JPH0150336B2 - - Google Patents
Info
- Publication number
- JPH0150336B2 JPH0150336B2 JP57233083A JP23308382A JPH0150336B2 JP H0150336 B2 JPH0150336 B2 JP H0150336B2 JP 57233083 A JP57233083 A JP 57233083A JP 23308382 A JP23308382 A JP 23308382A JP H0150336 B2 JPH0150336 B2 JP H0150336B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- copolymer
- methyl methacrylate
- maleic anhydride
- 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.)
- 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- 239000000113 methacrylic resin Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 9
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000008188 pellet Substances 0.000 description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 125000005395 methacrylic acid group Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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 2
- 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
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 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
- IIXADVXWTNTNQF-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-1-enylbenzene Chemical compound CC(=C)C(O)=O.CC=CC1=CC=CC=C1 IIXADVXWTNTNQF-UHFFFAOYSA-N 0.000 description 1
- VXVUDUCBEZFQGY-UHFFFAOYSA-N 4,4-dimethylpentanenitrile Chemical compound CC(C)(C)CCC#N VXVUDUCBEZFQGY-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 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-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 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
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 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
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 239000012778 molding material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 239000000049 pigment Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber 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
重合させた共重合体、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
させた共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−スチレン（また
はビニルトルエン）−無水マレイン酸の３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
50〜98重量％
(B) スチレンまたはビニルトルエン
１〜25重量％ および
(C) 無水マレイン酸 １〜25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％
からなる耐候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（）
と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。
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50〜90重量％となる量用いられ、50重量
％未満では上記の特性が失なわれ、また98重量％
を超えると耐熱性の向上が望めなくなる。
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１〜25重量％、好ましくは５〜15重量％
である。１重量％未満であると生産性と耐熱性の
面で劣り、25重量％を超えると機械的性質、光学
的性質が低下し、さらに耐煮沸性が劣る傾向を示
す。本発明において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１種または２種以上の混合物として使用さ
れる。また共重合体（）の構成成分である無水
マレイン酸は、共重合させる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示すものであり、共重合体
（）中１〜25重量％、好ましくは５〜25重量％
である。１重量％未満であると生産性と耐熱性の
点で劣り、25重量％を超えると機械的性質が低下
し、さらに耐煮沸性が悪くなる。
本発明の組成物においては、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の樹脂特性全般のバ
ランスを考慮すると、共重合体（）中のスチレ
ンまたはビニルトルエンのモル数をα、無水マレ
イン酸のモル数をβとしたとき、各成分の配合比
（α／β）を0.9〜1.7となる量的関係にすをこと
が最も望ましい。配合比（α／β）が0.9未満の
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を超える範囲では光学的性質、耐熱
性の低下が認められる。
本発明の組成粉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メタクリル酸メチル、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のメルトインデツ
クス（ASTM Ｄ−1238）に準拠した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１〜２、比較例１〜３
メタクリル酸メチルスチレンおよび無水マレイ
ン酸を表１に示すような割合で配合した単量体混
合物1000ｇに、分子量調節剤としてｔ−ドデシル
メルカプタン2.5ｇ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内容積２のセ
パラブルフラスコに入れた、次いで撹拌しなが
ら、窒素ガスを吹き込んで、系内の空気を追い出
した後、加熱して内温70℃で２，2′−アゾビス
（−2.4−ジメチルバレロニトリル）0.2ｇを添加
し、内温95℃から15分間保持した後保温まで冷却
して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ｔ−ドデシルメル
カプタン3.0ｇ、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）0.3ｇ、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“Mar K329”（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た鋳
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から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
時間熱処理した。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。
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 for copolymerizing methyl methacrylate in the presence of a crosslinked polymer using a polyfunctional monomer, a copolymer obtained by copolymerizing methyl methacrylate with methacrylic acid, methyl methacrylate, α-
Copolymers made by copolymerizing methylstyrene and acrylonitrile have been made. However, the above proposed method has an extremely low polymerization rate, resulting in extremely low productivity and impractical properties, a decrease in mechanical properties, weather resistance, and optical properties, and marked discoloration of the molded product, or Although the heat resistance is improved to some extent in both cases, many problems remain in practical application, such as poor moldability due to the narrow area. 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 with a terpolymer structure of methyl methacrylate-styrene (or vinyltoluene)-maleic anhydride with a specific composition and methyl methacrylate in an amount of 80% by weight or more It was discovered that a resin mixture consisting of a copolymer having This is the heading that led to the present invention. That is, the gist of the present invention is as follows: (A) 50 to 98% by weight of methyl methacrylate or a partial polymer thereof, (B) 1 to 25% by weight of styrene or vinyltoluene, and (C) 1 to 25% by weight of maleic anhydride. A copolymer obtained by polymerizing a monomer mixture consisting of 1 to 99% by weight and 80% by weight of methyl methacrylate.
Copolymer () containing 1 to 99% by weight or more
A weather-resistant methacrylic resin composition. The greatest features of the present invention are a high refractive index, heat-resistant copolymer () having the above-mentioned specific composition and a low refractive index resin () containing methyl methacrylate as a main component.
By blending and homogeneously dispersing the It is surprisingly possible to obtain a composition that has excellent weather resistance and colorless transparency of molded products, and is also extremely well-balanced in terms of heat resistance and moldability. 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 50 to 90% by weight in the copolymer (). If it is less than 50% by weight, the above properties will be lost, and if it is less than 98% by weight.
If it exceeds this value, no improvement in heat resistance can be expected. 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 contains 1 to 25% by weight, preferably 5 to 15% by weight in the copolymer ().
It is. If it is less than 1% by weight, productivity and heat resistance will be poor, and if it exceeds 25% by weight, mechanical properties and optical properties will deteriorate, and boiling resistance will tend to deteriorate. Vinyltoluene used in the present invention includes ortho-, meta-, and para-substituted vinyltoluenes, and these may be used alone or as a mixture of two or more. In addition, maleic anhydride, which is a component of the copolymer (), shows the effect of improving the heat resistance of the copolymer by interacting with the styrene or vinyltoluene to be copolymerized. 1-25% by weight, preferably 5-25% by weight
It is. If it is less than 1% by weight, productivity and heat resistance will be poor, and if it exceeds 25% by weight, mechanical properties will deteriorate and boiling resistance will further deteriorate. In the composition of the present invention, when considering the overall balance of resin properties such as heat resistance, mechanical properties, optical properties, and moldability of the final blended resin, it is important to consider that the styrene in the copolymer () Alternatively, when the number of moles of vinyltoluene is α and the number of moles of maleic anhydride is β, it is most desirable to maintain a quantitative relationship in which the blending ratio (α/β) of each component is 0.9 to 1.7. When the blending ratio (α/β) is less than 0.9, there is a tendency for water resistance and mechanical properties to decrease, and when it exceeds 1.7, optical properties and heat resistance decrease. The copolymer () constituting the powder 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. Examples of monomers used for copolymerization with methyl methacrylate include acrylic esters such as methyl methacrylate and ethyl acrylate, methacrylic esters such as ethyl methacrylate and butyl methacrylate, styrene, and acrylonitrile. 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 melt index of 0.5 to 75 (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 (),
A method of suspension polymerization or bulk polymerization in an aqueous medium containing a suspending dispersant, or a method of dissolving the copolymer () in a monomer mixture constituting the copolymer () and then performing bulk polymerization are adopted. . 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 1-2, Comparative Examples 1-3 2.5 g of t-dodecyl mercaptan was added as a molecular weight regulator to 1000 g of a monomer mixture containing methylstyrene methacrylate and maleic anhydride in the proportions shown in Table 1. This mixture is cooled in a tube,
The mixture was placed in a separable flask with an internal volume of 2 equipped with a thermometer and a stirring rod.Next, while stirring, nitrogen gas was blown in to drive out the air in the system, and the mixture was heated to an internal temperature of 70℃ for 2.2 hours. 0.2 g of '-azobis(-2.4-dimethylvaleronitrile) was added, the internal temperature was kept at 95 DEG C. for 15 minutes, and then cooled to keep warm to obtain a syrup-like partial polymer. 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, 0.3 g of the product name "Tinuvin-P" (manufactured by Ciba Geigy) as an ultraviolet absorber, and 0.3 g of the product name "JP-" as a release agent. 504” (manufactured by Johoku Kagaku Co., Ltd.) 0.2g,
1 g of the trade name "Mar K329" (manufactured by Adeka Argus Co., Ltd.) as a stabilizer and 1 g of stearic acid monoglyceride as a mold release agent were added and sufficiently stirred to dissolve them. This partial polymer mixture was injected through a polyvinyl chloride gasket into a mold in which a thermocouple was set in a cell formed by two tempered glass plates spaced 3 mm apart, and polymerized and cured in warm water at 80°C. I let it happen.
Then, after 30 minutes had elapsed after immersing the mold in hot water until the internal temperature reached its peak, the mold was removed from the warm water and placed in an air heating oven at 130°C.
Heat treated for hours. After cooling, the glass plate was removed to obtain a resin plate with a thickness of approximately 3 mm. Cut and crush this board, 3
It was made into pellets of about 4 mm.
【表】
これらのポリマーとメタクリル系重合体（三菱
レイヨン(株)製、商品名アクリペツトVH）とを
60／40の重量割合でブレンド後、２軸押出機を用
いて200〜270℃で賦形し、ペレツト化（押出温度
270℃）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×２mm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℃[Table] These polymers and methacrylic polymer (manufactured by Mitsubishi Rayon Co., Ltd., trade name Acrypet VH)
After blending at a weight ratio of 60/40, it is shaped using a twin-screw extruder at 200 to 270℃ and pelletized (extrusion temperature
270℃). This pellet was injection molded under the following conditions and the resulting test piece (110mm x 110mm x 2mm thick)
The evaluation results in Table 2 were obtained. Injection molding machine: V-17-65 screw type automatic injection molding machine manufactured by Japan Steel Works Co., Ltd. Injection molding conditions: Cylinder temperature 250-260℃, injection pressure 700Kg/cm 2 Mold temperature 60℃
【表】
比較例 ４〜６
メタクリル酸メチル、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配合した単量体
混合物1000ｇを実施例１と全く同様な方法で製造
し、６mm厚の板を得た。この板を切断、粉砕した
後、実施例１と同じように押出機で賦形し、ペレ
ツト化した。[Table] Comparative Examples 4 to 6 1000 g of a monomer mixture containing methyl methacrylate, styrene, and maleic anhydride in the proportions shown in Table 3 was manufactured in exactly the same manner as in Example 1, and a 6 mm thick plate was prepared. I got it. After cutting and crushing this plate, it was shaped into pellets using an extruder in the same manner as in Example 1.
【表】
このペレツトを使用して実施例１と同様に射出
成形し、得られた試験片についてその物性を評価
した。結果を表４に示す。[Table] This pellet was injection molded in the same manner as in Example 1, and the physical properties of the obtained test piece were evaluated. The results are shown in Table 4.
【表】
化の程度を目視判定する。
実施例３〜５、実施例７〜８
メタクリル酸メチル560ｇ、スチレン240ｇおよ
び無水マレイン酸200ｇからなる単量体混合物を
実施例１と全く同様な方法で重合させ厚さ３mmの
板状共重合体を得た。この共重合体を切断、粉砕
後実施例１のメタクリル系重合体と表５に示す割
合でブレンドし、２軸押出機で回転数250rpm、
温度260℃で賦形してペレツト化した後このペレ
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] Visually judge the degree of oxidation.
Examples 3 to 5, Examples 7 to 8 A monomer mixture consisting of 560 g of methyl methacrylate, 240 g of styrene, and 200 g of maleic anhydride was polymerized in exactly the same manner as in Example 1 to obtain a plate-shaped copolymer with a thickness of 3 mm. I got it. After cutting and pulverizing this copolymer, it was blended with the methacrylic polymer of Example 1 in the proportions shown in Table 5.
After shaping into pellets at a temperature of 260°C, the pellets were injection molded in the same manner as in Example 1, and the test pieces obtained were evaluated. The results are shown in Table 6.
【表】【table】
Claims (1)
分 重合体 50〜98重量％ (B) スチレンまたはビニルトルエン １〜25重量％ および (C) 無水マレイン酸 １〜25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％とからなる耐熱性メタクリル樹脂組成
物。 ２ 共重合体（）がスチレンまたはビニルトル
エンのモル数をα、無水マレイン酸のモル数をβ
としたとき各成分の配合比（α／β）が0.9〜1.7
となる量的関係で構成されているものであること
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 its portion polymer 50-98% by weight (B) Styrene or vinyltoluene 1-25% by weight and (C) Maleic anhydride 1-25% by weight A copolymer obtained by polymerizing a monomer mixture consisting of () 1 to 99% by weight and a copolymer () containing 80% by weight or more of methyl methacrylate () 1 to 99
A heat-resistant methacrylic resin composition consisting of % by weight. 2 The number of moles of styrene or vinyltoluene in the copolymer () is α, and the number of moles of maleic anhydride is β.
When the blending ratio (α/β) of each component is 0.9 to 1.7
The heat-resistant methacrylic resin composition according to claim 1, characterized in that the composition has the following quantitative relationship.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23308382A JPS59122537A (en) | 1982-12-28 | 1982-12-28 | Heat resistant methacrylic 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 |
|---|---|---|---|
| JP23308382A JPS59122537A (en) | 1982-12-28 | 1982-12-28 | Heat resistant methacrylic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59122537A JPS59122537A (en) | 1984-07-16 |
| JPH0150336B2 true JPH0150336B2 (en) | 1989-10-30 |
Family
ID=16949528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23308382A Granted JPS59122537A (en) | 1982-12-28 | 1982-12-28 | Heat resistant methacrylic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59122537A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011026563A (en) * | 2009-06-22 | 2011-02-10 | Asahi Kasei Chemicals Corp | Heat-resistant acrylic resin composition and molding thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1476215A (en) * | 1965-04-23 | 1967-04-07 | Roehm & Haas Gmbh | Process for the preparation of synthetic resins essentially from methyl methacrylate |
| JPS5998156A (en) * | 1982-11-29 | 1984-06-06 | Asahi Chem Ind Co Ltd | Acrylic resin composition having excellent heat resistance and impact resistance |
-
1982
- 1982-12-28 JP JP23308382A patent/JPS59122537A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1476215A (en) * | 1965-04-23 | 1967-04-07 | Roehm & Haas Gmbh | Process for the preparation of synthetic resins essentially from methyl methacrylate |
| JPS5998156A (en) * | 1982-11-29 | 1984-06-06 | Asahi Chem Ind Co Ltd | Acrylic resin composition having excellent heat resistance and impact resistance |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59122537A (en) | 1984-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4558098A (en) | Methacrylic resin composition | |
| JPS59221315A (en) | Preparation of methacrylic copolymer | |
| JPH0129220B2 (en) | ||
| JPS61162509A (en) | Thermoplastic resin and thermoplastic resin composition containing the same | |
| JPH0582405B2 (en) | ||
| EP0208291B1 (en) | Heat-resistant methacrylic resin composition | |
| CN115926415A (en) | PC/PMMA/ASA ternary alloy material and preparation method and application thereof | |
| JPH0150336B2 (en) | ||
| JP3215719B2 (en) | Polymer composition | |
| JPH0129219B2 (en) | ||
| JPH0510385B2 (en) | ||
| JPH04173863A (en) | Resin composition | |
| JP3061551B2 (en) | Method for producing methacrylic resin | |
| JPS61155443A (en) | Heat-resistant methacrylic resin composition | |
| JPS62270648A (en) | Heat-resistant methacrylate resin composition | |
| JPH0517941B2 (en) | ||
| JPS59122509A (en) | Methacrylic resin having low hygroscopicity | |
| JPS6136764B2 (en) | ||
| JPS6214565B2 (en) | ||
| JPS6143643A (en) | Heat-resistant resin composition | |
| CA1248674A (en) | Methylmethacrylate/n-phenylmaleimide copolymer- containing polymer alloys | |
| JPS58113214A (en) | Resin composition | |
| KR20040050146A (en) | Thermoplastic Resin Composition with Good Releasing Ability | |
| JPH0149181B2 (en) | ||
| JP3615875B2 (en) | Methacrylic resin casting polymer |