JPH0129219B2 - - Google Patents
Info
- Publication number
- JPH0129219B2 JPH0129219B2 JP22986482A JP22986482A JPH0129219B2 JP H0129219 B2 JPH0129219 B2 JP H0129219B2 JP 22986482 A JP22986482 A JP 22986482A JP 22986482 A JP22986482 A JP 22986482A JP H0129219 B2 JPH0129219 B2 JP H0129219B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- copolymer
- methyl methacrylate
- methylstyrene
- maleic anhydride
- 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.)
- Expired
Links
- 229920001577 copolymer Polymers 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 27
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- 239000000113 methacrylic resin Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 8
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- 239000008188 pellet Substances 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 5
- 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 4
- 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 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000006082 mold release agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 239000005341 toughened glass Substances 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 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
- FFZPLWBCVXNDIB-UHFFFAOYSA-N 3-(1-phenylprop-2-enyl)furan-2,5-dione Chemical compound C(=C)C(C1=CC=CC=C1)/C/1=C/C(=O)OC\1=O FFZPLWBCVXNDIB-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
- 229920005509 ACRYPET® VH Polymers 0.000 description 1
- 229920005497 Acrypet® Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-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-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 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
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- YYZBDKFCSODATN-UHFFFAOYSA-N methyl 2-methylprop-2-enoate prop-1-en-2-ylbenzene styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1.CC(=C)C1=CC=CC=C1 YYZBDKFCSODATN-UHFFFAOYSA-N 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、透明な耐熱性メタクリル樹脂組成物
に関する。
メタクリル酸メチル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
にお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。
しかし、一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、その用途展開が制約
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
チルと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）、メタクリル酸メチル、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ルに溶解した後メ
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49−8718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43−9753号）、メタクリル酸メ
チル、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、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。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つたり、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おいて
多くの問題点が残されているのが現状である。
本発明者ら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
に関して鋭意研究を行なつた結果、特定の配合組
成を有するメタクリル酸メチル−α−メチルスチ
レン−スチレンまたはビニルトルエン−無水マレ
イン酸の４元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80重量％以上を有する共重合
体とからなる樹脂混合物がその目的を達成するこ
とが出来、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にすぐれるという全く予
想外の効果があることを見い出し本発明に至つた
ものである。
すなわち、本発明の要旨とするところは、
(A) メタクリル酸メチルまたはそれの部分重合体
40〜97重量％
(B) α−メチルスチレン １〜20重量％
(C) スチレンまたはビニルトルエン
１〜20重量％および
(D) 無水マレイン酸 １〜20重量％
よりなる単量体混合物を重合して得られる共重合
体（）１〜99重量％とメタクリル酸メチルを80
重量％以上含有する共重合体（）１〜99重量％
からなる耐熱性メタクリル樹脂組成物にある。
本発明の最大の特徴は、上記の特定組成を有す
る高屈折率で耐熱性の共重合体（）とメタクリ
ル酸メチルを主成分とする低屈折率の樹脂をブレ
ンドして均質分散させることにより、前記特公昭
49−10156号、特公昭56−43242号および特開昭56
−81322号に記載される３元系、４元系の共重合
体に比較して耐候性、成型品の無色透明性にすぐ
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い出したことにある。
本発明の組成物において共重合体（）を構成
するメタクリル酸メチル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（）との
相溶性をよくするための成分であり、共重合体
（）中40〜97重量％となる量用いられ、40重量
％未満では上記の特性が失なわれ、また97重量％
を超えると耐熱性の向上が望めなくなる。
また共重合体（）の構成成分であるα−メチ
ルスチレンは耐熱性を向上させる成分であり、か
つ無水マレイン酸との共重合反応性を高めるため
の成分であり、共重合体（）中１〜20重量％、
好ましくは３〜10重量％である。１重量％未満で
あると耐熱性の面で劣り、20重量％を超えると生
産性および共重合体の耐熱分解性が低下する。
また共重合体（）の構成成分であるスチレン
またはビニルトルエンは直接的には耐熱性を向上
させる成分ではないが耐熱性向上成分である無水
マレイン酸の共重合反応性を高めることにより間
接的に耐熱性を向上させると同時に生産性の向上
に対して著しい効果を示すものであり、共重合体
（）中１〜20重量％が必要であり１重量％未満
であると間接的に耐熱性が低下し、生産性の面で
も劣る。20重量％を超えると光学的性質、耐候性
が低下するようになる。使用されるビニルトルエ
ンとしてはオルト、メタ、パラ置換体があげら
れ、これらは一種または２種以上の混合物として
使用される。
共重合体（）の構成成分である無水マレイン
酸はα−メチルスチレン、スチレンまたはビニル
トルエンとの相互作用により共重合体の耐熱性を
向上させる効果を有し、共重合体（）中１〜20
重量％、好ましくは５〜15重量％必要である。１
重量％未満であると、生産性と耐熱性の面で劣
り、20重量％を超えると機械的性質、光学的性質
が低下し、更に耐煮沸性が劣る。
本発明に於いては最終的に得られるブレンド樹
脂の耐熱性、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バランスを考慮す
ると、共重合体（）はα−メチルスチレンのモ
ル数をα、スチレンまたはビニルトルエンのモル
数をβ、無水マレイン酸のモル数をγとしたと
き、各成分の配合比（α＋β／γ）が0.9〜1.7と
なる量的関係となるように構成することが最も望
ましい。0.9未満である場合には耐水性、機械的
性質が低下する傾向が認められ、1.7より大きい
範囲では、光学的性質、耐熱性の低下が認められ
る。
本発明の組成物を構成する共重合体（）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ためのものである。
共重合体（）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あり、使
用量が80重量％未満であると前記物性が低下す
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
酸エチル等のアクリル酸エステル、メタクリル酸
エチル、メタクリル酸ブチル等のメタクリル酸エ
ステル、スチレン、アクリロニトリル等があげら
れ、これらの単量体は１種または２種以上20重量
％以下の量で共重合される。
本発明の樹脂組成物を構成する共重合体（）
の使用量は組成物中１〜99重量％、好ましくは５
〜95重量％であり、１重量％未満であると耐熱性
が劣り、99重量％を越えると機械的性質、耐候性
が劣る。
また共重合体（）の使用量は１〜99重量％、
好ましくは５〜95重量％である。１重量％未満で
は機械的性質、耐候性が劣り、99重量％を越える
と耐熱性の向上が望めない。
本発明の組成物は0.5〜75のフローレート
（FR）（ASTM Ｄ−1238に準拠して230℃、10
Kg／cm2荷重下での10分間の押出量（ｇ））を有す
る成形材料として特に有用なものである。
本発明の組成物を製造する方法としては特に限
定されず例えば共重合体（）を常法に従つて塊
状重合、懸濁重合などにより製造し、得られた共
重合体（）と共重合体（）とを混合後、200
〜300℃の温度で溶融、混練、押出を行なつてブ
レンド樹脂を製造する方法、共重合体（）を製
造する単量体混合物に共重合体（）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（）を共重合
体（）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。
また本発明の組成物にお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。
以下、実施例によつて本発明の内容をさらに詳
しく説明する。
実施例１〜３、比較例１〜２
メタクリル酸メチル650ｇ、α−メチルスチレ
ン50ｇ、スチレン150ｇおよび無水マレイン酸150
ｇからなる単量体混合物1000ｇに、分子量調節剤
としてｔ−ドデシルメルカプタン2.3ｇを加え、
この混合物を冷却管、温度計および撹拌棒をセツ
トした２のセパラブルフラスコに入れた。次い
で撹拌しながら窒素ガスを吹込んで系内の空気を
追い出した後、加熱して内温70℃で重合開始剤ア
ゾビスイソブチロニトリル0.2ｇを添加し、内温
95℃から15分間保持した後室温まで冷却し、600
センチポイズのシラツプ状部分重合物を得た。
この部分重合物1000ｇに対してラウロイルパー
オキサイド４ｇ、分子量調節剤としてｔ−ドデシ
ルメルカプタン3.0ｇ、剥離剤として商品名“JP
−504”（城北化学(株)製）0.2ｇ、紫外線吸収剤と
して商品名“チヌビン−Ｐ”（チバガイギー(株)製）
0.3ｇ、安定剤として商品名“MarK329”（アデ
カアーガス(株)製）１ｇ、離型剤としてステアリン
酸モノグリセライド１ｇを加え、充分撹拌して溶
解させた。この部分重合体混合物を、ポリ塩化ビ
ニル製ガスケツトを介して３mmの間隔とした２枚
の強化ガラス板で形成させたセルに熱電対をセツ
トしてなる鋳型中に注入し、80℃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確認して30分経過
後、温水中から鋳型を取り出し、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３mmの樹脂板を得た。この板を切断、粉
砕し３〜４mm程度のペレツト状とした。このペレ
ツトと三菱レイヨン(株)製商品名“アクリペツト
VH”と表１に示す割合でヘンシエルミキサーで
ブレンド後、二軸押出機で265℃の温度で賦形し
てペレツト化した。このペレツト、下記の条件で
射出成形し、得られた試験片（110mm×110mm×２
mm厚）から表２の評価結果を得た。
射出成形機：(株)日本製鋼所製、Ｖ−17−65型スク
リユー式自動射出成形機
射出成形条件：シリンダー温度250〜260℃、射出
圧700Kg／cm2
金型温度60℃
The present invention relates to a transparent heat-resistant methacrylic resin composition. Methyl methacrylate-based methacrylic resin has excellent optical properties and weather resistance, and has relatively well-balanced performance in terms of mechanical properties, thermal properties, and moldability. Taking advantage of these properties, it is widely used in many fields such as signboards, lighting covers, nameplates, automobile parts, electrical equipment parts, decorations, and miscellaneous goods, and further applications are being developed. However, on one side, the heat distortion temperature is around 100℃,
Due to insufficient heat resistance, there are many fields in which its application is restricted, and there is a deep-rooted demand for improved heat resistance. There have already been many proposals for ways to improve the heat resistance of methacrylic resins, such as copolymerization of methyl methacrylate and α-methylstyrene;
Method for copolymerizing methyl methacrylate, α-methylstyrene and maleic anhydride (Japanese Patent Publication No. 1973-
10156), a method for copolymerizing methyl methacrylate, styrene, and maleic anhydride (Japanese Patent Publication No. 1983-
43242), method of copolymerizing methyl methacrylate, α-methylstyrene, styrene, and maleic anhydride (JP-A-56-81322), methyl methacrylate after dissolving poly-α-methylstyrene in methyl methacrylate. Method of polymerizing
1616, Japanese Patent Publication No. 49-8718), a method for copolymerizing methyl methacrylate and N-allylmaleimide (Japanese Patent Publication No. 43-9753), a method for copolymerizing methyl methacrylate, α-methylstyrene, and maleimide. , a method of copolymerizing methyl methacrylate in the presence of a crosslinked polymer using a polyfunctional monomer, a polymer obtained by copolymerizing methyl methacrylate with methacrylic acid, and a method of copolymerizing methyl methacrylate, α-methylstyrene, and acrylonitrile. Polymerized polymers have been produced. However, in the method proposed above, the polymerization rate is extremely low, so the productivity is extremely low and it is not practical.
Weather resistance and optical properties may deteriorate, the molded product may be markedly colored, or the molding area may be narrow, resulting in poor molding processability.In either case, heat resistance may be improved to some extent, but there are many problems in practical use. At present, problems remain. In view of the current situation, the present inventors developed 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. As a result of intensive research, we found that a copolymer having a quaternary copolymer structure of methyl methacrylate-α-methylstyrene-styrene or vinyltoluene-maleic anhydride with a specific composition and methyl methacrylate at 80% A resin mixture consisting of a copolymer and a copolymer having a weight percentage of more than This discovery led to the present invention. That is, the gist of the present invention is that (A) methyl methacrylate or a partial polymer thereof
40-97% by weight (B) α-methylstyrene 1-20% by weight (C) Styrene or vinyltoluene
Copolymer () obtained by polymerizing a monomer mixture consisting of 1 to 20% by weight and (D) 1 to 20% by weight of maleic anhydride and 80% by weight of methyl methacrylate.
Copolymer () containing 1 to 99% by weight or more
A heat-resistant methacrylic resin composition. The greatest feature of the present invention is that by blending and homogeneously dispersing a high refractive index, heat-resistant copolymer () having the above-mentioned specific composition and a low refractive index resin whose main component is methyl methacrylate, Said Tokukosho
No. 49-10156, Japanese Patent Publication No. 56-43242, and Japanese Patent Publication No. 1983
-Compared to the ternary and quaternary copolymers described in No. 81322, this composition has excellent weather resistance and colorless transparency of molded products, and is also extremely well-balanced in terms of heat resistance and moldability. is surprisingly obtainable. 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. In the composition of the present invention, methyl methacrylate or its partial polymer component constituting the copolymer () retains the optical properties, weather resistance, or mechanical properties inherent to the methacrylic resin, and is compatible with the copolymer (). It is a component to improve solubility, and is used in an amount of 40 to 97% by weight in the copolymer ().If it is less than 40% by weight, the above properties will be lost, and if it is less than 97% by weight.
If it exceeds this value, no improvement in heat resistance can be expected. In addition, α-methylstyrene, which is a component of the copolymer (), is a component that improves heat resistance and is a component that increases copolymerization reactivity with maleic anhydride. ~20% by weight,
Preferably it is 3 to 10% by weight. If it is less than 1% by weight, the heat resistance will be poor, and if it exceeds 20% by weight, the productivity and heat decomposition resistance of the copolymer will decrease. In addition, styrene or vinyltoluene, which is a component of the copolymer (), does not directly improve heat resistance, but indirectly by increasing the copolymerization reactivity of maleic anhydride, which is a heat resistance improving component. It shows a remarkable effect on improving heat resistance and productivity at the same time, and it requires 1 to 20% by weight in the copolymer (), and if it is less than 1% by weight, it will indirectly reduce heat resistance. and productivity is also inferior. If it exceeds 20% by weight, optical properties and weather resistance will deteriorate. The vinyltoluene used includes ortho-, meta-, and para-substituted vinyltoluenes, and these are used singly or as a mixture of two or more. Maleic anhydride, which is a component of the copolymer (), has the effect of improving the heat resistance of the copolymer through interaction with α-methylstyrene, styrene, or vinyltoluene. 20
% by weight, preferably from 5 to 15% by weight. 1
If it is less than 20% by weight, productivity and heat resistance will be poor, and if it exceeds 20% by weight, mechanical properties and optical properties will be degraded, and boiling resistance will be poor. In the present invention, considering the overall balance of resin properties such as heat resistance, mechanical properties, optical properties, and moldability of the final blended resin, the copolymer () is made of α-methylstyrene. When the number of moles is α, the number of moles of styrene or vinyltoluene is β, and the number of moles of maleic anhydride is γ, the quantitative relationship is such that the blending ratio of each component (α + β / γ) is 0.9 to 1.7. It is most desirable to configure When it is less than 0.9, there is a tendency for water resistance and mechanical properties to decrease, and when it is greater than 1.7, optical properties and heat resistance tend to decrease. The copolymer () constituting the composition of the present invention is used to impart weather resistance, mechanical properties, optical properties, and moldability inherent to methacrylic resin.
Methyl methacrylate, which is the main component in the copolymer (), is used to impart weather resistance, optical properties, and mechanical properties inherent to methacrylic resin, and if the amount used is less than 80% by weight, the above physical properties will be impaired. decreases. Monomers used for copolymerization with methyl methacrylate include acrylic esters such as methyl acrylate and ethyl acrylate, methacrylic esters such as ethyl methacrylate and butyl methacrylate, styrene, acrylonitrile, etc. One or more of these monomers are copolymerized in an amount of 20% by weight or less. Copolymer () constituting the resin composition of the present invention
The amount used is 1 to 99% by weight in the composition, preferably 5% by weight.
If it is less than 1% by weight, the heat resistance will be poor, and if it exceeds 99% by weight, the mechanical properties and weather resistance will be poor. In addition, the amount of copolymer () used is 1 to 99% by weight,
Preferably it is 5 to 95% 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. The composition of the present invention has a flow rate (FR) of 0.5 to 75 (according to ASTM D-1238 at 230°C, 10
It is particularly useful as a molding material having an extrusion rate (g) in 10 minutes under a load of Kg/ cm2 . The method for producing the composition of the present invention is not particularly limited, and for example, the copolymer (2) is produced by bulk polymerization, suspension polymerization, etc. according to a conventional method, and the obtained copolymer (2) and the copolymer After mixing with (), 200
A method for producing a blended resin by melting, kneading, and extruding at a temperature of ~300°C. After dissolving the copolymer () in a monomer mixture to produce the copolymer (),
Methods of suspension polymerization or bulk polymerization in an aqueous medium containing a suspending dispersant, and methods of dissolving the copolymer () in a monomer mixture constituting the copolymer () and then performing bulk polymerization are adopted. Ru. In addition, in the composition of the present invention, if necessary,
Additives such as ultraviolet absorbers, release agents, antioxidants, mold release agents, dyes and pigments may be added. Hereinafter, the content of the present invention will be explained in more detail with reference to Examples. Examples 1-3, Comparative Examples 1-2 650 g of methyl methacrylate, 50 g of α-methylstyrene, 150 g of styrene, and 150 g of maleic anhydride
Add 2.3 g of t-dodecyl mercaptan as a molecular weight regulator to 1000 g of a monomer mixture consisting of
This mixture was placed in a second separable flask equipped with a condenser, a thermometer, and a stirring bar. Next, while stirring, nitrogen gas was blown in to drive out the air in the system, and then the polymerization initiator azobisisobutyronitrile (0.2 g) was added at an internal temperature of 70°C by heating.
After holding at 95℃ for 15 minutes, cool to room temperature and incubate at 600℃.
A centipoise syrup-like partial polymer was obtained. For 1000 g of this partially polymerized material, 4 g of lauroyl peroxide, 3.0 g of t-dodecyl mercaptan as a molecular weight regulator, and the product name "JP" as a release agent.
-504” (manufactured by Johoku Kagaku Co., Ltd.) 0.2 g, as an ultraviolet absorber, product name “Tinuvin-P” (manufactured by Ciba Geigy Co., Ltd.)
0.3 g, 1 g of trade name "MarK329" (manufactured by Adeka Argus Co., Ltd.) as a stabilizer, and 1 g of stearic acid monoglyceride as a mold release agent were added, and the mixture was sufficiently stirred to dissolve. This partial polymer mixture was injected through a polyvinyl chloride gasket into a mold consisting of a thermocouple set in a cell formed by two tempered glass plates spaced 3 mm apart, and then placed in a hot water bath at 80°C. It was polymerized and cured. After 30 minutes of checking the time from immersion in hot water until the internal temperature reached its peak, the mold was taken out of the hot water and treated in an air heating oven at 130°C for 2 hours. After cooling, the glass plate was removed to obtain a resin plate with a thickness of approximately 3 mm. This plate was cut and crushed into pellets of about 3 to 4 mm. These pellets and Mitsubishi Rayon Co., Ltd.'s product name "AcryPets"
VH" and blended in a Henschel mixer at the proportions shown in Table 1, the pellets were shaped into pellets using a twin-screw extruder at a temperature of 265°C. The pellets were injection molded under the following conditions, and test pieces were obtained. (110mm×110mm×2
The evaluation results shown in Table 2 were obtained based on the thickness (mm thickness). Injection molding machine: Japan Steel Works, Ltd., V-17-65 screw type automatic injection molding machine Injection molding conditions: Cylinder temperature 250-260℃, injection pressure 700Kg/cm 2 Mold temperature 60℃
【表】【table】
【表】
比較例 ３〜５
メタクリル酸メチル、α−メチルスチレン、ス
チレンおよび無水マレイン酸を表３に示すような
割合で混合した単量体混合物1000ｇに、分子量調
節剤としてｔ−ドデシルメルカプタン2.6ｇを加
え、冷却管、温度計および撹拌棒をセツトした２
のセパラブルフラスコに入れた。次いで撹拌し
ながら窒素置換を行つた後、加熱して内温70℃で
重合開始剤アゾビスイソブチロニトリル0.25ｇを
添加し、内温95℃から15分間保持して室温に冷却
し、シラツプ状部分重合物を得た。
この部分重合物1000ｇに対してラウロイルパー
オキサイド４ｇ、分子量調節剤としてｔ−ドデシ
ルメルカプタン3.0ｇ、剥離剤として商品名“JP
−504”（城北化学(株)製）0.2ｇ、安定剤として商
品名“MarK329”（アデカアーガス(株)製）１ｇ、
紫外線吸収剤として商品名“チヌビン−Ｐ”（チ
バガイギー社製）0.2ｇ、離型剤としてステアリ
ン酸モノグリセライド１ｇを入れ充分撹拌溶解さ
せた。この部分重合体混合物を、ポリ塩化ビニル
製ガスケツトを介して３mmの間隔とした２枚の強
化ガラス板でで成形させたセルに熱電対をセツト
してなる鋳型中に注入し、80℃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確認して30分経過後、
温水中から鋳型を取り出し、次いで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３mmの樹脂板を得た。このポリマー
を切断、粉砕し３〜４mm程度のペレツト状とし
た。[Table] Comparative Examples 3 to 5 2.6 g of t-dodecyl mercaptan was added as a molecular weight regulator to 1000 g of a monomer mixture in which methyl methacrylate, α-methylstyrene, styrene, and maleic anhydride were mixed in the proportions shown in Table 3. 2, and set up the cooling tube, thermometer, and stirring bar.
into a separable flask. Next, after purging with nitrogen while stirring, the polymerization initiator azobisisobutyronitrile (0.25 g) was added at an internal temperature of 70°C by heating, maintained at an internal temperature of 95°C for 15 minutes, and cooled to room temperature. A partially polymerized product was obtained. For 1000 g of this partially polymerized material, 4 g of lauroyl peroxide, 3.0 g of t-dodecyl mercaptan as a molecular weight regulator, and the product name "JP" as a release agent.
-504” (manufactured by Johoku Kagaku Co., Ltd.) 0.2 g, as a stabilizer product name “MarK329” (manufactured by Adeka Argus Co., Ltd.) 1 g,
0.2 g of "Tinuvin-P" (trade name, manufactured by Ciba Geigy) as an ultraviolet absorber and 1 g of stearic acid monoglyceride as a mold release agent were added and dissolved with sufficient stirring. This partial polymer mixture was injected into a mold consisting of a thermocouple set in a cell made of two tempered glass plates spaced 3 mm apart through a polyvinyl chloride gasket, and heated with 80℃ hot water. It was polymerized and cured inside. After 30 minutes, check the time it takes for the internal temperature to reach its peak after immersing it in hot water.
The mold was removed from the hot water and then placed in an air oven at 130°C for 2 hours. After cooling, the glass plate was removed to obtain a resin plate with a thickness of about 3 mm. This polymer was cut and crushed into pellets of about 3 to 4 mm.
【表】
このポリマーを40mmφの単軸押出機を用い265
℃で賦形した。このペレツトを用いて、実施例１
と同じ条件下で射出成形し、得られた試験片を評
価した。その結果を表４に示す。[Table] This polymer was produced using a 40mmφ single-screw extruder.
Shaped at ℃. Using this pellet, Example 1
The test pieces obtained by injection molding were evaluated under the same conditions as described above. The results are shown in Table 4.
【表】
実施例４〜６、比較例６
メタクリル酸メチル665ｇ、α−メチルスチレ
ン55ｇ、Ｐ−メチルスチレン140ｇ、および無水
マレイン酸140ｇよりなる単量体混合物を用いる
以外は実施例と全く同じ方法で３mm厚の樹脂板を
得た。これを切断、粉砕後、三菱レイヨン(株)製商
品名“アクリペツトVH”と表５に示す割合（重
量部）でブレンドした。次いでこのブレンド物を
２軸押出機（温度265℃）で賦形してペレツト化
した。[Table] Examples 4 to 6, Comparative Example 6 Exactly the same method as in Example except that a monomer mixture consisting of 665 g of methyl methacrylate, 55 g of α-methylstyrene, 140 g of P-methylstyrene, and 140 g of maleic anhydride was used. A resin plate with a thickness of 3 mm was obtained. After cutting and pulverizing this, it was blended with Mitsubishi Rayon Co., Ltd.'s product name "Acrypet VH" in the proportions (parts by weight) shown in Table 5. This blend was then shaped into pellets using a twin-screw extruder (temperature: 265°C).
【表】
このペレツトを実施例１と同じように射出成形
し、得られた試験片を評価した。その結果を表６
に示す。[Table] The pellets were injection molded in the same manner as in Example 1, and the test pieces obtained were evaluated. Table 6 shows the results.
Shown below.
Claims (1)
合体 40〜97重量％ (B) α−メチルスチレン １〜20重量％ (C) スチレンまたはビニルトルエン
１〜20重量％および (D) 無水マレイン酸 １〜20重量％ よりなる混合物を重合して得られる共重合体
（）１〜99重量％とメタクリル酸メチルを80重
量％以上含有する共重合体（）１〜99重量％と
からなる耐熱性メタクリル樹脂組成物。 ２ 共重合体（）がα−メチルスチレンのモル
数をα、スチレンまたはビニルトルエンのモル数
をβおよび無水マレイン酸のモル数をγとしたと
き各成分の配合比（α＋β／γ）が0.9〜1.7とな
る量的関係で構成されたものであることを特徴と
する特許請求の範囲第１項記載の耐熱性メタクリ
ル樹脂組成物。[Scope of Claims] 1 (A) Methyl methacrylate monomer or partial polymer 40 to 97% by weight (B) α-methylstyrene 1 to 20% by weight (C) Styrene or vinyltoluene
A copolymer obtained by polymerizing a mixture consisting of 1 to 20% by weight and (D) maleic anhydride (1 to 99% by weight) and 80% by weight or more of methyl methacrylate. () A heat-resistant methacrylic resin composition comprising 1 to 99% by weight. 2 The copolymer () has a blending ratio of each component (α+β/γ) of 0.9, where the number of moles of α-methylstyrene is α, the number of moles of styrene or vinyltoluene is β, and the number of moles of maleic anhydride is γ. The heat-resistant methacrylic resin composition according to claim 1, characterized in that the composition has a quantitative relationship of 1.7 to 1.7.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22986482A JPS59124946A (en) | 1982-12-29 | 1982-12-29 | Heat-resistant methacrylate resin composition |
| US06/563,021 US4558098A (en) | 1982-12-28 | 1983-12-19 | Methacrylic resin composition |
| CA000443790A CA1244573A (en) | 1982-12-28 | 1983-12-20 | Methacrylic resin composition |
| EP83112930A EP0113105B1 (en) | 1982-12-28 | 1983-12-21 | Methacrylic resin composition |
| DE8383112930T DE3371641D1 (en) | 1982-12-28 | 1983-12-21 | Methacrylic resin composition |
| AU22784/83A AU558525B2 (en) | 1982-12-28 | 1983-12-22 | Methacrylic resin composition |
| IT8324403A IT1170065B (en) | 1982-12-28 | 1983-12-27 | METHACRYLIC RESIN COMPOSITION |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22986482A JPS59124946A (en) | 1982-12-29 | 1982-12-29 | Heat-resistant methacrylate resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59124946A JPS59124946A (en) | 1984-07-19 |
| JPH0129219B2 true JPH0129219B2 (en) | 1989-06-08 |
Family
ID=16898889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22986482A Granted JPS59124946A (en) | 1982-12-28 | 1982-12-29 | Heat-resistant methacrylate resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59124946A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100909307B1 (en) * | 2006-06-26 | 2009-07-24 | 주식회사 엘지화학 | Transparent sheet with excellent heat resistance |
-
1982
- 1982-12-29 JP JP22986482A patent/JPS59124946A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59124946A (en) | 1984-07-19 |
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