JPS63199710A - Novel methyl methacrylate/styrene resin excellent in heat resistance and transparency - Google Patents
Novel methyl methacrylate/styrene resin excellent in heat resistance and transparencyInfo
- Publication number
- JPS63199710A JPS63199710A JP3235587A JP3235587A JPS63199710A JP S63199710 A JPS63199710 A JP S63199710A JP 3235587 A JP3235587 A JP 3235587A JP 3235587 A JP3235587 A JP 3235587A JP S63199710 A JPS63199710 A JP S63199710A
- Authority
- JP
- Japan
- Prior art keywords
- methyl methacrylate
- resin
- heat resistance
- weight
- styrene
- 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
- 239000011347 resin Substances 0.000 title claims abstract description 35
- 229920005989 resin Polymers 0.000 title claims abstract description 35
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 26
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 27
- -1 maleimide compound Chemical class 0.000 claims abstract description 26
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 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 4
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 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 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 abstract description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003505 polymerization initiator Substances 0.000 abstract description 3
- 239000012736 aqueous medium Substances 0.000 abstract description 2
- 239000012986 chain transfer agent Substances 0.000 abstract description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract 1
- 239000000375 suspending agent Substances 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 15
- 238000000034 method Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 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
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-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
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 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
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000007664 blowing Methods 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
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 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
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000003381 stabilizer Substances 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
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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−スチレン系樹脂
に関するものであシ、更に詳しくは、耐熱性と透明性と
に優れ、よって自動車部品、精密電気・電子部品、事務
用機器等に好ましく用いることができる新規メチルメタ
クリレート−スチレン系樹脂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-styrene resin, and more specifically, it has excellent heat resistance and transparency, and is therefore suitable for use in automobile parts, precision electronics, etc. - It relates to a new methyl methacrylate-styrene resin that can be preferably used for electronic parts, office equipment, etc.
（従来の技術及び問題点）
メチルメタクリレート−スチレン系樹脂（以下、ＭＳ樹
脂という。）は、ポリメチルメタクリレートの高い透明
性とポリスチレンの優れた成形加工性を兼ね備え、しか
も比較的安価であるために、成形材料としての潜在的需
要は大きい。しかしながら、通常のＭＳ樹脂の耐熱変形
温度は８５〜９０℃と耐熱性の面では必ずしも充分で無
く、高温での形状安定性を要求される自動車部品、電気
・電子部品等の用途等においては、その使用は著しく制
限されている。(Prior art and problems) Methyl methacrylate-styrene resin (hereinafter referred to as MS resin) combines the high transparency of polymethyl methacrylate and the excellent moldability of polystyrene, and is relatively inexpensive. , there is great potential demand as a molding material. However, the heat deformation temperature of ordinary MS resins is 85 to 90°C, which is not necessarily sufficient in terms of heat resistance, and in applications such as automobile parts and electrical/electronic parts that require shape stability at high temperatures, Its use is severely restricted.
一方、近年、Ｎ−置換マレイミド類を従来の樹脂成形材
料に配合することによシ、耐熱性が向上することが見い
出されるに至シ、その耐熱性向上のための応用研究はま
すます活発になってきている。しかし、Ｎ−置換マレイ
ミド類を含有するＭＳ樹脂は製造する上で多くの問題点
を有するために、工業的規模で生産されるに至っていな
い。すなわち、Ｎ−置換マレイミド類はスチレンとは通
常１：１の交互共重合体を与え易いのに対し、メチルメ
タクリレートとは共重合し難い。On the other hand, in recent years, it has been discovered that heat resistance can be improved by adding N-substituted maleimides to conventional resin molding materials, and applied research to improve heat resistance has become more and more active. It has become to. However, MS resins containing N-substituted maleimides have many problems in production and have not been produced on an industrial scale. That is, N-substituted maleimides tend to form a 1:1 alternating copolymer with styrene, but are difficult to copolymerize with methyl methacrylate.
従って、メチルメタクリレート−スチレン−Ｎ−置換マ
レイミド類よシなる重合性単量体混合物を重合して得ら
れる樹脂は通常組成物に不均一であるためＫ、透明性は
悪く、また耐熱性も期待した程には発現しないのである
。又、Ｎ−置換マレイミドのうち、メチルメタクリレー
トとの共重合性が比較的良いＮ−アリールマレイミド類
を用いた場合でも、共重合して得られる樹脂が微黄色〜
赤黄色に着色するという欠陥を有するために、床机な用
途に適用できないのが現状である。Therefore, the resin obtained by polymerizing a polymerizable monomer mixture such as methyl methacrylate-styrene-N-substituted maleimide usually has a non-uniform composition, has poor transparency, and has poor heat resistance. It doesn't manifest as much as it did. Furthermore, among N-substituted maleimides, even when N-arylmaleimides, which have relatively good copolymerizability with methyl methacrylate, are used, the resin obtained by copolymerization is slightly yellow to yellow.
Currently, it cannot be used for floor desks because it has the defect of being colored red-yellow.
このような現状に鑑み、本発明者らは鋭意研究の結果、
メチルメタクリレート、スチレン、特定のマレイミド化
合物及び不飽和カルボン酸を特定の割合で含む重合性単
量体成分を共重合した場合に限って、透明性と耐熱性と
に著しく優れた樹脂が得られることを見い出して本発明
に到達した。In view of this current situation, the inventors of the present invention have conducted extensive research and have found that
Only when a polymerizable monomer component containing methyl methacrylate, styrene, a specific maleimide compound, and an unsaturated carboxylic acid in a specific ratio is copolymerized, a resin with outstanding transparency and heat resistance can be obtained. The present invention was achieved by discovering the following.
（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Ａ４Ｉレメ９クリレート（Ａ、ｌコｔ−匁ＱＸ
、 スケレｙｔ８＞ｕ〜ｔｏ＊＊％、−＊’ｉ、ｔ’
Ｈ−Ｃ−Ｃ−Ｈ
■
（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
（Ｃ）５〜３０重ｆｉ％、不飽和カルボン酸［Ｆ］１〜
３０重ｆ％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■（以下、重合性単量体■という。）０〜
３０重量％（但し、前記単量体の合計は１００重量係量
子る。）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Ｍ−８樹脂に関するもので
ある。(Means and actions for solving problems) That is,
The present invention is directed to A4I 9 acrylate (A, 1-9 acrylate)
, scale yt8>u~to**%, -*'i, t'
H-C-C-H (wherein, R is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a cyclohexyl group) Maleimide compound (C) 5 to 30% by weight, unsaturated carboxylic acid [F]1~
30 weight f% and other polymerizable monomers (hereinafter referred to as polymerizable monomers) that can be copolymerized with these monomers (hereinafter referred to as polymerizable monomers) 0 to
This relates to a new M-8 resin with excellent heat resistance and transparency obtained by polymerizing a polymerizable monomer component consisting of 30% by weight (however, the total weight coefficient of the monomers is 100%). be.
本発明の新規ＭＳ樹脂はメチルメタクリレート囚、スチ
レン■、前記マレイミド化合物（ｑ及び不飽和カルボン
酸■をそれぞれ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が共に著しく優れた樹脂を得るこ
とができる。例えば、マレイミド化合物としてＮ−アリ
ールマレイミド等の本発明におけるマレイミド化合物（
Ｑ以外のマレイミド類を用いたシ、前記三成分のうち一
成分でも限定された量をはずれた場合は、もはや透明性
と耐熱性とに優れたＭＳ樹脂は得られないのである。The novel MS resin of the present invention is obtained from a polymerizable monomer component containing methyl methacrylate, styrene (2), the maleimide compound (q) and unsaturated carboxylic acid (2) in the above amounts, respectively. It is possible to obtain a resin with extremely excellent transparency and heat resistance only under certain conditions.For example, as a maleimide compound, the maleimide compound of the present invention such as N-arylmaleimide
If a maleimide other than Q is used, and even one of the above three components exceeds the specified amount, an MS resin with excellent transparency and heat resistance can no longer be obtained.
本発明の新規ＭＳ樹脂の製造に用いるマレイミド化合物
（Ｑ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５、Ｎ−メチルマレイミド、Ｎ−エチルマレイミ
ド、Ｎ−プロビルマ、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−シクロヘ
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。Maleimide compounds used in the production of the novel MS resin of the present invention (Q is represented by the above general formula, such as maleimide 5, N-methylmaleimide, N-ethylmaleimide, N-probilma, reimide, N-isopropylmaleimide) , N-butylmaleimide, N-inbutylmaleimide, N-tertiarybutylmaleimide, N-cyclohexylmaleimide, etc., and one or more of these can be used.
不飽和カルボン酸化合物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、或いはそれらの半エステル化物等が挙げられる。As the unsaturated carboxylic acid compound 0, for example, (meth)
Examples include acrylic acid, itaconic acid, maleic acid (anhydride), fumaric acid, and half-esterified products thereof.
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、スチレン（Ｂ）、マレイミド化合物（Ｑ及び
不飽和カルボン酸化合物■だけで構成されてもよいが、
本発明の特徴を損なわない範囲で、重合性単量体■を用
いてもよい。使用できる重合性単量体■としては、使用
するメチルメタクリレート囚、スチレン■、マレイミド
化合物（Ｑ、不飽和カルボン酸■のうちの少なくともｌ
ｆｉの単量体と共益金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を有するアクリレート類またはアルキル基
の炭素数２〜１２を有するメタクリレート類；α−メチ
ルスチレン、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。In the present invention, the polymerizable monomer component may be composed only of methyl methacrylate, styrene (B), a maleimide compound (Q and an unsaturated carboxylic acid compound (2),
Polymerizable monomer (2) may be used within a range that does not impair the characteristics of the present invention. The usable polymerizable monomers include methyl methacrylate, styrene, and maleimide compounds (Q, at least 1 of unsaturated carboxylic acids).
There is no particular restriction as long as it can covalently bond with the fi monomer, such as 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 (
Cycloalkyl groups such as meth)acrylate and benzyl(meth)acrylate, acrylates having an alkyl group having 1 to 12 carbon atoms including a benzyl group, or methacrylates having an alkyl group having 2 to 12 carbon atoms; α-methylstyrene; Vinyl aromatics other than styrene such as paramethylstyrene, impropenylstyrene, and vinyltoene; unsaturated nitriles such as (meth)'acrylonitrile;
Olefins such as ethylene and propylene; butadiene,
Dienes such as isoprene; Vinyl esters such as vinyl acetate; Vinyl halides such as vinyl chloride and vinyl fluoride; Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethyloltri(meth)acrylate, Examples include polyunsaturated compounds such as divinylbenzene, and one or more selected from these groups can be used.
重合性単量体■は必要によシ重合性単量体成分の合計量
に対して３０重重量板下の量で使用するものでアシ、使
用量が３０重量量子越えると、透明性と耐熱性に優れた
ＭＳ樹脂が得られなくまる。The polymerizable monomer (■) must be used in an amount less than 30% by weight based on the total amount of polymerizable monomer components, but if the amount used exceeds 30% by weight, the transparency and heat resistance may deteriorate. MS resin with excellent properties cannot be obtained.
本発明の新規ＭＳ樹脂は、メチルメタクリレート囚、ス
チレン■、マレイミド化合物０、不飽和カルボン酸０及
び必要によシ用いる重合性単量体（ト）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。The novel MS resin of the present invention is a polymerizable monomer containing methyl methacrylate, styrene (2), maleimide compound (0), unsaturated carboxylic acid (0), and optionally used polymerizable monomer ((3)) in the respective amounts described above. The components may be copolymerized according to known procedures.
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単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ＭＳ樹脂を得るには、例
えば前記重合性単量体成分、重合開始剤及び必要によシ
連鎖移動剤よシ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℃の過度条件下に重合す
ればよい。The polymerization method is not particularly limited and may be, for example, suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization, but suspension polymerization is preferred in the present invention. In order to obtain the novel MS resin of the present invention by the suspension polymerization method, for example, a mixture of the above-mentioned polymerizable monomer components, a polymerization initiator, and optionally a chain transfer agent is added in the presence of a suspension stabilizer. After suspending it in an aqueous medium, it may be polymerized under extreme conditions at 50 to 150°C.
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-butyl peroxy,
Organic peracids such as 2-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ＭＳ樹脂は、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
化して他の熱可重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 MS resin of the present invention thus obtained can be suitably used as it is as a molding resin with excellent heat resistance, weather resistance, moldability, and transparency, for example, in applications such as automobile parts and precision electronic equipment. It can also be degassed and extruded by a known method to pelletize and used as a heat resistance improver for other thermoplastic or thermosetting resins.
（発明の効果）
本発明の新規ＭＳ樹脂は、メチルメタクリレート囚、ス
チレンａ３）、マレイミド化合物（Ｑ及び不飽和カルボ
ン＃ＲＧ）ｌとを特定の割合で共重合して成るために、
従来のＭＳ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ＭＳ樹脂は種々の形状に
成形加工して自動車部品、精密電気・電子機器、事務用
機器等に好適に使用できるものである。(Effects of the Invention) The novel MS resin of the present invention is formed by copolymerizing methyl methacrylate, styrene a3), and a maleimide compound (Q and unsaturated carbon #RG) in a specific ratio.
While maintaining the high transparency, excellent weather resistance, and moldability of conventional MS resins, the heat resistance is also significantly improved. Therefore, the new MS resin according to the present invention can be molded into various shapes and suitably used for automobile parts, precision electric/electronic equipment, office equipment, etc.
（実施例）
以下、実施例によシ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°けない。尚
、例中％にととわシのない限シ部は重量による。(Examples) Hereinafter, the present invention will be explained in detail using Examples, but the present invention is not limited to the following Examples. In the examples, all percentages are by weight, unless otherwise noted.
実施例１
メチルメタクリレート３０部、スチレン４０部、Ｎ−シ
クロヘキシルマレイミド２０部、メタクリル［１０部、
ラウロイルパーオキサイド０．５部および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
。次いで、不活性ガス導入管よシ窒素ガスを吹き込みな
がら反応液を８０℃に加熱して重合反応を開始した。Example 1 30 parts of methyl methacrylate, 40 parts of styrene, 20 parts of N-cyclohexylmaleimide, methacrylic [10 parts,
A polymerizable monomer component consisting of 0.5 parts of lauroyl peroxide and 0.2 parts of n-dodecyl mercaptan was placed in a reaction vessel equipped with a reflux condenser, an inert gas inlet tube, a thermometer, and a stirrer with 300 g of deionized water. 1 part and 1.5 parts of polysodium methacrylate were stirred at high speed to form a suspension. 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。得られた共重合体を冷却、濾過、水洗、乾燥□して
％ＭＳＭＳ樹脂１のビーズを得た。次にこのＭＳ樹脂（
１１のビーズをベント付き３０ｍ押出機を用いてベント
圧３０１１ＩＩＨｇ１シリンダ一温度２５０℃の条件下
に溶融混練し、ペレット化した。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. The obtained copolymer was cooled, filtered, washed with water, and dried to obtain beads having % MSMS resin of 1. Next, this MS resin (
The beads of No. 11 were melt-kneaded using a vented 30 m extruder under the conditions of a vent pressure of 3011 II Hg, 1 cylinder, and a temperature of 250° C., and pelletized.
得られたＭＳ樹脂（１１のペレットを射出成型機（日精
樹脂工業■製ＰＳ６０Ｅ９Ａ型）を用いて成形源ｔ１２
５０℃で高圧・高速射出成型したところ、得られたＭＳ
樹脂（１１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 obtained MS resin (11 pellets) was molded into a molding source t12 using an injection molding machine (model PS60E9A manufactured by Nissei Plastics Co., Ltd.).
After high-pressure and high-speed injection molding at 50°C, the obtained MS
The appearance of the molded product of resin (No. 11) was colorless and transparent, and no silver was generated at all. The performance of this molded product was further 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−２５６ＩＣ
夫々に準じ、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, Izod impact strength is ASTM D-256IC
As in each case, the appearance was determined by visual observation.
実施例２および比較例１〜４
実施例１において用いた重合性単量体成分を、第１表に
示した通シとする以外は実施例１と同様の方法に従って
ＭＳ樹脂（２）および比較用樹脂（１）〜（４）の成形
品を得た。Example 2 and Comparative Examples 1 to 4 MS resin (2) and comparative examples were prepared in the same manner as in Example 1 except that the polymerizable monomer components used in Example 1 were as shown in Table 1. Molded products of resins (1) to (4) 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.
Claims (1)
チレン（Ｂ）４０〜６０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
（Ｃ）５〜３０重量％、不飽和カルボン酸（Ｄ）１〜３
０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１００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−スチレン系樹脂。[Claims] 1. Methyl methacrylate (A) 25-45% by weight, styrene (B) 40-60% by weight, General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is hydrogen, carbon 5 to 30% by weight of a maleimide compound (C) represented by a number 1 to 4 alkyl group or cyclohexyl group, 1 to 3% by weight of an unsaturated carboxylic acid (D)
0% by weight and other polymerizable monomers (E) copolymerizable with these monomers from 0 to 30% by weight (however, the total of the monomers is 100% by weight). A new methyl methacrylate-styrene resin with excellent heat resistance and transparency obtained by polymerizing monomer components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62032355A JPH07100725B2 (en) | 1987-02-17 | 1987-02-17 | Method for producing new methyl methacrylate-styrene resin with excellent heat resistance and transparency |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62032355A JPH07100725B2 (en) | 1987-02-17 | 1987-02-17 | Method for producing new methyl methacrylate-styrene resin with excellent heat resistance and transparency |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63199710A true JPS63199710A (en) | 1988-08-18 |
| JPH07100725B2 JPH07100725B2 (en) | 1995-11-01 |
Family
ID=12356652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62032355A Expired - Fee Related JPH07100725B2 (en) | 1987-02-17 | 1987-02-17 | Method for producing new methyl methacrylate-styrene resin with excellent heat resistance and transparency |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07100725B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5302679A (en) * | 1992-08-06 | 1994-04-12 | Loctite Corporation | Anaerobic compositions which expand when post-cured |
| EP0600332A1 (en) * | 1992-12-04 | 1994-06-08 | Röhm GmbH | Flame retardant noise protection wall made of acrylic glass |
| WO2007015512A1 (en) * | 2005-08-04 | 2007-02-08 | Nippon Shokubai Co., Ltd. | Low birefringent copolymer |
| JP2007063541A (en) * | 2005-08-04 | 2007-03-15 | Nippon Shokubai Co Ltd | Low birefringent copolymer |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311518B (en) * | 2010-06-29 | 2013-09-04 | 中国石油天然气股份有限公司 | Preparation method of (methyl) acrylate polymer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61166807A (en) * | 1985-01-18 | 1986-07-28 | Sumitomo Naugatuck Co Ltd | Production of copolymer |
| JPS61174209A (en) * | 1985-01-29 | 1986-08-05 | Sumitomo Naugatuck Co Ltd | Production of copolymer |
| JPS61278509A (en) * | 1985-06-05 | 1986-12-09 | Toray Ind Inc | Optical disc base |
| JPS63154712A (en) * | 1986-12-17 | 1988-06-28 | Japan Synthetic Rubber Co Ltd | Production of transparent heat-resistant resin |
-
1987
- 1987-02-17 JP JP62032355A patent/JPH07100725B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61166807A (en) * | 1985-01-18 | 1986-07-28 | Sumitomo Naugatuck Co Ltd | Production of copolymer |
| JPS61174209A (en) * | 1985-01-29 | 1986-08-05 | Sumitomo Naugatuck Co Ltd | Production of copolymer |
| JPS61278509A (en) * | 1985-06-05 | 1986-12-09 | Toray Ind Inc | Optical disc base |
| JPS63154712A (en) * | 1986-12-17 | 1988-06-28 | Japan Synthetic Rubber Co Ltd | Production of transparent heat-resistant resin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5302679A (en) * | 1992-08-06 | 1994-04-12 | Loctite Corporation | Anaerobic compositions which expand when post-cured |
| US5373075A (en) * | 1992-08-06 | 1994-12-13 | Loctite Corporation | Anaerobic compositions which expand when post-cured |
| EP0600332A1 (en) * | 1992-12-04 | 1994-06-08 | Röhm GmbH | Flame retardant noise protection wall made of acrylic glass |
| WO2007015512A1 (en) * | 2005-08-04 | 2007-02-08 | Nippon Shokubai Co., Ltd. | Low birefringent copolymer |
| JP2007063541A (en) * | 2005-08-04 | 2007-03-15 | Nippon Shokubai Co Ltd | Low birefringent copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07100725B2 (en) | 1995-11-01 |
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