JPH0129218B2 - - Google Patents
Info
- Publication number
- JPH0129218B2 JPH0129218B2 JP57211870A JP21187082A JPH0129218B2 JP H0129218 B2 JPH0129218 B2 JP H0129218B2 JP 57211870 A JP57211870 A JP 57211870A JP 21187082 A JP21187082 A JP 21187082A JP H0129218 B2 JPH0129218 B2 JP H0129218B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- resin
- impact
- methacrylic resin
- molecular weight
- 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
- 239000000113 methacrylic resin Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 18
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- 229920001971 elastomer Polymers 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 229920006222 acrylic ester polymer Polymers 0.000 claims description 7
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 239000011347 resin Substances 0.000 description 29
- 229920005989 resin Polymers 0.000 description 29
- 239000000178 monomer Substances 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 125000005395 methacrylic acid group Chemical group 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- KCMITHMNVLRGJU-CMDGGOBGSA-N Allyl cinnamate Chemical compound C=CCOC(=O)\C=C\C1=CC=CC=C1 KCMITHMNVLRGJU-CMDGGOBGSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 206010015915 eye discharge Diseases 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 229940071089 sarcosinate Drugs 0.000 description 1
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は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
透明性ならびに耐候性に極めて優れた特性を有し
ているばかりでなく、機械的性質、熱的性質、成
形加工性などにもバランスのとれた性質を有して
おり、これらの特徴を生かしてシート材料あるい
は成形材料として看板、照明機器部品、電気機器
部品、自動車部品、雑貨など多方面に使用されて
いる。しかし市場においては耐衝撃性を向上させ
たメタクリル樹脂の要求は強い。このような背景
より現在２〜３品種の耐衝撃性メタクリル樹脂が
上市されている。しかし、これらのものは耐衝撃
性向上の観点よりゴム含量を増しているために樹
脂の流動性が悪い。一方自動車の軽量化、コスト
低減の傾向から市場では部品の薄肉が求められ、
したがつて使用する樹脂の流動性の向上が強く望
まれている。樹脂の流動性を向上させる方法とし
ては、例えばマトリツクス樹脂の分子量を小さく
する方法があるが、この方法では同時に耐衝撃性
も劣るため好ましくない。このような背景から本
発明者らは耐衝撃性でかつ流動性にすぐれたメタ
クリル樹脂を開発すべく鋭意検討した結果、架橋
アクリル酸エステル系重合体をゴム成分とした耐
衝撃性メタクリル樹脂と特定の分子量分布を有す
るメタクリル系樹脂とを特定配合することによ
り、上記の欠点が解消できることを見出し本発明
に到つた。
すなわち、本発明の要旨とするところは、架橋
アクリル酸エステル系重合体をゴム成分とした耐
衝撃性メタクリル樹脂とメタクリル酸メチル単位
を70重量％以上含有し重量平均分子量（Mw）と
数平均分子量（MN）の比（Mw／MN）が2.2〜5.0
の範囲の分子量分布を有するメタクリル系樹脂と
から成る組成物であつて、かつ該組成物中に１〜
50重量％の架橋アクリル酸エステル系重合体を含
有せしめてなるメタクリル樹脂組成物にある。
本発明の組成物を構成する架橋アクリル酸エス
テル系重合体をゴム成分とする耐衝撃性メタクリ
ル樹脂（以下、耐衝撃性樹脂と呼ぶ）は、樹脂組
成物の耐衝撃性を改良させる成分であつて、かつ
耐溶剤性も改良する成分である。この耐衝撃性樹
脂は本発明の目的を阻害しないものであれば特に
限定されず、種々の層構造をもつ架橋アクリル酸
エステル系重合体をゴム成分とする耐衝撃性のメ
タクリル樹脂が使用できる。例えば、アルキル基
の炭素数が１〜８のアクリル酸アルキルエステル
の少なくとも１種70〜90重量％とスチレン単独ま
たはスチレンとその誘導体の混合物9.9〜29.9重
量％ならびにこれと共重合可能で１分子中に２個
以上の二重結合を有する例えばアリル（メタ）ア
クリレート、トリアリルシアヌレート、ケイ皮酸
アリル等の多官能単量体0.1〜10重量％を用いて
得られた架橋アクリル酸エステル重合体ラテツク
ス、もしくは、メタクリル酸メチル単位を80重量
％以上含む硬質架橋樹脂を粒子内部に含有し、ア
ルキル基の炭素数が１〜８のアクリル酸アルキル
エステルの少なくとも１種とスチレン単独または
スチレンとその誘導体の混合物90〜99.9重量％な
らびにこれと共重合可能で１分子中に２個以上の
二重結合を有する例えばアリル（メタ）アクリレ
ート、トリアリルシアヌレート、ケイ皮酸アリル
等の多官能単量体0.1〜10重量％よりなる単量体
混合物の架橋アクリル酸エステル系共重合体が外
層を構成する多重構造アクリル系弾性体ラテツク
スの存在下に、メタクリル酸メチル80〜100重量
％、アルキルの炭素数１〜８のアクリル酸アルキ
ルエステルの少なくとも１種０〜20重量、および
これと共重合可能な他のビニル単量体０〜10重量
％以下よりなる単量体または単量体混合物を乳化
重合することにより得られる。
また本発明の組成物を構成するメタクリル酸メ
チル単位を70重量％以上含有し、重量平均分子量
（Mw）と数平均分子量（MN）の比（Mw／MN）
が2.2〜5.0の範囲の分子量分布を有するメタクリ
ル系樹脂（以下、メタクリル樹脂と呼ぶ）は、透
明性、耐候性等メタクリル樹脂の特性を保持する
ものであり、特に耐衝撃性の発現性及び流動性を
向上させる成分である。しかしメタクリル樹脂の
分子量を大きくすると耐衝撃性は大となるが流動
性を低下させる。また分子量を小さくすると流動
性は向上するが耐衝撃性は低下する。そこで本発
明者らが鋭意検討した結果、耐衝撃性と流動性と
の両方を満足する分子量範囲として重量平均分子
量（Mw）／数平均分子量（MN）の比（Mw／
MN）が2.2〜5.0なる範囲であることを見い出し
た。またメタクリル樹脂においては、メタクリル
酸メチル単位を70重量％以上含有することが必要
である。メタクリル樹脂中メタクリル酸メチル単
位が70重量％未満であるとメタクリル樹脂として
の特性が低下する、したがつてメタクリル樹脂中
のメタクリル酸メチル単位の含有量としては、好
ましくは80〜99.5重量％である。メタクリル樹脂
を得るための共重合成分としては不飽和ビニル単
量体であり、例えばアクリル酸メチル、アクリル
酸エチル、アクリル酸ブチル、アクリル酸２−エ
チルヘキシル等のアクリル酸エステル；スチレ
ン、α−メチルスチレン、アクリロニトリル等が
あげられる。
メタクリル樹脂における（Mw）／（MN）が
2.2未満であると流動性と耐衝撃性のバランスが
とれず、また（Mw）／（MN）が5.0を越えると
成形品にブツ（フイツシユアイ）が発生しやすく
なる。メタクリル樹脂を製造する方法としては、
特に限定されず公知の懸濁重合法により、上記の
単量体を用いて重合途中で重合系内のメルカプタ
ン等の連鎖移動剤添加する方法、重合初期より連
鎖移動定数の異なる２種以上の連鎖移動剤を使用
する方法、分解温度の異なる２種以上の開始剤を
使用する方法、あるいは極限粘度〔η〕の異なる
２種以上のアクリル系樹脂をブレンドする方法等
があげられる。
本発明の組成物を構成する耐衝撃性樹脂とメタ
クリル樹脂との配合割合は、耐衝撃性樹脂中の架
橋アクリル酸エステル系重合体のゴム含有量によ
り一概に決められないが、一般的には、耐衝撃性
樹脂10〜80重量％、メタクリル樹脂20〜90重量％
の範囲である。また樹脂組成物中の架橋アクリル
酸エステル系重合体ゴム量は、１〜50重量％、好
ましくは、５〜35重量％である。樹脂組成物中、
架橋アクリル酸エステル系重合体ゴム含量が１重
量％未満では耐衝撃性が十分でなく、また50重量
％を越えると流動性が低下したり、曇価が増加し
たりする。
以上が本発明を構成している必須成分とその配
合比であるが、本発明の樹脂組成物を具体的に得
るには前記した耐衝撃性樹脂とメタクリル樹脂を
本発明の範囲内に秤量した後、ヘンシエルミキサ
ーあるいはＶ型ブレンダーで混合した後、押出機
を用い賦形して得ることもできるし、耐衝撃性樹
脂を秤量後、メタクリル酸メチルを主成分とする
単量体混合物に溶解後公知の懸濁重合を行ない、
重合途中にメルカプタンを追加し重合を完結させ
て得ることもできる。
本発明の組成物においては、必要に応じて染顔
料、紫外線吸収剤、酸化防止剤、離型剤等を添加
することもできる。
以下、実施例により本発明の内容を更に詳しく
説明する。なお本実施例における樹脂の物性詳価
は次のような方法を用いて行なつた。
(1) メタクリル樹脂の重量平均分子量（Mw）／
数平均分子量（MN）の測定
測定装置：島津製作所製（品番 島津 LC
−3A）カラムとしてGMH−６ ２本を使用
し、東洋ソーダ(株)製の標準ポリスチレンを用い
て検量線を作り、0.5重量％／容積％のメタク
リル樹脂について得られた溶出曲線を等分割
し、分割点における曲線の高さを測定して重量
平均分子量（Mw）および数平均分子量（MN）
を求めた。なお、溶剤としてテトラヒドロフラ
ンを使用した。
(2) 耐衝撃性
アイゾツト−ASTM Ｄ 256
ダインスタツト−DIN 53453
(3) 曇価−ASTM Ｄ 1003
(4) FR−ASTM Ｄ 1238
(5) 耐溶剤性（カンチレバー法）
長さ10cm、巾２cm、厚さ２mmの試片の一端を
支持し、他方へ2000psiを加え、支点上部ヘイ
ソプロピルアルコールを含浸させたガーゼを置
き、破断するまでの時間を測定する。
実施例 １
５セバラブルフラスコに3.000ｇの純水を入
れ、これに乳化剤としてザルコシネートLN（日
光ケミカル(株)製）30ｇ、助触媒系としてエチレン
ジアミンテトラアセテート２ナトリウム塩0.06ｇ
およびFeSO4・7H2Oを0.015ｇ、還元剤ロンガリ
ツト（三菱ガス化学工業(株)製）６ｇを溶解後、窒
素置換を行い、75℃に昇温した。一方窒素置換を
し、触媒としてｔ−ブチルハイドロパーオキサイ
ド３ｇを溶解したｎ−ブチルアクリレート800ｇ、
スチレン200ｇおよびアリルメタクリレート15ｇ
の単量体混合物を３時間かけて滴下重合させ、２
時間保持した。次いで窒素置換したｔ−ブチルハ
イドロパーオキサイド１ｇとｎ−オクチルメルカ
プタン１ｇを溶解したメタクリル酸メチル495ｇ
およびメチルアクリレート５ｇの単量体混合物を
１時間かけて滴下した後１時間保持してラテツク
スを得た。このラテツクス4.000ｇを凝固剤とし
てH2SO420ｇを使い80℃で凝固し、洗浄、脱水、
乾燥して粉状の重合体（耐衝撃性樹脂）を得た。
一方、メタクリル酸メチル980ｇおよび、アク
リル酸メチル20ｇの単量体混合物にアゾビスイソ
ブチロニトリル１ｇ、およびｎ−オクチルメルカ
プタン2.0ｇを溶解した後、分割剤（メタクリル
酸メチルとスルホアルキルメタクリル酸ソーダと
の共重合体）0.1ｇおよびNa2SO45ｇを溶解した
水1.500ｇに入れ、撹拌下80℃で重合し、昇温開
始後7.5分でｎ−オクチルメルカプタンを1.5ｇ入
れて重合させ、ピーク後95℃で１時間保持した。
得られたポリマーを洗浄、脱水、乾燥して
（Mw）／（MN）＝2.5および〔η〕（極限粘度）
／ｇ＝0.054のビーズ状ポリマー（メタクリル
樹脂）を得た。次にこのポリマー700ｇと前記の
耐衝撃性樹脂300ｇとをヘンシエルミキサーでブ
レンド後、255℃で賦形し、ペレツト化した。こ
のペレツトを用いて種々の物性を測定した。得ら
れた結果を表１に示す。
比較例 １
実施例１で得られた耐衝撃性樹脂300ｇとｎ−
オクチルメルカプタン2.5ｇをモノマーに最初溶
解させて重合させる他は実施例１と同様な方法で
製造した（Mw）／（MN）＝1.9および〔η〕（極
限粘度）／ｇ＝0.054のビーズポリマー（メタ
クリル樹脂）700ｇとをヘンシエルミキサーでブ
レンドし、255℃で賦形しペレツト化した。この
ベレツトについても実施例１と同様に物性を測定
した。得られた結果を表１に示す。
The present invention relates to methacrylic resin compositions. Methyl methacrylate-based methacrylic resin not only has excellent transparency and weather resistance, but also has well-balanced properties such as mechanical properties, thermal properties, and moldability. Taking advantage of these characteristics, it is used as a sheet material or molding material in a wide variety of fields, including signboards, lighting equipment parts, electrical equipment parts, automobile parts, and miscellaneous goods. However, there is a strong demand in the market for methacrylic resins with improved impact resistance. Against this background, two to three types of impact-resistant methacrylic resins are currently on the market. However, these resins have poor resin fluidity because the rubber content is increased from the viewpoint of improving impact resistance. On the other hand, due to the trend towards lighter weight and lower cost automobiles, the market is demanding thinner parts.
Therefore, it is strongly desired to improve the fluidity of the resin used. As a method for improving the fluidity of the resin, for example, there is a method of reducing the molecular weight of the matrix resin, but this method is not preferable because it also deteriorates the impact resistance. Against this background, the present inventors conducted intensive studies to develop a methacrylic resin that is impact resistant and has excellent fluidity, and as a result, they identified an impact resistant methacrylic resin containing a crosslinked acrylic ester polymer as a rubber component. The present inventors have discovered that the above-mentioned drawbacks can be overcome by specifically blending a methacrylic resin with a molecular weight distribution of . That is, the gist of the present invention is to combine an impact-resistant methacrylic resin containing a crosslinked acrylic acid ester polymer as a rubber component and containing methyl methacrylate units in an amount of 70% by weight or more to have a weight average molecular weight (M w ) and a number average The ratio of molecular weight (M N ) (M w /M N ) is 2.2 to 5.0
A composition comprising a methacrylic resin having a molecular weight distribution in the range of
A methacrylic resin composition containing 50% by weight of a crosslinked acrylic ester polymer. The impact-resistant methacrylic resin (hereinafter referred to as impact-resistant resin) whose rubber component is a crosslinked acrylic ester polymer that constitutes the composition of the present invention is a component that improves the impact resistance of the resin composition. It is a component that also improves solvent resistance. This impact-resistant resin is not particularly limited as long as it does not impede the object of the present invention, and impact-resistant methacrylic resins whose rubber components are crosslinked acrylic acid ester polymers having various layer structures can be used. For example, 70 to 90% by weight of at least one acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms, 9.9 to 29.9% by weight of styrene alone or a mixture of styrene and its derivatives, and copolymerizable with this in one molecule. A crosslinked acrylic acid ester polymer obtained using 0.1 to 10% by weight of a polyfunctional monomer having two or more double bonds, such as allyl (meth)acrylate, triallyl cyanurate, allyl cinnamate, etc. Latex or a hard crosslinked resin containing 80% by weight or more of methyl methacrylate units is contained inside the particles, and at least one acrylic acid alkyl ester having an alkyl group of 1 to 8 carbon atoms and styrene alone or styrene and its derivatives are used. 90 to 99.9% by weight of a mixture of and polyfunctional monomers copolymerizable with this and having two or more double bonds in one molecule, such as allyl (meth)acrylate, triallyl cyanurate, allyl cinnamate, etc. In the presence of a multilayer acrylic elastic latex whose outer layer is a crosslinked acrylic ester copolymer of a monomer mixture of 0.1 to 10% by weight, 80 to 100% by weight of methyl methacrylate and a carbon number of alkyl Emulsion polymerization of a monomer or a monomer mixture consisting of 0 to 20% by weight of at least one of the acrylic acid alkyl esters 1 to 8 and 0 to 10% by weight or less of other vinyl monomers copolymerizable therewith. It can be obtained by Furthermore, the composition of the present invention contains 70% by weight or more of methyl methacrylate units, and has a ratio of weight average molecular weight (M w ) to number average molecular weight (M N ) (M w /M N ).
Methacrylic resins (hereinafter referred to as methacrylic resins) with a molecular weight distribution in the range of 2.2 to 5.0 retain the properties of methacrylic resins such as transparency and weather resistance, and in particular have excellent impact resistance and fluidity. It is an ingredient that improves sex. However, when the molecular weight of the methacrylic resin is increased, the impact resistance increases, but the fluidity decreases. Furthermore, when the molecular weight is decreased, fluidity improves, but impact resistance decreases. As a result of intensive study by the present inventors, the ratio of weight average molecular weight (M w )/number average molecular weight (M N ) (M w /
M N ) was found to be in the range of 2.2 to 5.0. Furthermore, the methacrylic resin needs to contain 70% by weight or more of methyl methacrylate units. If the content of methyl methacrylate units in the methacrylic resin is less than 70% by weight, the properties as a methacrylic resin will deteriorate. Therefore, the content of methyl methacrylate units in the methacrylic resin is preferably 80 to 99.5% by weight. . Copolymerization components for obtaining methacrylic resin include unsaturated vinyl monomers, such as acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; styrene, α-methylstyrene. , acrylonitrile, etc. (M w )/(M N ) in methacrylic resin is
When it is less than 2.2, fluidity and impact resistance cannot be balanced, and when (M w )/(M N ) exceeds 5.0, spots (sticky eyes) are likely to occur in the molded product. The method for producing methacrylic resin is as follows:
A method in which a chain transfer agent such as a mercaptan is added to the polymerization system during polymerization using the above-mentioned monomers by a known suspension polymerization method without particular limitation, or two or more chains with different chain transfer constants from the early stage of polymerization. Examples include a method of using a transfer agent, a method of using two or more types of initiators having different decomposition temperatures, and a method of blending two or more types of acrylic resins having different intrinsic viscosities [η]. Although the blending ratio of the impact-resistant resin and methacrylic resin constituting the composition of the present invention cannot be determined unconditionally depending on the rubber content of the crosslinked acrylic ester polymer in the impact-resistant resin, it is generally , impact resistant resin 10-80% by weight, methacrylic resin 20-90% by weight
is within the range of The amount of crosslinked acrylic ester polymer rubber in the resin composition is 1 to 50% by weight, preferably 5 to 35% by weight. In the resin composition,
If the content of the crosslinked acrylic ester polymer rubber is less than 1% by weight, the impact resistance will not be sufficient, and if it exceeds 50% by weight, the fluidity will decrease or the haze value will increase. The above are the essential components constituting the present invention and their blending ratios. In order to specifically obtain the resin composition of the present invention, the above-mentioned impact resistant resin and methacrylic resin are weighed within the range of the present invention. After mixing with a Henschel mixer or a V-type blender, it can be shaped using an extruder, or after weighing the impact-resistant resin, it is dissolved in a monomer mixture containing methyl methacrylate as the main component. After that, a known suspension polymerization is carried out,
It can also be obtained by adding mercaptan during polymerization and completing the polymerization. In the composition of the present invention, dyes and pigments, ultraviolet absorbers, antioxidants, mold release agents, etc. can also be added as necessary. Hereinafter, the content of the present invention will be explained in more detail with reference to Examples. The detailed physical properties of the resin in this example were determined using the following method. (1) Weight average molecular weight of methacrylic resin (M w )/
Measurement of number average molecular weight (M N ) Measuring device: Shimadzu Corporation (product number Shimadzu LC)
-3A) Using two GMH-6 columns, a calibration curve was created using standard polystyrene manufactured by Toyo Soda Co., Ltd., and the elution curve obtained for 0.5% by weight/volume methacrylic resin was divided into equal parts. , measure the height of the curve at the split point to determine the weight average molecular weight (M w ) and number average molecular weight (M N )
I asked for Note that tetrahydrofuran was used as a solvent. (2) Impact resistance Izotsu - ASTM D 256 Dyn Stat - DIN 53453 (3) Haze value - ASTM D 1003 (4) FR - ASTM D 1238 (5) Solvent resistance (cantilever method) Length 10 cm, width 2 cm, thickness Support one end of a 2 mm thick specimen, apply 2000 psi to the other end, place gauze impregnated with heisopropyl alcohol above the fulcrum, and measure the time until it breaks. Example 1 3.000g of pure water was placed in a 5-separable flask, and 30g of Sarcosinate LN (manufactured by Nikko Chemical Co., Ltd.) was added as an emulsifier, and 0.06g of ethylenediaminetetraacetate disodium salt was added as a cocatalyst.
After dissolving 0.015 g of FeSO 4 .7H 2 O and 6 g of the reducing agent Rongalit (manufactured by Mitsubishi Gas Chemical Industries, Ltd.), the solution was purged with nitrogen and the temperature was raised to 75°C. On the other hand, the atmosphere was replaced with nitrogen, and 800 g of n-butyl acrylate in which 3 g of t-butyl hydroperoxide was dissolved as a catalyst,
200g styrene and 15g allyl methacrylate
A monomer mixture of 2
Holds time. Next, 495 g of methyl methacrylate in which 1 g of nitrogen-substituted t-butyl hydroperoxide and 1 g of n-octyl mercaptan were dissolved.
A monomer mixture containing 5 g of methyl acrylate was added dropwise over 1 hour, and the mixture was kept for 1 hour to obtain a latex. 4.000g of this latex was coagulated at 80℃ using 20g of H 2 SO 4 as a coagulant, washed, dehydrated,
After drying, a powdery polymer (impact resistant resin) was obtained. On the other hand, 1 g of azobisisobutyronitrile and 2.0 g of n-octyl mercaptan were dissolved in a monomer mixture of 980 g of methyl methacrylate and 20 g of methyl acrylate. 0.1 g of copolymer (copolymer with copolymer) and 5 g of Na 2 SO 4 were dissolved in 1.500 g of water, and polymerized at 80°C with stirring. 7.5 minutes after the start of heating, 1.5 g of n-octyl mercaptan was added and polymerized. After the peak, the temperature was kept at 95°C for 1 hour.
The obtained polymer was washed, dehydrated, and dried to obtain (M w )/(M N ) = 2.5 and [η] (intrinsic viscosity).
A bead-like polymer (methacrylic resin) having a weight of 0.054/g was obtained. Next, 700 g of this polymer and 300 g of the above-mentioned impact-resistant resin were blended in a Henschel mixer, shaped at 255° C., and pelletized. Various physical properties were measured using this pellet. The results obtained are shown in Table 1. Comparative Example 1 300g of impact resistant resin obtained in Example 1 and n-
Beads with (M w )/(M N )=1.9 and [η] (intrinsic viscosity)/g=0.054 were produced in the same manner as in Example 1, except that 2.5 g of octyl mercaptan was first dissolved in the monomer and polymerized. The mixture was blended with 700 g of polymer (methacrylic resin) using a Henschel mixer, and shaped into pellets at 255°C. The physical properties of this beret were also measured in the same manner as in Example 1. The results obtained are shown in Table 1.
【表】
実施例 ２
実施例１で得られた耐衝撃性樹脂300ｇと、ｎ
−オクチルメルカプタンの量を1.65ｇに変更する
以外は実施例１と同様な方法をくり返して得た
（Mw）／（MN）＝1.9で〔η〕（極限粘度）／ｇ
＝0.070のビーズ状のメタクリル樹脂〔〕400ｇ
およびｎ−オクチルメルカプタンの量を6.5ｇに
変更する以外は実施例１と同様な方法をくり返し
て得た（Mw）／（WN）＝1.9で〔η〕（極限粘度）
／ｇ＝0.030のビーズ状メタクリル樹脂〔２〕
300ｇとをブレンドした樹脂〔（Mw）／（MN）＝
2.7、〔η〕（極限粘度）／ｇ＝0.054〕とをブレ
ンド賦形してペレツト化した。このペレツトにつ
いて実施例１と同様物性を測定した。得られた結
果を表２に示す。
比較例 ２〜３
実施例１で得られた耐衝撃性樹脂300ｇと実施
例２のメタクリル樹脂〔１〕700ｇとをブレンド
賦形した樹脂（比較例２）及び実施例１の耐衝撃
性樹脂と実施例２のメタクリル樹脂〔２〕700ｇ
とをブレンド賦形した樹脂についても実施例２と
同様物性を評価した。得られた結果を表２に示
す。[Table] Example 2 300g of impact-resistant resin obtained in Example 1 and n
- Obtained by repeating the same method as in Example 1 except that the amount of octyl mercaptan was changed to 1.65 g (M w )/(M N ) = 1.9 [η] (limiting viscosity)/g
=0.070 bead-shaped methacrylic resin []400g
and [η] (intrinsic viscosity) obtained by repeating the same method as in Example 1 except that the amount of n-octyl mercaptan was changed to 6.5 g (M w )/(W N ) = 1.9.
/g=0.030 bead-shaped methacrylic resin [2]
300g of resin [(M w )/(M N )=
2.7 and [η] (intrinsic viscosity)/g=0.054] were blended and formed into pellets. The physical properties of this pellet were measured in the same manner as in Example 1. The results obtained are shown in Table 2. Comparative Examples 2-3 Resin obtained by blending 300 g of the impact-resistant resin obtained in Example 1 and 700 g of methacrylic resin [1] of Example 2 (Comparative Example 2) and the impact-resistant resin of Example 1 Methacrylic resin of Example 2 [2] 700g
The physical properties of the blend-shaped resin were also evaluated in the same manner as in Example 2. The results obtained are shown in Table 2.
Claims (1)
とした耐衝撃性メタクリル樹脂とメタクリル酸メ
チル単位を70重量％以上含有し重量平均分子量
（Mw）と数平均分子量（MN）の比（Mw／MN）
が2.2〜5.0の範囲の分子量分布を有するメタクリ
ル系樹脂とから成る組成物であつて、かつ該組成
物中に１〜50重量％の架橋アクリル酸エステル系
重合体を含有せしめてなるメタクリル樹脂組成
物。1 Impact-resistant methacrylic resin containing a crosslinked acrylic acid ester polymer as a rubber component and containing methyl methacrylate units in an amount of 70% by weight or more, and having a ratio of weight average molecular weight (M w ) to number average molecular weight (M N ) (M w /M N )
and a methacrylic resin having a molecular weight distribution in the range of 2.2 to 5.0, and the composition contains 1 to 50% by weight of a crosslinked acrylic ester polymer. thing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21187082A JPS59102947A (en) | 1982-12-02 | 1982-12-02 | Methacrylic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21187082A JPS59102947A (en) | 1982-12-02 | 1982-12-02 | Methacrylic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59102947A JPS59102947A (en) | 1984-06-14 |
| JPH0129218B2 true JPH0129218B2 (en) | 1989-06-08 |
Family
ID=16612975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21187082A Granted JPS59102947A (en) | 1982-12-02 | 1982-12-02 | Methacrylic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59102947A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000204220A (en) * | 1999-01-13 | 2000-07-25 | Kanegafuchi Chem Ind Co Ltd | Modifier for methacrylic resin |
| DE19927769A1 (en) * | 1999-06-17 | 2000-12-21 | Roehm Gmbh | Polymethacrylate molding composition, useful for the production of molded articles, is prepared by mixing toughened polymethacrylate and low mol. wt. polymethacrylate |
| US9605121B2 (en) * | 2013-05-16 | 2017-03-28 | Kuraray Co., Ltd. | Film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54112987A (en) * | 1978-02-22 | 1979-09-04 | Asahi Chem Ind Co Ltd | Solvent-resistant acrylic resin |
| JPS5527576A (en) * | 1978-06-23 | 1980-02-27 | Griswold Controls | Counter flow preventing device |
-
1982
- 1982-12-02 JP JP21187082A patent/JPS59102947A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54112987A (en) * | 1978-02-22 | 1979-09-04 | Asahi Chem Ind Co Ltd | Solvent-resistant acrylic resin |
| JPS5527576A (en) * | 1978-06-23 | 1980-02-27 | Griswold Controls | Counter flow preventing device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59102947A (en) | 1984-06-14 |
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