat-resistant resin composition containing the sameInfo
- Publication number
- JPS63215705A JPS63215705A JP4870787A JP4870787A JPS63215705A JP S63215705 A JPS63215705 A JP S63215705A JP 4870787 A JP4870787 A JP 4870787A JP 4870787 A JP4870787 A JP 4870787A JP S63215705 A JPS63215705 A JP S63215705A
- Authority
- JP
- Japan
- Prior art keywords
- methyl methacrylate
- weight
- methacrylate copolymer
- resin composition
- polymerizable monomer
- 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000011342 resin composition Substances 0.000 title claims description 18
- 229920006015 heat resistant resin Polymers 0.000 title claims description 9
- 229920006026 co-polymeric resin Polymers 0.000 title 1
- 229920001577 copolymer Polymers 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 28
- -1 maleimide compound Chemical class 0.000 claims abstract description 26
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 12
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 13
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 abstract description 4
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 abstract description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003505 polymerization initiator Substances 0.000 abstract description 3
- 239000000725 suspension Substances 0.000 abstract description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 abstract description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012986 chain transfer agent Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 2
- 239000001530 fumaric acid Substances 0.000 abstract description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 abstract description 2
- 239000011976 maleic acid Substances 0.000 abstract description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 150000001451 organic peroxides Chemical class 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 25
- 239000011347 resin Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 9
- 229920001169 thermoplastic Polymers 0.000 description 7
- 229920001187 thermosetting polymer Polymers 0.000 description 7
- 239000004416 thermosoftening plastic Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000113 methacrylic resin Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- NQDOCLXQTQYUDH-UHFFFAOYSA-N 1-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)N1C(=O)C=CC1=O NQDOCLXQTQYUDH-UHFFFAOYSA-N 0.000 description 1
- DABFKTHTXOELJF-UHFFFAOYSA-N 1-propylpyrrole-2,5-dione Chemical compound CCCN1C(=O)C=CC1=O DABFKTHTXOELJF-UHFFFAOYSA-N 0.000 description 1
- YEKDUBMGZZTUDY-UHFFFAOYSA-N 1-tert-butylpyrrole-2,5-dione Chemical compound CC(C)(C)N1C(=O)C=CC1=O YEKDUBMGZZTUDY-UHFFFAOYSA-N 0.000 description 1
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 description 1
- DUVLBLUUAPRXLD-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid;prop-2-enenitrile Chemical compound C=CC#N.OC(=O)C(=C)CC=CC1=CC=CC=C1 DUVLBLUUAPRXLD-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 101100208721 Mus musculus Usp5 gene Proteins 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- SMUVTFSHWISULV-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enenitrile Chemical compound C=CC#N.COC(=O)C(C)=C SMUVTFSHWISULV-UHFFFAOYSA-N 0.000 description 1
- HTEAGOMAXMOFFS-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C HTEAGOMAXMOFFS-UHFFFAOYSA-N 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は新規なメチルメタクリレート系共重合体並びに
それを含んでなる耐熱性樹脂組成物に関するものであり
、更に詳しくは耐熱変形性、耐熱分解性、成形加工性、
透明性等の性能に優れ、よって車輛、電気・電子機器、
事務用機器等の部材に好ましく用いることができる新規
メチルメタクＩＪ ｌ／ −１−系共重合体並びにこれ
を含んでなる耐熱性樹脂組成物に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel methyl methacrylate copolymer and a heat-resistant resin composition containing the same. properties, moldability,
It has excellent performance such as transparency, so it is suitable for vehicles, electrical/electronic equipment,
The present invention relates to a novel methylmethac IJ l/-1-based copolymer that can be preferably used for members of office equipment and the like, and a heat-resistant resin composition containing the same.
（従来の技術）
メタクリル酸メチルを主成分とするメタクリル樹脂は耐
候性、光学的性質に優れ且つ機械的性質、熱的性質及び
成形加工性においても比較的バランスのとれた性能を有
しているので、これらの特性を生かして自動車部品、電
気機器部品、銘板、看板、照明用カバー、装飾用或いは
雑貨品など多くの分野で実用化されている。(Prior art) Methacrylic resin whose main component is methyl methacrylate has excellent weather resistance and optical properties, and has relatively well-balanced performance in mechanical properties, thermal properties, and moldability. Therefore, by taking advantage of these characteristics, they have been put to practical use in many fields such as automobile parts, electrical equipment parts, nameplates, signboards, lighting covers, decorations, and miscellaneous goods.
しかし一方では耐熱性については必ずしも充分ではなく
、高温での形状安定性が要求される分野ではその使用が
制限されており、耐熱性向上に対する要求には根強いも
のがある。However, on the other hand, their heat resistance is not necessarily sufficient, and their use is limited in fields where shape stability at high temperatures is required, and there is a deep-rooted demand for improved heat resistance.
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とＮ−ア
リールマレイン酸イミドとを共重合させる方法（特公昭
４３−９７５３号）、メタクリル酸メチル、α−メチル
スチレン及び無水マレイン酸との共重合体とメタクリル
酸メチル重合体とをブレンドする方法（特開昭５９−１
２２５３６号）などがなされている。しかし、これらの
方法では耐熱性はある程度改善されるものの、機械的性
質、耐候性及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、或いは成形加工性が悪いなど問題を
残している。For information on how to improve the heat resistance of methacrylic resin,
Many proposals have already been made, such as a method for copolymerizing methyl methacrylate and N-arylmaleimide (Japanese Patent Publication No. 43-9753), a method for copolymerizing methyl methacrylate, α-methylstyrene, and maleic anhydride, and methacrylate. Method of blending with acid methyl polymer (Japanese Patent Application Laid-open No. 59-1
No. 22536). However, although these methods improve heat resistance to some extent, they still have problems such as deterioration of mechanical properties, weather resistance, and optical properties, marked discoloration of molded products, and poor moldability. There is.
（発明が解決しようとする問題点）
本発明者らは鋭意研究の結果、メチルメタクリレートに
特定のマレイミド化合物、特定の芳香族ビニル化合物及
び不飽和カルボン酸を特定量導入して得られるメチルメ
タクリレート系共重合体が、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、成形加工性等の緒
特性を損われることなく、優れた耐熱性を有すると共に
、該メチルメタクリレート系共重合体を他の熱可塑性又
は熱硬化性樹脂に混合することによシ、これらの樹脂の
特徴を損うことなく耐熱性の向上した樹脂組成物が得ら
れることを見い出し、本発明を完成するに至った。(Problems to be Solved by the Invention) As a result of intensive research, the present inventors found that a methyl methacrylate system obtained by introducing specific amounts of a specific maleimide compound, a specific aromatic vinyl compound, and an unsaturated carboxylic acid into methyl methacrylate. The copolymer has excellent heat resistance without impairing the excellent optical properties, mechanical properties, weather resistance, moldability, etc. inherent to methacrylic resin, and the methyl methacrylate copolymer The present inventors have discovered that a resin composition with improved heat resistance can be obtained without impairing the characteristics of these resins by mixing them with other thermoplastic or thermosetting resins, leading to the completion of the present invention. Ta.
（問題点を解決するための手段および作用）すなわち、
本発明は、
メチルメタクリレート（Ａ）４０〜８５重量係、一般式
％式％
（式中、Ｒは水素、炭素数１〜４のアルキル基又はシク
ロヘキシル基である。）で表わされるマレイミド化合物
（Ｂ）５〜３０重量体、α−メチルスチレン（０５〜４
０重量係、不飽和カルボン酸０１〜３０重量係及びこれ
らの単量体と共重合し７うるその他の重合性単量体■（
以下、重合性単量体［Ｆ］という。）０〜３０重量係（
但し、前記単量体の合計はｉｏｏ重量係である。）から
なる重合性単量体成分を重合して得られる耐熱性と透明
性に優れた新規メチルメタクリレート系共重合体並びに
これを必須成分として含む耐熱性樹脂組成物に関するも
のである。(Means and actions for solving problems) That is,
The present invention provides a maleimide compound (B) represented by methyl methacrylate (A) with a weight ratio of 40 to 85 and a general formula % (wherein R is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a cyclohexyl group). ) 5-30 weight body, α-methylstyrene (05-4
0 weight ratio, unsaturated carboxylic acids 01 to 30 weight ratio, and other polymerizable monomers that can be copolymerized with these monomers (
Hereinafter, it will be referred to as a polymerizable monomer [F]. ) 0-30 weight section (
However, the total of the monomers is based on ioo weight. The present invention relates to a novel methyl methacrylate copolymer with excellent heat resistance and transparency obtained by polymerizing a polymerizable monomer component consisting of the following: and a heat-resistant resin composition containing this as an essential component.
本発明の新規メチルメタクリレート系共重合体は、メチ
ルメタクリレート囚、マレイミド化合物ＣＢ）、α−メ
チルスチレン（ｑ１不飽和カルボン酸（至）を夫々前記
の量で含む重合性単量体成分から得られるもので、本発
明において限定された条件においてのみ、透明性と耐熱
性とに著しく優れたメタクリレート系共重合体を得るこ
とができる。例えば、マレイミド化合物としてＮ−アリ
ールマレイミドを用いたり、α−メチルスチレンの換わ
りにスチレン、パラメチルスチレン、ビニルトルエン等
の他の芳香族ビニル単量体を用いたり、前記四成分のう
ち、−成分でも本発明において限定された量を外れた量
で用いた場合は、もはや透明性と耐熱性とに優れたメチ
ルメタクリレート系共重合体は得られないのである。The novel methyl methacrylate copolymer of the present invention is obtained from polymerizable monomer components containing methyl methacrylate, maleimide compound CB), and α-methylstyrene (q1 unsaturated carboxylic acid) in the above amounts. A methacrylate copolymer with outstanding transparency and heat resistance can be obtained only under the conditions specified in the present invention.For example, N-arylmaleimide is used as the maleimide compound, α-methyl When other aromatic vinyl monomers such as styrene, paramethylstyrene, vinyltoluene, etc. are used in place of styrene, or when even the - component among the above four components is used in an amount outside the amount limited in the present invention. It is no longer possible to obtain a methyl methacrylate copolymer with excellent transparency and heat resistance.
特に、本発明のメチルメタクリレート系共重合体をこれ
自体で靭性を必要とされる成形品に加工して用いる場合
は、重合性単量体成分として、メチルメタクリレート（
Ａ）５０〜８５重量係、マレイミド化合物（Ｂ）５〜３
０重量係重量−メチルスチレンＣＣ） ５〜１５重量係
重量節和カルボン酸０）） １〜１５重量係重量型合性
単量体■Ｏ〜３０重量％（但し前記重合性単量体成分の
合計は１００重量係である。）の割合とするのが好まし
い。In particular, when the methyl methacrylate copolymer of the present invention is processed into molded products that require toughness by itself, methyl methacrylate (
A) 50-85 weight ratio, maleimide compound (B) 5-3
0 weight ratio - methyl styrene CC) 5-15 weight ratio weight-saving carboxylic acid 0)) 1-15 weight ratio weight type polymerizable monomer ■O-30% by weight (however, the amount of the polymerizable monomer component The total is 100 parts by weight).
本発明において用いるマレイミド化合物（Ｉ３）は前記
一般式で表わされるものであシ、例えばマレイミド、Ｎ
−メチルマレイミド、Ｎ−エチルマレイミド、Ｎ−プロ
ピルマレイミド、Ｎ−イソプロピルマレイミド、Ｎ−ブ
チルマレイミド、Ｎ−インブチルマレイミド、Ｎ−ター
シャリ−ブチルマレイミド、Ｎ−シクロへキシルマレイ
ミド等を挙げることができ、これらのうち１種又は２種
以上を使用することができる。The maleimide compound (I3) used in the present invention is represented by the above general formula, for example, maleimide, N
- Methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-inbutylmaleimide, N-tert-butylmaleimide, N-cyclohexylmaleimide, etc. One or more of these can be used.
不飽和゛カルボン酸０としては、例えば（メタ）アクリ
ル酸、イタコン酸、（無水）マレイン酸、フマール酸本
しくはそれらの半エステル化物等が挙げられる。Examples of the unsaturated carboxylic acid include (meth)acrylic acid, itaconic acid, (anhydrous) maleic acid, and fumaric acid or their half esters.
本発明において、重合性単量体成分は、メチルメタクリ
レート囚、マレイミド化合物（Ｂ）、α−メチルスチレ
ン（Ｑ、不飽和カルボン酸■だけで構成されてもよいが
、本発明の特徴を損わない範囲で重合性単量体口を用い
てもよい。使用できる重合性単量体［Ｆ］としては、メ
チルメタクリレート囚、マレイミド化合物ＣＢ）、α−
メチルスチレン（Ｃ１，不飽和カルボン酸（２）のうち
の少なくとも１種の単量体と共重合しうるものであれば
特に制限されず、例えばメチルアクリレート、エチル（
メタ）アクリレート、プロピル（メタ）アクリレート、
ブチル（メタ）アクリレート、ターシャリ−ブチル（メ
タ）アクリレート、アミル（メタ）アクリレート、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、ラウリル（メタ）アクリレート、シク
ロヘキシル（メタ）アクリレート、ベンジル（メタ）ア
クリレート等のシクロアルキル基、ベンジル基を含むア
ルキル基の炭素数１〜１２を有するアクリル酸エステル
類またはアルキル基の炭素数２〜１２を有するメタクリ
ル酸エステル類；スチレン、パラメチルスチレン、イン
プロペニルスチレン、ビニルトエン等のα−メチルスチ
レンを除くビニル芳香族類；（メタ）アクリロニトリル
等の不飽和ニトリル類；エチレン、プロピレン等のオレ
フィン類；ブタジェン、イソプレン等のジエン類；酢酸
ビニル等のビニルエステル類；塩化ビニル、フッ化ビニ
ル等のハロゲン化ビニル類；エチレングリコールジ（メ
タ）アクリレート、ジエチレングリコールジ（メタ）ア
クリレート、トリメチロールトリ（メタ）アクリレート
、ジビニルベンゼン等の多不飽和化合物類等を挙げるこ
とができ、これらの群から選ばれる１種または２種以上
を用いることができる。重合性単量体［Ｆ］は必要によ
り重合性単量体成分の合計量に対して３０重量係以下の
量で使用するものであシ、使用量が３０重量係を越える
と透明性と耐熱性とに優れた共重合体が得られなくなる
。 ゛本発明の新規メチルメタクリレート系共重合体は
、メチルメタクリレート囚、マレイミド化合物（Ｂ）、
α−メチルスチレン（Ｑ１不飽和カルボン酸［Ｆ］及び
必要（よシ用いる重合性単量体図を夫々前記の量で含む
重合性単量体成分を公知の手順に従って共重合すればよ
い。In the present invention, the polymerizable monomer component may be composed only of methyl methacrylate, maleimide compound (B), α-methylstyrene (Q, and unsaturated carboxylic acid (2), but this may impair the characteristics of the present invention. Polymerizable monomers may be used to the extent that they are not included. Examples of polymerizable monomers [F] that can be used include methyl methacrylate, maleimide compound CB), α-
It is not particularly limited as long as it can be copolymerized with at least one monomer of methylstyrene (C1, unsaturated carboxylic acid (2), for example, methyl acrylate, ethyl (
meth)acrylate, propyl(meth)acrylate,
Butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate Cycloalkyl groups such as acrylates, acrylic esters having an alkyl group having 1 to 12 carbon atoms, including benzyl groups, or methacrylic esters having an alkyl group having 2 to 12 carbon atoms; styrene, paramethylstyrene, impropenylstyrene , vinyl aromatics excluding α-methylstyrene such as vinyltoene; unsaturated nitriles such as (meth)acrylonitrile; olefins such as ethylene and propylene; dienes such as butadiene and isoprene; vinyl esters such as vinyl acetate; Vinyl halides such as vinyl chloride and vinyl fluoride; polyunsaturated compounds such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylol tri(meth)acrylate, and divinylbenzene. One or more types selected from these groups can be used. The polymerizable monomer [F] may be used in an amount of 30 parts by weight or less based on the total amount of polymerizable monomer components, if necessary, and if the amount used exceeds 30 parts by weight, transparency and heat resistance may deteriorate. A copolymer with excellent properties cannot be obtained.゛The novel methyl methacrylate copolymer of the present invention comprises a methyl methacrylate prisoner, a maleimide compound (B),
A polymerizable monomer component containing α-methylstyrene (Q1 unsaturated carboxylic acid [F]) and the necessary polymerizable monomers in the amounts described above may be copolymerized according to a known procedure.
重合方法としては特に制限されず、例えば懸濁重合、乳
化重合、溶液重合及び塊状重合を挙げることができるが
、本発明においては懸濁重合法によるのが好ましい。懸
濁重合法によシ本発明の新規メチルメタクリレート系共
重合体を得るには、例えば前記重合性単量体成分、重合
開始剤及び必要により連鎖移動剤よりなる混合物を懸濁
安定剤の存在下に水媒体に懸濁した後、５０〜１５０℃
の温度条件下に重合すればよい。The polymerization method is not particularly limited, and examples thereof include suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization, but suspension polymerization is preferred in the present invention. In order to obtain the novel methyl methacrylate copolymer of the present invention by the suspension polymerization method, for example, a mixture consisting of the above-mentioned polymerizable monomer components, a polymerization initiator, and optionally a chain transfer agent is mixed in the presence of a suspension stabilizer. After suspending in water medium, 50-150℃
The polymerization may be carried out under the temperature conditions of
この際、使用できる重合開始剤としては、例えば２，２
′−アゾビスインブチロニトリル、２，２′−アゾビス
−２，４−ジメチルバレロニトリルの如きアゾ系開始剤
、ベンゾイルパーオキサイド、ｔ−ブチルパーオキシ２
−エチルヘキサノエートの如き有機過酸物を用いること
ができ、又、連鎖移動剤としては、例えばブチルメルカ
プタン、オクチルメルカプタン等のアルキルメルカプタ
ンが挙げられる。At this time, the polymerization initiator that can be used is, for example, 2,2
Azo initiators such as '-azobisinbutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, benzoyl peroxide, t-butylperoxy 2
Organic peracids such as -ethylhexanoate can be used, and examples of chain transfer agents include alkyl mercaptans such as butyl mercaptan and octyl mercaptan.
こうして得られる本発明の新規メチルメタクリレート系
共重合体は、そのまま耐熱性、耐候性、成形加工性、透
明性に優れた成形用樹脂として、例えば自動車部品、精
密電子機器の用途に好適に使用できる。又、公知の方法
で脱気押出し、ペレット化して他の熱可塑性や熱硬化性
樹脂の耐熱性改良剤として用いることもできる。The novel methyl methacrylate copolymer of the present invention thus obtained can be used as it is as a molding resin with excellent heat resistance, weather resistance, moldability, and transparency, and can be suitably used for applications such as automobile parts and precision electronic equipment. . It can also be used as a heat resistance improver for other thermoplastic or thermosetting resins by deaerating extrusion and pelletizing by a known method.
本発明の耐熱性樹脂組成物は、前記方法により得られた
メチルメタクリレート系共重合体を従来から公知の熱可
塑性又は熱硬化性樹脂と混合して成るものである。適用
できる熱可塑性又は熱硬化性樹脂としては、例えばメチ
ルメタクリレート樹脂、メチルメタクリレート−アクリ
レート樹脂、メチルメタクリレート−スチレン樹脂、ポ
リカーボネート樹脂、ポリエチレンテレフタレート樹脂
、ポリブチレンテレフタレート樹脂、ポリフェニレンオ
キサイド樹脂、塩化ビニル樹脂、塩素化塩化ビニル樹脂
、アクリロニトリル−スチレン樹脂、アクリロニトリル
−メチルメタクリレート樹脂、スチレン−メタクリル酸
樹脂、スチレン−メタクリル酸−アクリロニトリル樹脂
、スチレン−イミド樹脂、不飽和ポリエステル樹脂等を
挙げることができるが、特にポリカーボネート樹脂、ポ
リエチレンテレフタレート樹脂、塩化ビニル樹脂、塩素
化塩化ビニル樹脂に適用すると、これらの樹脂の特徴を
損うことなく耐熱性が向上し、しかも成形加工性も改良
できるので好ましい。The heat-resistant resin composition of the present invention is made by mixing the methyl methacrylate copolymer obtained by the above method with a conventionally known thermoplastic or thermosetting resin. Applicable thermoplastic or thermosetting resins include, for example, methyl methacrylate resin, methyl methacrylate-acrylate resin, methyl methacrylate-styrene resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene oxide resin, vinyl chloride resin, and chlorine. Vinyl chloride resin, acrylonitrile-styrene resin, acrylonitrile-methyl methacrylate resin, styrene-methacrylic acid resin, styrene-methacrylic acid-acrylonitrile resin, styrene-imide resin, unsaturated polyester resin, etc. can be mentioned, but in particular polycarbonate resin , polyethylene terephthalate resin, vinyl chloride resin, and chlorinated vinyl chloride resin, it is preferable because heat resistance can be improved without impairing the characteristics of these resins, and moldability can also be improved.
耐熱性樹脂組成物を得るに際し、前記メチルメタクリレ
ート系共重合体と他の熱可塑性又は熱硬化性樹脂との好
ましい使用割合は、メチルメタクリレート系共重合体５
〜９５重量％、他の熱可塑性又は熱硬化性樹脂９０〜５
重量係の比率である。When obtaining a heat-resistant resin composition, a preferable ratio of the methyl methacrylate copolymer and other thermoplastic or thermosetting resin is methyl methacrylate copolymer 5
~95% by weight, other thermoplastic or thermosetting resins 90-5
This is the weight ratio.
（発明の効果）
本発明の新規メチルメタクリレート系共重合体は、メチ
ルメタクリレート囚、マレイミド化合物（Ｂ）、α−メ
チルスチレン（０及び不飽和カルボン酸の）とを特定の
割合で共重合して成るためＫ、従来のメタクリル樹脂が
有する高い透明性と優れた耐候性、成形加工性とを保持
しながら、耐熱性も著しく改良されている。従って本発
明による新規メチルメタクリレート系共重合体は穏々の
形状に成形加工して自動車部品、精密電気・電子機器等
に好適に使用できるものである。(Effects of the invention) The novel methyl methacrylate copolymer of the present invention is produced by copolymerizing methyl methacrylate, a maleimide compound (B), and α-methylstyrene (0 and unsaturated carboxylic acid) in a specific ratio. Therefore, while maintaining the high transparency, excellent weather resistance, and moldability of conventional methacrylic resins, the heat resistance is also significantly improved. Therefore, the novel methyl methacrylate copolymer according to the present invention can be molded into a moderate shape and suitably used for automobile parts, precision electric/electronic equipment, etc.
また、該メチルメタクリレート系共重合体を必須成分と
して含む本発明の耐熱性樹脂組成物は従来の熱可塑性や
熱硬化性樹脂の特徴をそのまま保持しながら耐熱性と成
形加工性とが改良されたものである。従って本発明の耐
熱性樹脂組成物は種々の形状に成形加工して建材、車輛
、電気製品等の用途に好適に使用できる。Furthermore, the heat-resistant resin composition of the present invention containing the methyl methacrylate copolymer as an essential component has improved heat resistance and moldability while retaining the characteristics of conventional thermoplastic and thermosetting resins. It is something. Therefore, the heat-resistant resin composition of the present invention can be molded into various shapes and suitably used for applications such as building materials, vehicles, and electrical products.
（実施例）
以下、実施例により本発明の詳細な説明するが、本発明
は以下の実施例によって限定されるものではない。なお
、例中特にことわりのない限り部は重量による。(Examples) Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to the following Examples. In the examples, unless otherwise specified, parts are by weight.
実施例１
メチルメタクリレート６０部、Ｎ−シクロへキシルマレ
イミド２０部、α−メチルスチレン１０部、メタクリル
酸１０部、ラウロイルパーオキサイド０．５部、ｎ−ド
デシルメルカプタン０．２部からなる重合性単量体成分
を還流冷却器、不活性ガス導入管、温度計及び撹拌機を
備えた反応容器に脱イオン水３００部、ポリメタクリル
酸ソーダ１．５部と共に仕込み、高速で撹拌して懸濁液
とした。Example 1 A polymerizable monomer consisting of 60 parts of methyl methacrylate, 20 parts of N-cyclohexylmaleimide, 10 parts of α-methylstyrene, 10 parts of methacrylic acid, 0.5 part of lauroyl peroxide, and 0.2 part of n-dodecylmercaptan. The mass components were charged into a reaction vessel equipped with a reflux condenser, an inert gas inlet tube, a thermometer, and a stirrer together with 300 parts of deionized water and 1.5 parts of sodium polymethacrylate, and stirred at high speed to form a suspension. And so.
次いで、不活性ガス導入管より窒素ガスを吹き込みなが
ら、反応液を８０°Ｃに加熱して重合反応を開始した。Next, the reaction solution was heated to 80° C. while blowing nitrogen gas through an inert gas introduction tube to initiate a polymerization reaction.
重合反応が開始してから５時間後に、反応液温度を９５
℃に昇温し、更に２時間撹拌を続行して重合を完結させ
た。5 hours after the start of the polymerization reaction, the temperature of the reaction solution was increased to 95%.
The temperature was raised to 0.degree. C., and stirring was continued for an additional 2 hours to complete polymerization.
得られた共重合体を冷却、濾過、水洗、乾燥してメチル
メタクリレート系共重合体（１）のビーズを得た。The obtained copolymer was cooled, filtered, washed with water, and dried to obtain beads of methyl methacrylate copolymer (1).
次にこのメチルメタクリレート系共重合体ｆｌ）のビー
ズをベント付き３０ｒｎｒｎ押出機を用いてベント圧３
０ ｍｍＨｇ５シリンダ一温度２５０’Ｃの条件下に溶
融混練し、ペレット化した。Next, beads of this methyl methacrylate copolymer (fl) were processed using a vented 30rnrn extruder at a vent pressure of 3.
The mixture was melted and kneaded under conditions of 0 mmHg, 5 cylinders, and a temperature of 250'C, and pelletized.
得られたメチルメタクリレート系共重合体（１）のペレ
ットを射出成型機（日清樹脂工業■製、ＰＳ６０Ｅ９Ａ
型）を用いて成形温度２５０°Ｃで高圧高速射出成型し
たところ、得られたメチルメタクリレート系共重合体（
１）の成形品の外観は無色透明でシルバーの発生は全く
なかった。更にこの成形品の性能をテストし、その結果
を第１表に示した。The pellets of the obtained methyl methacrylate copolymer (1) were molded using an injection molding machine (manufactured by Nisshin Jushi Kogyo ■, PS60E9A).
The resulting methyl methacrylate copolymer (
The appearance of the molded product 1) was colorless and transparent, and no silver was generated at all. Furthermore, the performance of this molded article was tested and the results are shown in Table 1.
なお、性能の熱変形温度の測定方法はＡＳＴＭ Ｄ−６
４８、アイゾツト衝撃強度はＡＳＴＭ Ｄ−２５６に夫
々準じ、外観は目視観察に依った。The method for measuring the heat distortion temperature of performance is ASTM D-6.
48, Izot impact strength was determined according to ASTM D-256, and appearance was determined by visual observation.
実施例２および比較例１〜６
実施例１において用いた重合性単量体成分を、第１表に
示した通りとする以外は実施例１と同様の方法に従って
メチルメタクリレート系共重合体（２）および比較用（
共）重合体（１１〜（６）の成形品を得た。Example 2 and Comparative Examples 1 to 6 Methyl methacrylate copolymer (2 ) and for comparison (
Molded articles of co)polymers (11 to (6)) were obtained.
これらの成形品の性能をテストし、その結果を第１表に
示した。The performance of these molded articles was tested and the results are shown in Table 1.
実施例３〜５
実施例２で得られたメチルメタクリレート系共 く重
合体（２）と塩化ビニル樹脂（スミリット５Ｘ−１１Ｆ
、 ；住友化学■製、重合度１０５０ ）を用い、
第２表に ２示した配合から成る樹脂組成物（１］〜
（３）を調製した。Examples 3 to 5 Methyl methacrylate copolymer (2) obtained in Example 2 and vinyl chloride resin (Sumilit 5X-11F)
, manufactured by Sumitomo Chemical ■, polymerization degree 1050),
Resin composition (1) consisting of the formulations shown in Table 2.
(3) was prepared.
得られた樹脂組成物（１）〜（３）をそれぞれ表面温度
１９０°Ｃに加熱された直径８インチの熱ロールで５分
間混練してシート状樹脂組成物を得、これを平板プレス
を用いて１９０℃、１００に９／ｉの圧力下で１０分間
プレス成形して、試験片を作製した。得られた試験片を
用いて、熱変形温度、アイゾツト衝撃強度、作業性、促
進耐候性を測定した結果を第２表に示すが、本発明の樹
脂組成物は良好な結果を示すことがわかった。また、各
実施例において、樹脂組成物の熱ロール混練時の作業性
の評価結果も第２表に示すが、支障なく良好であった。The obtained resin compositions (1) to (3) were each kneaded for 5 minutes using a hot roll with a diameter of 8 inches heated to a surface temperature of 190°C to obtain a sheet-shaped resin composition, which was then kneaded using a flat plate press. A test piece was prepared by press molding at 190° C. for 10 minutes under a pressure of 100 to 9/i. Using the obtained test pieces, the heat distortion temperature, isot impact strength, workability, and accelerated weather resistance were measured. The results are shown in Table 2, and it was found that the resin composition of the present invention showed good results. Ta. Further, in each Example, the evaluation results of the workability during hot roll kneading of the resin composition are also shown in Table 2, and the results were good without any problems.
なお、熱変形温度の測定方法はＡＳＴＭＤ−６４８、ア
イゾツト衝撃強度はＡＳＴＭ Ｄ−２５６に準じ、促進
耐候性はサンシャイン型つエザオメーターでの１０００
時間照射後の外観を観察することによりＤ：良好、Δ：
やや悪い、×：悪いで、作業性は春ロール混線状態を観
察することによシ、○：良子、△：やや悪い、×：悪い
で評価した。The heat distortion temperature was measured according to ASTM D-648, the Izod impact strength was measured according to ASTM D-256, and the accelerated weather resistance was measured at 1000 using a sunshine-type ezaometer.
By observing the appearance after time irradiation, D: Good, Δ:
Workability was evaluated by observing the spring roll cross-wire condition, ○: good, △: somewhat poor, ×: poor.
比較例７
実施例３におけるメチルメタクリレート系共重合体（１
）を用いない以外は、実施例３と同様にして比較用の樹
脂組成物（１）を調製したのち、試験片を作製し、同様
の評価を行った。その結果を第２表に示す。比較用の樹
脂組成物（１）は実施例３〜５で得られた樹脂組成物（
１）〜（３）に比較して劣る結果を示した。Comparative Example 7 Methyl methacrylate copolymer (1
) was prepared in the same manner as in Example 3, except that the resin composition (1) was not used, and then test pieces were prepared and evaluated in the same manner. The results are shown in Table 2. Comparative resin composition (1) was the resin composition obtained in Examples 3 to 5 (
Results were inferior to those of 1) to (3).
Claims (1)
般式 ▲数式、化学式、表等があります▼ （式中、Ｒは水素、炭素数１〜４のアルキル基又はシク
ロヘキシル基である。）で表わされるマレイミド化合物
（Ｂ）５〜３０重量％、α−メチルスチレン（Ｃ）５〜
４０重量％、不飽和カルボン酸（Ｄ）１〜３０重量％及
びこれらの単量体と共重合しうるその他の重合性単量体
（Ｅ）０〜３０重量％（但し、前記単量体の合計は１０
０重量％である。） からなる重合性単量体成分を重合して得られる耐熱性と
透明性に優れた新規メチルメタクリレート系共重合体。 ２、メチルメタクリレート（Ａ）４０〜８５重量％、一
般式 ▲数式、化学式、表等があります▼ （式中、Ｒは水素、炭素数１〜４のアルキル基又はシク
ロヘキシル基である。）で表わされるマレイミド化合物
（Ｂ）５〜３０重量％、α−メチルスチレン（Ｃ）５〜
４０重量％、不飽和カルボン酸（Ｄ）１〜３０重量％及
びこれらの単量体と共重合しうるその他の重合性単量体
（Ｅ）０〜３０重量％（但し、前記単量体の合計は１０
０重量％である。） からなる重合性単量体成分を重合して得られるメチルメ
タクリレート系共重合体を必須成分として含む耐熱性樹
脂組成物。[Claims] 1. Methyl methacrylate (A) 40 to 85% by weight, general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a cyclohexyl group) 5 to 30% by weight of maleimide compound (B) represented by
40% by weight, 1 to 30% by weight of unsaturated carboxylic acid (D) and 0 to 30% by weight of other polymerizable monomers (E) that can be copolymerized with these monomers (however, The total is 10
It is 0% by weight. ) A novel methyl methacrylate copolymer with excellent heat resistance and transparency obtained by polymerizing a polymerizable monomer component consisting of 2. Methyl methacrylate (A) 40-85% by weight, represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a cyclohexyl group.) Maleimide compound (B) 5-30% by weight, α-methylstyrene (C) 5-30% by weight
40% by weight, 1 to 30% by weight of unsaturated carboxylic acid (D) and 0 to 30% by weight of other polymerizable monomers (E) that can be copolymerized with these monomers (however, The total is 10
It is 0% by weight. ) A heat-resistant resin composition containing as an essential component a methyl methacrylate copolymer obtained by polymerizing a polymerizable monomer component consisting of:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62048707A JPH0696658B2 (en) | 1987-03-05 | 1987-03-05 | Heat resistant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62048707A JPH0696658B2 (en) | 1987-03-05 | 1987-03-05 | Heat resistant resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63215705A true JPS63215705A (en) | 1988-09-08 |
| JPH0696658B2 JPH0696658B2 (en) | 1994-11-30 |
Family
ID=12810790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62048707A Expired - Lifetime JPH0696658B2 (en) | 1987-03-05 | 1987-03-05 | Heat resistant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0696658B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02142809A (en) * | 1988-11-22 | 1990-05-31 | Kyowa Gas Chem Ind Co Ltd | Methacrylate copolymer |
| JPH0639894A (en) * | 1992-07-23 | 1994-02-15 | Tsutsunaka Plast Ind Co Ltd | Preparation of artificial marble by extrusion molding |
| JP2001146506A (en) * | 1999-09-06 | 2001-05-29 | Nippon Shokubai Co Ltd | Resin sheet and molded article using the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101295306B1 (en) * | 2010-11-23 | 2013-08-12 | 엘지엠엠에이 주식회사 | Methacrylic copolymer and Phase difference film comprising the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6195011A (en) * | 1984-10-17 | 1986-05-13 | Toray Ind Inc | Optical disk substrate |
| JPS61162509A (en) * | 1985-01-10 | 1986-07-23 | Nippon Shokubai Kagaku Kogyo Co Ltd | Thermoplastic resin and thermoplastic resin composition containing the same |
| JPS61255913A (en) * | 1985-05-09 | 1986-11-13 | Sumitomo Naugatuck Co Ltd | Heat-resistant copolymer |
| JPS61278509A (en) * | 1985-06-05 | 1986-12-09 | Toray Ind Inc | Optical disc base |
| JPS627516A (en) * | 1985-07-04 | 1987-01-14 | Mitsubishi Rayon Co Ltd | Continuous manufacture of heat-resistant methacrylate resin sheet |
-
1987
- 1987-03-05 JP JP62048707A patent/JPH0696658B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6195011A (en) * | 1984-10-17 | 1986-05-13 | Toray Ind Inc | Optical disk substrate |
| JPS61162509A (en) * | 1985-01-10 | 1986-07-23 | Nippon Shokubai Kagaku Kogyo Co Ltd | Thermoplastic resin and thermoplastic resin composition containing the same |
| JPS61255913A (en) * | 1985-05-09 | 1986-11-13 | Sumitomo Naugatuck Co Ltd | Heat-resistant copolymer |
| JPS61278509A (en) * | 1985-06-05 | 1986-12-09 | Toray Ind Inc | Optical disc base |
| JPS627516A (en) * | 1985-07-04 | 1987-01-14 | Mitsubishi Rayon Co Ltd | Continuous manufacture of heat-resistant methacrylate resin sheet |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02142809A (en) * | 1988-11-22 | 1990-05-31 | Kyowa Gas Chem Ind Co Ltd | Methacrylate copolymer |
| JPH0639894A (en) * | 1992-07-23 | 1994-02-15 | Tsutsunaka Plast Ind Co Ltd | Preparation of artificial marble by extrusion molding |
| JP2001146506A (en) * | 1999-09-06 | 2001-05-29 | Nippon Shokubai Co Ltd | Resin sheet and molded article using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0696658B2 (en) | 1994-11-30 |
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