JPS6245886B2 - - Google Patents
Info
- Publication number
- JPS6245886B2 JPS6245886B2 JP7166880A JP7166880A JPS6245886B2 JP S6245886 B2 JPS6245886 B2 JP S6245886B2 JP 7166880 A JP7166880 A JP 7166880A JP 7166880 A JP7166880 A JP 7166880A JP S6245886 B2 JPS6245886 B2 JP S6245886B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- polymerization
- crosslinkable monomer
- acrylic
- 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
- 239000000178 monomer Substances 0.000 claims description 90
- 239000000203 mixture Substances 0.000 claims description 76
- 238000006116 polymerization reaction Methods 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 36
- 239000000113 methacrylic resin Substances 0.000 claims description 33
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229920000800 acrylic rubber Polymers 0.000 claims description 8
- 229920000058 polyacrylate Polymers 0.000 claims description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 7
- 230000009257 reactivity Effects 0.000 claims description 7
- 239000004816 latex Substances 0.000 description 19
- 229920000126 latex Polymers 0.000 description 19
- 229920001971 elastomer Polymers 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 13
- 238000004132 cross linking Methods 0.000 description 12
- 230000007423 decrease Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000011342 resin composition Substances 0.000 description 9
- -1 acrylic ester Chemical class 0.000 description 8
- 239000013013 elastic material Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 6
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 6
- 125000005396 acrylic acid ester group Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 5
- 238000010559 graft polymerization reaction Methods 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 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 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 229940071089 sarcosinate Drugs 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- NNNLYDWXTKOQQX-UHFFFAOYSA-N 1,1-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OC(CC)(OC(=O)C=C)OC(=O)C=C NNNLYDWXTKOQQX-UHFFFAOYSA-N 0.000 description 1
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- 229920005509 ACRYPET® VH Polymers 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- VERSKQYXUOVYBF-UHFFFAOYSA-M [Na+].O=C.[O-]O.OSO Chemical compound [Na+].O=C.[O-]O.OSO VERSKQYXUOVYBF-UHFFFAOYSA-M 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
Description
本発明は耐衝撃性を付与したメタクリル樹脂組
成物の製造方法に関する。
メタクリル樹脂はプラスチツク材料の中でも透
明性及び光学的性質に卓越した特性を有し、また
表面光沢、耐候性、染顔料着色性、成形加工性等
においても極めて優れており、これらの特性を生
かして、照明、看板、窓材、光学レンズ、テール
レンズ、メーターカバー、ダストカバー、デイス
プレイ、テーブルウエアーなど、光学用途、建
材、電気機器部品、車輌部品、装飾分野、雑貨な
ど多方面の分野で使用されている。
しかしメタクリル樹脂は、耐衝撃性が不足して
いるという問題があり、個々の用途分野において
その改良が強く要望されている。
メタクリル樹脂の耐衝撃性を改良する方法とし
ては、古くから種々の提案がなされている。最も
一般的で且つ効果的な方法として、メタクリル酸
メチルを主成分とする連続樹脂相中に、常温でゴ
ム状を示す弾性体、例えばブタジエンを主成分と
した不飽和ゴム状重合体、ブチルアクリレート、
２―エチルヘキシルアクリレートなどを主成分と
したアクリル酸エステル系重合体、あるいはエチ
レン／酢酸ビニル共重合体などの飽和ゴム状弾性
体を粒子状で不連続的に分散せしめる方法がとら
れている。
不飽和ゴム状弾性体の導入は耐衝撃性の発現性
の面では優れているが、ポリマー主鎖の不飽和結
合に起因する耐候性不良の問題があり、一方不飽
和ゴム状弾性体の導入は、耐候性の面では優れて
いるものの、ゴム成分自体の弾性率と弾性回復性
が低く、さらに硬質樹脂成分とのグラフト重合性
に乏しいため、耐衝撃性の発現性、透明性、表面
光沢等が劣り、また流動模様を生ずるなど表面外
観にも問題がある。
一般にこれらゴム状弾性体が粒子状の不連続相
としてメタクリル樹脂などの硬質樹脂の連続相中
に均一に分散した２成分系よりなる耐衝撃性樹脂
組成物を合成する場合、重要な因子としてゴム状
弾性体の粒子径、架橋度、ゴム相への硬質樹脂相
のグラフト重合性および硬質樹脂相の分子量など
の挙げられており、事実、樹脂の最終組成物の樹
脂特性の優劣とバランスはこれらの因子によつて
大きな影響を受ける。
すなわち、ゴム状弾性体の粒子径は小さい程透
明性の面ではメリツトがあるものの、耐衝撃性の
発現効果に劣り、架橋度については、架橋密度が
高い程表面光沢、流動模様など表面外観の面では
優れているが耐衝撃性に劣る欠点を生ずる。
また硬質樹脂相のゴム状弾性体へのグラフト重
合性の程度はゴム状弾性体の連続樹脂相への相溶
性、分散性を大きく支配し、耐衝撃性、透明性、
耐ストレス白化性、表面光沢、流動加工性など多
くの特性に影響を及ぼし、飽和ゴム状弾性体を使
用する場合、一般にグラフト重合性は低く、特別
な考慮を払う必要がある。しかしグラフトの程度
は樹脂の最終物性のなかで特に透明性、表面光
沢、流動加工性に多大の影響を及ぼすため、グラ
フト重合反応をコントロールする必要がある。さ
らに硬質樹脂相の分子量は大きい方が耐衝撃性の
面では効果的であるが、表面外観と成形加工性の
面では逆に劣る。
以上の如く、個々の因子の挙動は個別的で、一
長一短を有しており、耐衝撃性メタクリル樹脂の
樹脂特性全般のバランスを効率よく品質設計する
ことは極めて困難であり、ストレートのメタクリ
ル樹脂に匹敵する透明性、表面光沢ならびに成形
加工性を具備した耐衝撃性メタクリル樹脂成形材
料は未だ出現していないのが実状である。
近年耐候性に優れたアクリル酸エステル系弾性
体をゴム相とした耐衝撃性樹脂組成物あるいは耐
衝撃性メタクリル樹脂組成物において、ゴム相の
耐衝撃性の発現効果、成形品の透明性、耐ストレ
ス白化性あるいは成形過程でのゴム粒子の変形に
起因する真珠様光沢、耐候性を改良する目的でゴ
ム粒子内部に硬質樹脂を含有せしめる方法が提案
されており（特公昭52−30996号および特開昭48
−55233号）、これらの方法は確かにその効果は認
められるものの、メタクリル樹脂材料として見た
場合、透明性、表面光沢の面ではまだかなり劣る
上に、これらの特性が成形条件によつて変動する
という成形加工上の問題がある。
またアクリル酸エステル系弾性体への硬質樹脂
相のグラフト重合性を改良する目的でゴム弾性体
相にアリルメタクリレートのような反応性の異な
る２重結合を２個有する単量体（グラフト交叉性
モノマーと呼ばれている）を共重合により導入す
る処方が提案されている（特公昭48−18593号お
よび特開昭48−55233号）。これらの方法はグラフ
ト重合性は確かに改良される方向にあるが、この
種の２官能性単量体は架橋性単量体としての作用
とグラフト重合性の向上作用の２つの作用効果を
有しており、ゴム相の重合条件によつては、２つ
の作用効果の割合が異なつたり、さらには前記し
た如く適正値がそれぞれ存在するため、ゴム弾性
体の架橋度およびグラフト重合性を同時に最適正
値とすべくコントロールすることは極めて困難で
あり、この処方を用いても品質性能に極めて優れ
た耐衝撃性メタクリル樹脂材料を得ることは不可
能である。
本発明者等は以上の現状に鑑み、透明性、表面
光沢、耐候性などメタクリル樹脂本来の優れた特
性を損ずることなくこれに耐衝撃性を付与したメ
タクリル樹脂材料の製造方法について鋭意検討し
た結果、メタクリル酸メチルを主成分とした硬質
架橋樹脂を粒子内部に含有し、特定の組成を有す
る架橋アクリル酸エステル系重合体が外層部を構
成する２重構造のアクリル酸エステル系弾性体
と、これにメタクリル酸メチルを主成分とした硬
質樹脂をグラフト重合する際、これを２分割し、
初期に重合する部分を架橋せしめつつグラフト重
合し、残りの部分を非架橋硬質樹脂として重合す
るという特珠な処方を組み合せ、且つ架橋グラフ
ト重合部と非架橋グラフト重合部の割合が一定範
囲の場合のみ当初の目的が達成されることを見い
出し、本発明に到達した。
すなわち、本発明の要旨とするところは、メタ
クリル酸メチル単位を80重量％以上を含む硬質架
橋樹脂(A)５〜50重量部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
ステルの少くとも１種69.9〜89.9重量％とスチレ
ン単独又はスチレンとその誘導体の混合物30〜10
重量％ならびにこれと共重合可能で１分子中に炭
素―炭素２重結合を２個以上有する多官能単量体
0.1〜10重量％よりなる架橋アクリル酸エステル
系共重合体(B)95〜50重量部が外層を構成する２重
構造アクリル系弾性体〔〕100重量部の存在下
に、メタクリル酸メチル80〜99.9重量％、アルキ
ル基の炭素数１〜８のアクリル酸アルキルエステ
ルの少くとも１種０〜19.9重量％、これと共重合
可能な他のビニル系単量体０〜10重量％およびこ
れと共重合可能で１分子中に重合反応性の近い、
炭素―炭素２重結合を少くとも２個以上有する多
官能架橋性単量体0.1〜10重量％よりなる架橋性
単量体混合物(C)５〜100重量部を重合し、次いで
メタクリル酸メチル80100重量％、アルキル基の
炭素数１〜８のアクリル酸アルキルエステルの少
くとも１種０〜20重量％ならびにこれと共重合可
能な他のビニル系単量体０〜10重量％よりなる非
架橋性単量体または単量体混合物(D)５〜1000重量
部を前記架橋性単量体混合物(C)に対して重量比
〔(D)／(C)〕で0.5〜200となる量、更に添加して重
合することからなる耐衝撃性に優れたメタクリル
樹脂組成物の製造方法にある。
本発明の特徴は上記したような重合処方で示さ
れる如く、特性の異なる少くとも４段階の重合を
行ない、得られる重合体を多重構造化した所にあ
る。
このような方法によつて製造されたメタクリル
樹脂組成物は耐衝撃性の発現性に優れ、且つ透明
性、表面光沢あるいは成形加工性に極めて優れた
特性を有する。
本発明の樹脂組成物の製造方法としては、特に
限定されないが、乳化重合法で実施することが好
ましい。
本発明の樹脂組成物の製造を実施するに際して
は、得られる樹脂組成物に良好な透明性を付与す
るために、各重合段階において得られる樹脂相の
屈折率をできるだけ同一とするか、または極めて
近似させることが必要である。
また、本発明の樹脂組成物の製造に際しては、
得られる樹脂組成物の、透明性および表面外観と
耐衝撃性の発現性能のバランスのため、分散させ
るゴム粒子径も考慮する必要がある。本発明の組
成物においては、透明性耐衝撃性何れにも優れた
組成物を得るため、架橋アクリル酸エステル系共
重合体(B)の重合が実質上完了し、２重構造アクリ
ル系弾性体〔〕が得られた時点で0.13〜0.45μ
ｍ、より好ましくは0.2〜0.35μｍの粒子径範囲
とすることが好ましい。
本発明において用いられる２重構造アクリル系
弾性体〔〕は、メタクリル酸メチル単位を80重
量％以上を含有する硬質架橋樹脂(A)を粒子内部に
もち、その外層に架橋アクリル酸エステル系共重
合体(B)を有するものである。
本発明でいう硬質架橋樹脂(A)はメタクリル酸メ
チル単独またはメタクリル酸メチル80重量％以上
と他の共重合性ビニル単量体20重量％以下の単量
体または混合物100重量部に、0.1〜10重量部、よ
り好ましくは0.5〜５重量部の架橋性単量体を加
えて重合した共重合体であり、２重構造アクリル
系弾性体100重量部の内５〜50重量部、より好ま
しくは10〜40重量部含有せしめることが必要であ
る。その量が５重量部未満では耐衝撃性の発現性
向上効果が少なく、透明性も低下する。逆に50重
量％をこえる場合には表面光沢が低下すると共に
耐衝撃性も低下する傾向がある。
硬質架橋樹脂(A)の重合に用いられる共重合性ビ
ニル単量体としては特に限定されないが、好まし
いものとしては、アルキル基の炭素数１〜４のア
クリル酸アルキルエステル、スチレン等があげら
れる。
また硬質架橋樹脂(A)の重合に用いる架橋性単量
体は、メタクリル酸メチルと共重合するものであ
れば特に限定する必要はなく、通常用いられる、
エチレングリコールジメタクリレート、エチレン
グリコールジアクリレート、1.3―ブチレンジメ
タクリレート、テトラエチレングリコールジアク
リレート等の２官能性単量体、またはトリメチロ
ールプロパントリアクリレート、トリアリルシア
ヌレート、トリアリルイソシアヌレート等の３官
能性単量体、またはペンタエリスリトールテトラ
アクリレート等の４官能性単量体をそれぞれ単独
でまたは組み合せて用いることができる。
架橋アクリル酸エステル系共重合体(B)はアルキ
ル基の炭素数が１〜８のアクリル酸アルキルエス
テル群の中で、好ましくはｎ―ブチルアクリレー
ト、２―エチルヘキシルアクリレートの少くとも
１種69.9〜89.9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30〜10重量％ならびに
これと共重合可能で１分子中に炭素―炭素２重結
合を２個以上有する多官能性単量体0.1〜10重量
％よりなる単量体混合物の共重合体であつて、硬
質架橋樹脂(A)の存在下に、その外層に重合せしめ
る。アクリル酸エステル系単量体とスチレンまた
はその誘導体との組成割合は透明性を付与するた
めに重要な因子の一つであり、上記組成範囲以外
では透明性が低下する。
多官能性単量体の添加は、耐衝撃性ならびに表
面外観の面から必要であり、多官能性単量体の種
類によつて最適添加量が異なるが一般に上記の
0.1〜10重量％の範囲がよい。
架橋アクリル酸エステル系共重合体(B)の重合に
用いる多官能性単量体は特に限定する必要はない
が、架橋度をコントロールする意味から少くとも
２つの２重結合の反応性が比較的近いものが好ま
しく、具体的な化合物としてはエチレングリコー
ルジメタクリレート、エチレングリコールジアク
リレート、1.3―ブチレンジメタクリレート、テ
トラエチレングリコールジアクリレート、ジビニ
ルベンゼンなどの２官能性単量体、またはトリメ
チロールプロパントリアクリレート、トリアリル
シアヌレート、トリアリルイソシアヌレート等の
３官能性単量体、またはペンタエリスリトールテ
トラアクリレートなどの４官能性単量体はそれぞ
れ単独で、または組合せて用いることができる。
アリルメタクリレートなどのような反応性の異
なる２重結合を有する単量体を単独で使用するこ
とは好ましくなく、この種の単量体を用いる必要
がある場合には、上記の如き反応性の等しい２重
結合を２個以上有する架橋性単量体と併用する必
要がある。
次いで２重構造アクリル系弾性体〔〕の存在
下で架橋性単量体混合物(C)を重合せしめる。架橋
性単量体混合物(C)の成分組成は、メタクリル酸メ
チル80〜99.9重量％、アルキル基の炭素数１〜８
のアクリル酸アルキルエステルの少くとも１種０
〜19.9重量％、これと共重合可能な他のビニル系
単量体０〜10重量％および１分子中に重合反応性
の近い炭素―炭素２重結合を２個以上有する共重
合性の多官能架橋性単量体0.1〜10重量％よりな
る。
前記単量体混合物(C)中のメタクリル酸メチルの
含有量が80重量％末満の場合には、透明性、耐熱
性および耐候性などの特性に劣り、またこれと共
重合するアクリル酸アルキルエステルとしては、
メチルアクリレート、エチルアクリレート、ブチ
ルアクリレートなどがあげられ、また更に共重合
成分として使用することが可能な他のビニル単量
体としては、スチレン、アクリロニトリル、メタ
クリル酸などがあげられる。
架橋性単量体混合物(C)中、アクリル酸エステル
が19.9重量％をこえる場合には最終組成物の耐熱
性や透明性の点で好ましくなく、また共重合可能
な他のビニル単量体が10重量％をこえると透明
性、耐候性あるいは耐水性などの性質が低下する
傾向が認められる。
多官能架橋性単量体としては分子中に反応性の
近い炭素―炭素２重結合を２個以上有する化合物
を用いる必要があり、これ以外の化合物例えばア
リルメタクリレートのように２個の２重結合の反
応性が異なる場合は、多官能架橋性単量体の添加
効果が得られず、表面光沢が低下したり、表面光
沢の成形条件依存性を生じたり、更には流動性が
低下することが認められる。
架橋性単量体混合物(C)は２重構造アクリル系弾
性体〔〕100重量部に対して５〜100重量部、好
ましくは５〜50重量部である。５重量部未満の場
合には、表面光沢ならびに流動性の改良効果が得
られず、また100重量部をこえると表面光沢と流
動性が逆に低下する傾向があり、耐衝撃性も低下
する。
架橋性単量体混合物(C)の必須成分である多官能
架橋性単量体の具体例としてはエチレングリコー
ルジメタクリレート、エチレングリコールジアク
リレート、1.3―ブチレンジメタクリレート、テ
トラエチレングリコールジアクリレート、トリメ
チロールプロパントリアクリレート、トリアリル
シアヌレート、トリアリルイソシアヌレート、ペ
ンタエリスリトールテトラアクリレート等の多官
能単量体をそれぞれ単独でまたは組み合せて用い
ることができる。
多官能架橋性単量体の使用量が0.1重量％未満
の場合には耐ストレス白化性や表面光沢の点で好
ましくなく、またその使用量が10重量％をこえる
場合には耐衝撃性の発現の点で好ましくない。
本発明の方法においては、架橋性単量体混合物
(C)の重合が実質上終了した時点で、メタクリル酸
メチル80〜100重量％、アルキル基の炭素数１〜
８のアクリル酸アルキルエステルの少くとも１種
０〜20重量％ならびにこれと共重合可能な他のビ
ニル系単量体０〜10重量％よりなる非架橋性単量
体またはその混合物(D)を２重構造アクリル系弾性
体〔〕100重量部に対して５〜1000重量部、よ
り好ましくは10〜700重量部を重合せしめるが、
架橋性単量体混合物(C)に対して重量比〔(D)／(C)〕
が0.5〜200の範囲に入るように選択する必要があ
り、２重構造アクリル系弾性体〔〕100重量部
に対して５重量部未満の場合には、耐衝撃性が低
下し、一方1000重量部をこえる場合には生産性が
低下し好ましくない。
また非架橋性単量体またはその混合物(D)の前段
の架橋性単量体混合物(C)に対する重量比〔(D)／
(C)〕が0.5未満の場合には表面光沢、透明性、流
動性あるいは耐衝撃性などの性質が低下し、また
一方200をこえる場合には生産性に劣る。非架橋
性単量体または混合物(D)中のメタクリル酸メチル
の含有量が80重量％未満になると透明性、耐熱性
あるいは機械的性質などの特性が低下し、メタク
リル樹脂本来の性質が損失する。
メタクリル酸メチルと共重合する炭素数１〜８
のアクリル酸アルキルエステルとしては０〜20重
量％のメチルアクリレート、エチルアクリレー
ト、ブチルアクリレートなどのアクリレートより
選ばれたものが使用され、その量が20重量％をこ
える場合には耐熱性と透明性の点で好ましくな
い。また共重合可能な他のビニル単量体としては
０〜10重量％のスチレン、アクリロニトリル、メ
タクリル酸などが用いられる。その量が10重量％
をこえると透明性、耐候性あるいは耐水性などの
性質が損じるので好ましくない。
本発明の方法においては非架橋性単量体または
単量体混合物(D)中に、分子量を調節するためメル
カプタン等の重合度調節剤等を必要に応じて用い
ることも可能である。用い得る重合度調節剤とし
ては、アルキルメルカプタン、チオグリコール酸
およびそのエステル、β―メルカプトプロピオン
酸およびそのエステル、チオフエノール、チオク
レゾール等の芳香族メルカプタンなどである。
以上述べたような一連の重合プロセスにより得
られた多重構造メタクリル樹脂組成物〔〕はそ
のままでも使用できるが、必要に応じて他の熱可
塑性樹脂、好ましくはメタクリル酸メチル80〜
100重量％と20〜０重量％の他のビニル単量体、
例えば炭素数１〜４のアルキル基をもつアクリル
酸エステルとの重合体であるメタクリル酸メチル
系樹脂と混合して２重構造アクリル系弾性体
〔〕を１〜70重量％含有させて使用することも
できる。
本発明で用いる多重構造メタクリル樹脂組成物
の製造は、乳化重合法によるのが特に好ましいこ
とより、乳化重合法による場合の例について説明
する。
反応容器に脱イオン水、必要があれば乳化剤を
加えた後、硬質架橋樹脂(A)を構成する単量体混合
物を重合し、次いで架橋アクリル酸エステル系重
合体(B)を構成する単量体混合物を重合し、次いで
架橋性単量体混合物(C)を重合せしめ、さらに非架
橋性単量体又は単量体混合物(D)を重合せしめる。
重合温度は30〜120℃、より好ましくは50〜100
℃である。
重合時間は、重合開始剤および乳化剤の種類と
量、重量温度等によつて異なるが、通常は各重合
段階(A)，(B)，(C)および(D)でそれぞれ0.5〜７時間
である。
単量体と水の比は単量体／水＝1/20〜1/1が好
ましい。
重合開始剤および乳化剤は、水相単量体相のい
ずれか片方または双方に添加することができる。
重合段階(A)，(B)，(C)および(D)における各々の単
量体の仕込方法は、一括または分割で行なうこと
ができるが重合発熱等の点で分割仕込法がより好
ましい。
乳化剤は通常用いられる乳化剤であれば特に限
定する必要はなく、用いられる乳化剤の例として
は、長鎖アルキルカルボン酸塩、スルホコハク酸
アルキルエステル塩、アルキルベンゼンスルホン
酸塩等である。
重合開始剤の種類も特に限定する必要はなく通
常用いられる、水溶性の過硫酸塩、過硼酸塩等の
無機開始剤を単独で、または亜硫酸塩、チオ硫酸
塩等と組み合せてレドツクス開始剤として用いる
こともできる。また有機ヒドロパーオキシド―第
１鉄塩、有機ヒドロパーオキシド―ソジウムホル
ムアルデヒドスルホキシレートのようなレドツク
ス開始系、ベンゾイルパーオキシド、アゾビスイ
ソブチロニトリル等の開始系も用いることができ
る。
乳化重合法により得られたポリマーラテツクス
は公知の方法により凝固乾燥させる。
得られた多重構造メタクリル樹脂組成物をメタ
クリル酸メチル系樹脂に配合分散せしめる場合に
は、溶融混合する方法が最も理想的である。溶融
混合に先立つて樹脂組成物以外に必要があれば安
定剤、滑剤、可塑剤、染料、顔料、充てん剤等を
適宜加え、Ｖ型ブレンダー、ヘンシエルミキサ
ー、ミキシングロール、スクリユー型を押出機を
用いて150〜300℃で溶融混練する。
かくして得られた組成物を、押出成形機、射出
成形機により成形することにより、透明性、表面
光沢に優れ、耐衝撃性に富んだ成形品を得ること
ができる。
以下実施例に基き、本発明をさらに詳しく説明
する。実施例中の部は重量部を、％は重量％を表
わす。
実施例 １
(1) 硬質架橋樹脂(A)の製造
内容積50のステンレススチール製反応容器に
先ず下記の原料(イ)を入れ、撹拌下に窒素を吹き込
み実質的に酸素の影響のない状態とした後、70℃
に昇温して下記の原料(ロ)を添加し、２時間重合を
行ない硬質架橋樹脂体のラテツクスを得た。
The present invention relates to a method for producing a methacrylic resin composition imparted with impact resistance. Methacrylic resin has excellent transparency and optical properties among plastic materials, and is also extremely superior in surface gloss, weather resistance, dye and pigment colorability, and moldability. It is used in a wide variety of fields, including lighting, signboards, window materials, optical lenses, tail lenses, meter covers, dust covers, displays, tableware, optical applications, building materials, electrical equipment parts, vehicle parts, decorative fields, and miscellaneous goods. ing. However, methacrylic resins have a problem of insufficient impact resistance, and there is a strong demand for improvement in each field of use. Various proposals have been made for a long time as methods for improving the impact resistance of methacrylic resins. The most common and effective method is to add an elastomer that is rubbery at room temperature, such as an unsaturated rubbery polymer mainly composed of butadiene, butyl acrylate, to a continuous resin phase mainly composed of methyl methacrylate. ,
A method of discontinuously dispersing an acrylic acid ester polymer mainly composed of 2-ethylhexyl acrylate or the like, or a saturated rubbery elastic material such as an ethylene/vinyl acetate copolymer in the form of particles has been adopted. Although the introduction of an unsaturated rubber-like elastic material is excellent in terms of impact resistance, there is a problem of poor weather resistance due to unsaturated bonds in the polymer main chain. Although it has excellent weather resistance, the elastic modulus and elastic recovery of the rubber component itself are low, and it also has poor graft polymerization with hard resin components, so it has poor impact resistance, transparency, and surface gloss. There are also problems with the surface appearance, such as a flow pattern. In general, when synthesizing a two-component impact-resistant resin composition in which these rubber-like elastic bodies are uniformly dispersed as particulate discontinuous phases in a continuous phase of hard resin such as methacrylic resin, rubber is an important factor. These include the particle size of the elastic material, the degree of crosslinking, the graft polymerizability of the hard resin phase to the rubber phase, and the molecular weight of the hard resin phase.In fact, these factors determine the quality and balance of the resin properties of the final resin composition. It is greatly influenced by the following factors. In other words, the smaller the particle size of the rubber-like elastic material, the more advantageous it is in terms of transparency, but the less effective it is in developing impact resistance.As for the degree of crosslinking, the higher the crosslinking density, the lower the surface appearance such as surface gloss and flow pattern. Although it has excellent properties, it has the disadvantage of poor impact resistance. In addition, the degree of graft polymerization of the hard resin phase onto the rubber-like elastic body largely controls the compatibility and dispersibility of the rubber-like elastic body into the continuous resin phase, resulting in impact resistance, transparency,
It affects many properties such as stress whitening resistance, surface gloss, and flow processability, and when using saturated rubber-like elastomers, graft polymerizability is generally low and special consideration must be taken. However, since the degree of grafting has a great effect on the final physical properties of the resin, particularly transparency, surface gloss, and flow processability, it is necessary to control the graft polymerization reaction. Furthermore, a larger molecular weight of the hard resin phase is more effective in terms of impact resistance, but is conversely inferior in terms of surface appearance and moldability. As mentioned above, the behavior of each factor is individual and has advantages and disadvantages, and it is extremely difficult to efficiently design the balance of the overall resin properties of impact-resistant methacrylic resin. The reality is that no impact-resistant methacrylic resin molding material with comparable transparency, surface gloss, and moldability has yet appeared. In recent years, impact-resistant resin compositions or impact-resistant methacrylic resin compositions in which the rubber phase is an acrylic acid ester elastomer with excellent weather resistance have been studied. A method of incorporating a hard resin into rubber particles has been proposed for the purpose of improving stress whitening properties, pearl-like luster caused by deformation of rubber particles during the molding process, and weather resistance (Japanese Patent Publication No. 52-30996 and 1977
Although these methods are certainly effective, when viewed as a methacrylic resin material, it is still quite inferior in terms of transparency and surface gloss, and these properties vary depending on the molding conditions. There is a problem with the molding process. In addition, in order to improve the graft polymerization of the hard resin phase to the acrylic ester elastomer, monomers (graft cross-reactive monomers) having two double bonds with different reactivities such as allyl methacrylate are added to the rubber elastomer phase. A formulation has been proposed in which a copolymer is introduced by copolymerization. Although these methods are certainly in the direction of improving graft polymerizability, this type of bifunctional monomer has two effects: acting as a crosslinking monomer and improving graft polymerizability. Depending on the polymerization conditions of the rubber phase, the ratio of the two effects may differ, and furthermore, as mentioned above, there are appropriate values for each, so the degree of crosslinking and graft polymerization of the rubber elastic body can be simultaneously controlled. It is extremely difficult to control to achieve the optimum positive value, and even if this formulation is used, it is impossible to obtain an impact-resistant methacrylic resin material with extremely excellent quality performance. In view of the above-mentioned current situation, the inventors of the present invention have conducted intensive studies on a method for producing methacrylic resin materials that impart impact resistance to methacrylic resin without impairing its original excellent properties such as transparency, surface gloss, and weather resistance. , a double-structured acrylic ester-based elastic body containing a hard cross-linked resin mainly composed of methyl methacrylate inside the particles, and a cross-linked acrylic ester-based polymer having a specific composition forming the outer layer; When graft polymerizing a hard resin mainly composed of methyl methacrylate, it is divided into two parts,
When a special recipe is combined in which the initially polymerized part is crosslinked and graft polymerized, and the remaining part is polymerized as a non-crosslinked hard resin, and the ratio of the crosslinked graft polymerized part and the non-crosslinked graft polymerized part is within a certain range. The inventors have found that only the original purpose can be achieved, and have arrived at the present invention. That is, the gist of the present invention is that 5 to 50 parts by weight of a hard crosslinked resin (A) containing 80% by weight or more of methyl methacrylate units is contained inside the particles, and the alkyl group has 1 to 8 carbon atoms. 69.9-89.9% by weight of at least one acrylic acid alkyl ester and 30-10% of styrene alone or a mixture of styrene and its derivatives
Weight% and polyfunctional monomers copolymerizable with this and having two or more carbon-carbon double bonds in one molecule
In the presence of 100 parts by weight of a double structure acrylic elastomer whose outer layer is composed of 95 to 50 parts by weight of a crosslinked acrylic ester copolymer (B) consisting of 0.1 to 10% by weight, 80 to 80 parts by weight of methyl methacrylate is added. 99.9% by weight, 0 to 19.9% by weight of at least one type of acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms, 0 to 10% by weight of other vinyl monomers copolymerizable with this, and copolymerizable with this. Polymerizable and has close polymerization reactivity in one molecule.
5 to 100 parts by weight of a crosslinkable monomer mixture (C) consisting of 0.1 to 10% by weight of a polyfunctional crosslinkable monomer having at least two or more carbon-carbon double bonds is polymerized, and then methyl methacrylate 80100 Non-crosslinkable material consisting of 0-20% by weight of at least one type of acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms and 0-10% by weight of another vinyl monomer copolymerizable therewith. 5 to 1000 parts by weight of the monomer or monomer mixture (D) to the crosslinkable monomer mixture (C) in an amount such that the weight ratio [(D)/(C)] is 0.5 to 200, and A method for producing a methacrylic resin composition with excellent impact resistance, which comprises adding and polymerizing the methacrylic resin composition. The feature of the present invention is that, as shown in the above-mentioned polymerization recipe, polymerization is carried out in at least four stages with different characteristics, and the resulting polymer is made into a multilayer structure. The methacrylic resin composition produced by such a method exhibits excellent impact resistance, and has extremely excellent properties such as transparency, surface gloss, and moldability. The method for producing the resin composition of the present invention is not particularly limited, but emulsion polymerization is preferably carried out. When producing the resin composition of the present invention, in order to impart good transparency to the resulting resin composition, the refractive index of the resin phase obtained in each polymerization step should be made as similar as possible or extremely It is necessary to approximate. In addition, when producing the resin composition of the present invention,
In order to balance the transparency, surface appearance, and impact resistance performance of the resulting resin composition, it is also necessary to consider the diameter of the rubber particles to be dispersed. In the composition of the present invention, in order to obtain a composition excellent in both transparency and impact resistance, the polymerization of the crosslinked acrylic ester copolymer (B) is substantially completed, and the double structure acrylic elastomer is 0.13~0.45μ when [] is obtained
The particle size is preferably in the range of 0.2 to 0.35 μm, more preferably 0.2 to 0.35 μm. The double structure acrylic elastic body [] used in the present invention has a hard crosslinked resin (A) containing 80% by weight or more of methyl methacrylate units inside the particles, and a crosslinked acrylic ester copolymer in the outer layer. It has coalescence (B). The hard crosslinked resin (A) in the present invention is methyl methacrylate alone or 100 parts by weight of a monomer or mixture of 80% by weight or more of methyl methacrylate and 20% by weight or less of other copolymerizable vinyl monomers, and 0.1 to 100 parts by weight of the mixture. It is a copolymer polymerized by adding 10 parts by weight, more preferably 0.5 to 5 parts by weight of a crosslinkable monomer, and more preferably 5 to 50 parts by weight out of 100 parts by weight of the double structure acrylic elastic body. It is necessary to contain 10 to 40 parts by weight. If the amount is less than 5 parts by weight, the effect of improving impact resistance will be small and transparency will also decrease. On the other hand, if it exceeds 50% by weight, the surface gloss tends to decrease and the impact resistance also tends to decrease. The copolymerizable vinyl monomer used in the polymerization of the hard crosslinked resin (A) is not particularly limited, but preferred examples include acrylic acid alkyl esters having an alkyl group of 1 to 4 carbon atoms, styrene, and the like. Further, the crosslinkable monomer used in the polymerization of the hard crosslinked resin (A) does not need to be particularly limited as long as it copolymerizes with methyl methacrylate, and commonly used,
Bifunctional monomers such as ethylene glycol dimethacrylate, ethylene glycol diacrylate, 1.3-butylene dimethacrylate, and tetraethylene glycol diacrylate, or trifunctional monomers such as trimethylolpropane triacrylate, triallyl cyanurate, and triallyl isocyanurate. A functional monomer or a tetrafunctional monomer such as pentaerythritol tetraacrylate can be used alone or in combination. The crosslinked acrylic ester copolymer (B) is preferably at least one of n-butyl acrylate and 2-ethylhexyl acrylate among the acrylic alkyl ester group in which the alkyl group has 1 to 8 carbon atoms. 30-10% by weight of styrene alone or a mixture of styrene and its derivatives, and 0.1-10% by weight of a polyfunctional monomer copolymerizable with this and having two or more carbon-carbon double bonds in one molecule. It is a copolymer of a monomer mixture consisting of the following, and is polymerized into the outer layer in the presence of the hard crosslinked resin (A). The composition ratio of the acrylic acid ester monomer and styrene or its derivative is one of the important factors for imparting transparency, and transparency decreases outside the above composition range. Addition of a polyfunctional monomer is necessary from the viewpoint of impact resistance and surface appearance, and the optimum amount of addition differs depending on the type of polyfunctional monomer, but in general, the above amount is required.
A range of 0.1 to 10% by weight is preferable. The polyfunctional monomer used in the polymerization of the crosslinked acrylic ester copolymer (B) does not need to be particularly limited, but from the viewpoint of controlling the degree of crosslinking, it is necessary to Similar compounds are preferred, and specific examples include difunctional monomers such as ethylene glycol dimethacrylate, ethylene glycol diacrylate, 1,3-butylene dimethacrylate, tetraethylene glycol diacrylate, divinylbenzene, or trimethylolpropane triacrylate. , trifunctional monomers such as triallyl cyanurate and triallyl isocyanurate, or tetrafunctional monomers such as pentaerythritol tetraacrylate, each can be used alone or in combination. It is not preferable to use monomers having double bonds with different reactivities, such as allyl methacrylate, alone, and if it is necessary to use monomers of this type, it is necessary to use It is necessary to use it in combination with a crosslinkable monomer having two or more double bonds. Next, the crosslinkable monomer mixture (C) is polymerized in the presence of the double structure acrylic elastomer []. The component composition of the crosslinkable monomer mixture (C) is 80 to 99.9% by weight of methyl methacrylate, and the number of carbon atoms in the alkyl group is 1 to 8.
At least one type of acrylic acid alkyl ester of
~19.9% by weight, 0 to 10% by weight of other vinyl monomers that can be copolymerized with this, and a copolymerizable polyfunctional compound having two or more carbon-carbon double bonds with similar polymerization reactivity in one molecule. Consists of 0.1 to 10% by weight of crosslinkable monomer. If the content of methyl methacrylate in the monomer mixture (C) is less than 80% by weight, properties such as transparency, heat resistance, and weather resistance will be poor, and the alkyl acrylate copolymerized with it will be inferior. As an ester,
Examples include methyl acrylate, ethyl acrylate, butyl acrylate, and other vinyl monomers that can be used as copolymerization components include styrene, acrylonitrile, methacrylic acid, and the like. If the amount of acrylic ester exceeds 19.9% by weight in the crosslinkable monomer mixture (C), it is unfavorable in terms of heat resistance and transparency of the final composition, and other copolymerizable vinyl monomers may When the amount exceeds 10% by weight, properties such as transparency, weather resistance, and water resistance tend to decrease. As the polyfunctional crosslinking monomer, it is necessary to use a compound that has two or more carbon-carbon double bonds with similar reactivity in the molecule, and other compounds such as allyl methacrylate that have two or more double bonds must be used. If the reactivity of the polyfunctional crosslinking monomer is different, the effect of adding the polyfunctional crosslinking monomer may not be obtained, the surface gloss may decrease, the surface gloss may become dependent on molding conditions, and the fluidity may also decrease. Is recognized. The amount of the crosslinkable monomer mixture (C) is 5 to 100 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the double structure acrylic elastomer. If the amount is less than 5 parts by weight, the effect of improving surface gloss and fluidity cannot be obtained, and if it exceeds 100 parts by weight, surface gloss and fluidity tend to decrease, and impact resistance also decreases. Specific examples of the polyfunctional crosslinkable monomer that is an essential component of the crosslinkable monomer mixture (C) include ethylene glycol dimethacrylate, ethylene glycol diacrylate, 1,3-butylene dimethacrylate, tetraethylene glycol diacrylate, and trimethylol. Polyfunctional monomers such as propane triacrylate, triallyl cyanurate, triallyl isocyanurate, and pentaerythritol tetraacrylate can be used alone or in combination. If the amount of polyfunctional crosslinking monomer used is less than 0.1% by weight, it is unfavorable in terms of stress whitening resistance and surface gloss, and if the amount used exceeds 10% by weight, impact resistance will be impaired. Unfavorable in this respect. In the method of the present invention, a crosslinkable monomer mixture
When the polymerization of (C) is substantially completed, 80 to 100% by weight of methyl methacrylate, 1 to 1 carbon atoms in the alkyl group,
A non-crosslinkable monomer or a mixture thereof (D) consisting of 0 to 20% by weight of at least one of the acrylic acid alkyl esters of No. 8 and 0 to 10% by weight of other vinyl monomers copolymerizable therewith. 5 to 1000 parts by weight, more preferably 10 to 700 parts by weight, is polymerized to 100 parts by weight of the double structure acrylic elastic body.
Weight ratio to crosslinkable monomer mixture (C) [(D)/(C)]
must be selected so that the amount falls within the range of 0.5 to 200. If the amount is less than 5 parts by weight per 100 parts by weight of the double structure acrylic elastic material, the impact resistance will decrease; If it exceeds 100%, productivity will decrease and this is not preferable. In addition, the weight ratio of the non-crosslinkable monomer or its mixture (D) to the crosslinkable monomer mixture (C) in the first stage [(D)/
(C)] is less than 0.5, properties such as surface gloss, transparency, fluidity or impact resistance are reduced, while when it exceeds 200, productivity is poor. If the content of methyl methacrylate in the non-crosslinking monomer or mixture (D) is less than 80% by weight, properties such as transparency, heat resistance or mechanical properties will decrease, and the original properties of the methacrylic resin will be lost. . 1 to 8 carbon atoms copolymerized with methyl methacrylate
As the acrylic acid alkyl ester, an acrylate selected from 0 to 20% by weight of acrylate such as methyl acrylate, ethyl acrylate, and butyl acrylate is used, and if the amount exceeds 20% by weight, heat resistance and transparency may be affected. Unfavorable in some respects. Further, as other copolymerizable vinyl monomers, 0 to 10% by weight of styrene, acrylonitrile, methacrylic acid, etc. are used. Its amount is 10% by weight
Exceeding this is not preferable because properties such as transparency, weather resistance, or water resistance will be impaired. In the method of the present invention, it is also possible to use a polymerization degree regulator such as mercaptan in the non-crosslinkable monomer or monomer mixture (D) to adjust the molecular weight, if necessary. Examples of the polymerization degree regulator that can be used include alkyl mercaptans, thioglycolic acid and its esters, β-mercaptopropionic acid and its esters, and aromatic mercaptans such as thiophenol and thiocresol. The multi-layered methacrylic resin composition [] obtained by the series of polymerization processes described above can be used as is, but if necessary, it may be mixed with other thermoplastic resin, preferably methyl methacrylate 80~
100% by weight and 20-0% by weight of other vinyl monomers,
For example, it may be mixed with a methyl methacrylate resin, which is a polymer with an acrylic ester having an alkyl group having 1 to 4 carbon atoms, to contain 1 to 70% by weight of a double structure acrylic elastic material. You can also do it. Since it is particularly preferable to manufacture the multilayer methacrylic resin composition used in the present invention by the emulsion polymerization method, an example in which the emulsion polymerization method is used will be described. After adding deionized water and an emulsifier if necessary to the reaction vessel, the monomer mixture constituting the hard crosslinked resin (A) is polymerized, and then the monomer mixture constituting the crosslinked acrylic acid ester polymer (B) is polymerized. The crosslinkable monomer mixture (C) is then polymerized, and the non-crosslinkable monomer or monomer mixture (D) is further polymerized. Polymerization temperature is 30-120℃, more preferably 50-100℃
It is ℃. The polymerization time varies depending on the type and amount of the polymerization initiator and emulsifier, weight temperature, etc., but usually it takes 0.5 to 7 hours for each polymerization step (A), (B), (C), and (D). be. The ratio of monomer to water is preferably monomer/water=1/20 to 1/1. A polymerization initiator and an emulsifier can be added to either or both of the aqueous monomer phases. The monomers in the polymerization steps (A), (B), (C), and (D) can be charged all at once or in portions, but the split charging method is more preferable from the viewpoint of heat generation during polymerization. The emulsifier is not particularly limited as long as it is a commonly used emulsifier, and examples of emulsifiers that can be used include long-chain alkyl carboxylates, sulfosuccinic acid alkyl ester salts, alkylbenzene sulfonates, and the like. There is no need to particularly limit the type of polymerization initiator, and commonly used inorganic initiators such as water-soluble persulfates and perborates can be used alone or in combination with sulfites, thiosulfates, etc. as redox initiators. It can also be used. Also usable are redox initiation systems such as organic hydroperoxide-ferrous salts, organic hydroperoxide-sodium formaldehyde sulfoxylate, benzoyl peroxide, azobisisobutyronitrile, and the like. The polymer latex obtained by the emulsion polymerization method is coagulated and dried by a known method. When blending and dispersing the obtained multi-structure methacrylic resin composition into a methyl methacrylate resin, the most ideal method is melt mixing. Prior to melt mixing, stabilizers, lubricants, plasticizers, dyes, pigments, fillers, etc. are added as necessary in addition to the resin composition, and the mixture is mixed using a V-type blender, Henschel mixer, mixing roll, or screw type extruder. Melt and knead at 150-300°C. By molding the composition thus obtained using an extrusion molding machine or an injection molding machine, a molded product having excellent transparency, surface gloss, and high impact resistance can be obtained. The present invention will be explained in more detail below based on Examples. In the examples, parts represent parts by weight, and % represents weight %. Example 1 (1) Production of hard crosslinked resin (A) First, the following raw materials (a) were placed in a stainless steel reaction vessel with an internal volume of 50 mm, and nitrogen was blown into the vessel while stirring to create a state substantially free from the influence of oxygen. After that, 70℃
The temperature was raised to , and the following raw materials (b) were added, followed by polymerization for 2 hours to obtain a latex of hard crosslinked resin.
【表】【table】
【表】
このラテツクスのMMAの重合率は98.5％で粒
子径は0.13μｍであつた。
(2) ２重構造アクリル系弾性体〔〕の製造
上記硬質架橋樹脂ラテツクス（固形分約15％）
のはいつた上記容器内に、ソジウムホルムアルデ
ヒドスルホキシレート（以下ロンガリツトとい
う）およびザルコシネートLNの水溶液を加え、
80℃に昇温した後、これに下記の組成割合のアク
リル酸エステル系単量体混合物を170分にわたつ
て連続的に添加し、添加終了後、更に３時間重合
を継続して、硬質架橋樹脂(A)を粒子内部に含有
し、架橋アクリル酸エステル系共重合体(B)がその
外層を構成する２重構造アクリル系弾性体〔〕
のラテツクスを得た。[Table] The polymerization rate of MMA in this latex was 98.5%, and the particle size was 0.13 μm. (2) Production of double structure acrylic elastic body [] The above hard crosslinked resin latex (solid content approximately 15%)
Add an aqueous solution of sodium formaldehyde sulfoxylate (hereinafter referred to as Rongarit) and sarcosinate LN to the above-mentioned container.
After raising the temperature to 80°C, an acrylic acid ester monomer mixture having the composition ratio shown below was added continuously over 170 minutes, and after the addition was completed, polymerization was continued for an additional 3 hours to form a hard crosslink. Double structure acrylic elastic material containing resin (A) inside the particles and crosslinked acrylic ester copolymer (B) forming the outer layer []
of latex was obtained.
【表】
この時のBAの重合収率は97％、STの重合収率
は99.5％以上で、得られたラテツクス粒子の粒子
径は0.23μｍであつた。
(3) 多重構造メタクリル樹脂組成物〔〕の製造
上記(2)で得られた２重構造アクリル系弾性体
〔〕の固形分100部に相当するラテツクスを入れ
た上記の容器内に、ザルコシネートLN0.32部及
び脱イオン水10部を添加して撹拌した後、下記の
架橋性単量体混合物(C)を45分間にわたつて連続的
に添加した。その後更に１時間重合を継続した。
次にこの反応容器に下記に示す非架橋性単量体混
合物(D)を400分にわたつて連続的に添加し、更に
１時間重合を継続して、多重構造メタクリル樹脂
組成物〔〕をラテツクス状で得た。単量体混合
物(C)及び(D)の重合収率はそれぞれ99.5％及び99.5
％以上であつた。[Table] At this time, the polymerization yield of BA was 97%, the polymerization yield of ST was 99.5% or more, and the particle size of the obtained latex particles was 0.23 μm. (3) Production of multi-layered methacrylic resin composition [] Sarcosinate LN0 After adding and stirring .32 parts and 10 parts of deionized water, the following crosslinking monomer mixture (C) was added continuously over 45 minutes. Thereafter, polymerization was continued for an additional hour.
Next, a non-crosslinkable monomer mixture (D) shown below was continuously added to this reaction vessel over 400 minutes, and polymerization was continued for an additional hour to form a multilayer methacrylic resin composition [] into a latex. I got it in a state. The polymerization yields of monomer mixtures (C) and (D) were 99.5% and 99.5%, respectively.
% or more.
【表】
このラテツクスを以下に述べる方法により凝
固、洗浄、乾燥して多重構造メタクリル樹脂組成
物〔〕の粉体を得た。
ステンレス製容器に1.0％硫酸水1400部を仕込
み、撹拌下80℃に昇温し先に製造したラテツクス
700部を20分間にわたつて連続的に添加し、その
後内温を95℃まで昇温して５分間保持した。室温
まで冷却した後ポリマーを別し、脱イオン水で
洗滌し白色のクリーム状ポリマーを得、これを70
℃で24時間乾燥して白色粉体状のポリマーを得
た。
次にこの粉体を、外径40mmφのスクリユー型押
出機（日本製鋼所製、Ｐ―40―26AB―Ｖ型、
Ｌ／Ｄ＝26）を使用し、シリンダー温度200〜260
℃、ダイ温度250℃で溶融混練してペレツトと
し、２重構造アクリル系弾性体〔〕を25％含有
する耐衝撃性メタクリル樹脂組成物〔〕を得
た。
これを下記の条件で射出成形し、得られた試験
片から表１の評価結果を得た。
射出成形機；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℃、射出圧50
Kg／cm2
試験片サイズ；110mm×110mm×２mm（厚さ）[Table] This latex was coagulated, washed and dried by the method described below to obtain a powder of a multi-structure methacrylic resin composition. 1400 parts of 1.0% sulfuric acid water was placed in a stainless steel container, and the temperature was raised to 80°C while stirring to produce the latex produced earlier.
700 parts were added continuously over 20 minutes, and then the internal temperature was raised to 95°C and held for 5 minutes. After cooling to room temperature, the polymer was separated and washed with deionized water to obtain a white creamy polymer.
It was dried at ℃ for 24 hours to obtain a white powdery polymer. Next, this powder was transferred to a screw type extruder with an outer diameter of 40 mm (manufactured by Japan Steel Works, P-40-26AB-V type,
L/D=26), cylinder temperature 200-260
The pellets were melted and kneaded at a die temperature of 250°C to obtain an impact-resistant methacrylic resin composition containing 25% of a double-structured acrylic elastomer. This was injection molded under the following conditions, and the evaluation results shown in Table 1 were obtained from the obtained test pieces. Injection molding machine: Made by Japan Steel Works, V-17-65 type screw type automatic injection molding machine Injection molding conditions: Cylinder temperature 250℃, injection pressure 50
Kg/cm 2 Test piece size: 110mm x 110mm x 2mm (thickness)
【表】【table】
【表】
実施例 ２
非架橋性単量体混合物(D)を構成する単量体成分
が下記に示す組成割合である以外は、実施例１と
全く同様にして耐衝撃性メタクリル樹脂組成物
〔〕を得た。その物性評価結果を表２に示す。[Table] Example 2 An impact-resistant methacrylic resin composition [ ] was obtained. The physical property evaluation results are shown in Table 2.
【表】【table】
【表】
実施例 ３
(1) 硬質架橋樹脂(A)の製造
内容積50のステンレススチール製の反応容器
に下記の割合の原料を仕込み、窒素を吹き込み実
質的に酸素の影響のない状態とした後、撹拌下に
65℃で２時間重合を行ない硬質架橋樹脂体のラテ
ツクスを得た。
Ｓ―LN 0.6部
脱イオン水 150〃
過硫酸カリウム（KPS） 0.3〃
硼酸 1.0〃
炭酸ナトリウム 0.1〃
MMA 97〃
MA １〃
C4―DA ２〃
このラテツクスのMMAの重合率は98.5％で粒
子径は0.15μであつた。
(2) ２重構造アクリル系弾性体〔〕の製造
上記(1)の重合によつて得られた硬質架橋樹脂(A)
ラテツクスの一部を別のステンレススチール製反
応釜に取り、これにロンガリツトおよびＳ―LN
水溶液を加え、70℃に昇温した後、これに下記の
組成割合のアクリル酸エステル系単量体混合物を
30部／時間の添加速度で連続的に添加し、添加終
了後更に180分間重合を継続して、架橋アクリル
酸エステル系共重合体を重合し、硬質架橋樹脂を
粒子内部部に含有した２重構造アクリル系弾性体
〔〕をラテツクス状で得た。[Table] Example 3 (1) Production of hard crosslinked resin (A) Raw materials in the proportions shown below were charged into a stainless steel reaction vessel with an internal volume of 50 mm, and nitrogen was blown into the container to make it substantially free from the influence of oxygen. After that, under stirring
Polymerization was carried out at 65°C for 2 hours to obtain a hard crosslinked resin latex. S-LN 0.6 parts Deionized water 150〃 Potassium persulfate (KPS) 0.3〃 Boric acid 1.0〃 Sodium carbonate 0.1〃 MMA 97〃 MA 1〃 C 4 -DA 2〃 The polymerization rate of MMA in this latex is 98.5% and the particle size was 0.15μ. (2) Production of double structure acrylic elastic body [] Hard crosslinked resin (A) obtained by polymerization in (1) above
A portion of the latex was placed in another stainless steel reactor and was added to Rongalit and S-LN.
After adding the aqueous solution and raising the temperature to 70℃, add an acrylic acid ester monomer mixture with the composition ratio shown below.
The crosslinked acrylic acid ester copolymer was added continuously at a rate of 30 parts/hour, and the polymerization was continued for an additional 180 minutes after the addition was completed. A structural acrylic elastic body [ ] was obtained in the form of latex.
【表】
この重合におけるBAの重合収率は98％、STの
重合収率99％で、得られたラテツクス粒子の粒子
径は0.22μであつた。
(3) 多重構造メタクリル樹脂組成物〔〕の製造
前記(2)で得られた２重構造アクリル系弾性体
〔〕を固形分100重量部に相当するラテツクスを
反応容器にとり、これに脱イオン水225部および
Ｓ―LN0.25部を添加撹拌した後、80℃に昇温
し、下記の架橋性単量体混合物(C)を40部／時間の
速度で連続的に添加した後、更に１時間重合を継
続した。次にこの反応容器に下記に示す非架橋性
単量体混合物(D)を40部／時間の速度で連続的に添
加し、更に１時間重合を継続して、多重構造メタ
クリル樹脂組成物〔〕をラテツクス状で得た。
(C)および(D)単量体の重合収率はそれぞれ99.5％、
99％であつた。[Table] The polymerization yield of BA in this polymerization was 98%, the polymerization yield of ST was 99%, and the particle size of the obtained latex particles was 0.22μ. (3) Production of multi-layered methacrylic resin composition [] A latex containing the double-structured acrylic elastomer [] obtained in (2) above with a solid content of 100 parts by weight was placed in a reaction vessel, and deionized water was added to the latex. After adding and stirring 225 parts and 0.25 parts of S-LN, the temperature was raised to 80°C, and the following crosslinkable monomer mixture (C) was continuously added at a rate of 40 parts/hour. Polymerization was continued for hours. Next, a non-crosslinkable monomer mixture (D) shown below was continuously added to this reaction vessel at a rate of 40 parts/hour, and polymerization was continued for an additional hour to form a multi-structure methacrylic resin composition [] was obtained in latex form.
The polymerization yield of monomers (C) and (D) was 99.5%, respectively.
It was 99%.
【表】
このラテツクスを以下に述べる方法により凝
固、洗浄、乾燥して多重構造メタクリル樹脂組成
物〔〕の粉体を得た。
ステンレス製容器に1.0％硫酸水1200部を仕込
み、撹拌下70℃に昇温し、先に製造したラテツク
ス600部を15分間にわたつて連続的に添加し、そ
の後内温を90℃まで昇温し５分間保持した。室温
まで冷却した後ポリマーを別し脱イオン水で洗
滌し白色のクリーム状ポリマーを得、これを70℃
×24時間の条件下で乾燥し白色粉体状のポリマー
を得た。
次にこの粉体の多重構造メタクリル樹脂組成物
〔〕250部とアクリペツトVH（メタクリル樹脂
成形材料、三菱レイヨン(株)社製）250部をヘンシ
エルミキサーにより混合した後、実施例１で用い
たスクリユー型押出機を使用して、シリンダー温
度200〜270℃、ダイ温度260℃で溶融混練しペレ
ツト化することにより、２重構造アクリル系弾性
体〔〕の含有量20％耐衝撃性メタクリル樹脂組
成物を得た。
これを実施例１と同じ条件で射出成形し、得ら
れた試験片から表３の評価結果を得た。[Table] This latex was coagulated, washed and dried by the method described below to obtain a powder of a multi-structure methacrylic resin composition. Pour 1200 parts of 1.0% sulfuric acid water into a stainless steel container, raise the temperature to 70°C while stirring, add 600 parts of the previously produced latex continuously over 15 minutes, and then raise the internal temperature to 90°C. and held for 5 minutes. After cooling to room temperature, the polymer was separated and washed with deionized water to obtain a white creamy polymer, which was heated at 70°C.
It was dried under conditions of x24 hours to obtain a white powdery polymer. Next, 250 parts of this powdered multi-structure methacrylic resin composition [] and 250 parts of ACRYPET VH (methacrylic resin molding material, manufactured by Mitsubishi Rayon Co., Ltd.) were mixed using a Henschel mixer, and the mixture was used in Example 1. By melt-kneading and pelletizing using a screw type extruder at a cylinder temperature of 200 to 270°C and a die temperature of 260°C, an impact-resistant methacrylic resin composition with a double structure acrylic elastomer content of 20%. I got something. This was injection molded under the same conditions as in Example 1, and the evaluation results shown in Table 3 were obtained from the obtained test pieces.
【表】
実施例４〜５、比較例１
硬質架橋樹脂(A)を構成する単量体成分が表４に
示す割合である以外は、実施例３の(1)〜(3)の重合
処方と全く同様にして耐衝撃性メタクリル樹脂組
成物〔〕を得た。その物性評価結果を表５に示
す。なお射出成形条件の中で金型温度は500℃と
した。[Table] Examples 4 to 5, Comparative Example 1 The polymerization recipe of Example 3 (1) to (3) except that the monomer components constituting the hard crosslinked resin (A) are in the proportions shown in Table 4. An impact-resistant methacrylic resin composition [] was obtained in exactly the same manner. The physical property evaluation results are shown in Table 5. Note that the mold temperature was 500°C among the injection molding conditions.
【表】【table】
【表】
実施例６〜９、比較例２〜５
架橋アクリル酸エステル系共重合体(B)の単量体
成分の種類と割合を表６に示した如く変更した以
外は、実施例３と全く同様にしてメタクリル樹脂
組成物〔〕を得た。その物性評価結果を表７に
示す。[Table] Examples 6 to 9, Comparative Examples 2 to 5 Same as Example 3 except that the type and proportion of the monomer components of the crosslinked acrylic ester copolymer (B) were changed as shown in Table 6. A methacrylic resin composition [] was obtained in exactly the same manner. The physical property evaluation results are shown in Table 7.
【表】【table】
【表】
実施例10〜12、比較例６〜７
２重構造アクリル系弾性体〔〕を構成する、
硬質架橋樹脂(A)と架橋アクリル酸エステル系共重
合体(B)の構成割合〔(A)／(B)〕を表８に示した如く
変更した以外は、実施例３と全く同様にしてメタ
クリル樹脂組成物を得た。その物性評価結果を表
８に示す。[Table] Examples 10 to 12, Comparative Examples 6 to 7 Constituting the double structure acrylic elastic body []
Example 3 was carried out in exactly the same manner as in Example 3, except that the composition ratio [(A)/(B)] of the hard crosslinked resin (A) and the crosslinked acrylic ester copolymer (B) was changed as shown in Table 8. A methacrylic resin composition was obtained. The physical property evaluation results are shown in Table 8.
【表】
実施例13〜15、比較例８〜10
架橋性単量体混合物(C)ならびに非架橋性単量体
混合物(D)の単量体成分およびその使用割合〔(D)／
(C)〕を、表９に示したように変更した以外は、実
施例３と全く同様にしてメタクリル樹脂組成物を
得た。その物性の評価結果を表10に示す。[Table] Examples 13 to 15, Comparative Examples 8 to 10 Monomer components and usage ratios of crosslinkable monomer mixture (C) and non-crosslinkable monomer mixture (D) [(D)/
(C)] was changed as shown in Table 9, a methacrylic resin composition was obtained in exactly the same manner as in Example 3. Table 10 shows the evaluation results of its physical properties.
【表】【table】
【表】【table】
Claims (1)
む硬質架橋樹脂(A)５〜50重量部を粒子内部に含有
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くとも１種69.9〜89.9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30〜10重量％ならびにこれと共重合可能で１
分子中に炭素―炭素２重結合を２個以上有する多
官能単量体0.1〜10重量％よりなる架橋アクリル
酸エステル系共重合体(B)95〜50重量部が外層を構
成する２重構造アクリル系弾性体〔〕100重量
部の存在下に、メタクリル酸メチル80〜99.9重量
％、アルキル基の炭素数１〜８のアクリル酸アル
キルエステルの少くとも１種０〜19.9重量％、こ
れと共重合可能な他のビニル系単量体０〜10重量
％およびこれと共重合可能で１分子中に重合反応
性の近い、炭素―炭素２重結合を少くとも２個以
上有する多官能架橋性単量体0.1〜10重量％より
なる架橋性単量体混合物(C)５〜100重量部を重合
し、次いでメタクリル酸メチル80〜100重量％、
アルキル基の炭素数１〜８のアクリル酸アルキル
エステルの少くとも１種０〜20重量％ならびにこ
れと共重合可能な他のビニル単量体０〜10重量％
からなる非架橋性単量体または単量体混合物(D)５
〜1000重量部を前記架橋性単量体混合物(C)に対し
て重量比〔(D)／(C)〕で0.5〜200となる量、更に添
加して重合することからなる耐衝撃性に優れたメ
タクリル樹脂組成物の製造方法。[Scope of Claims] 1. An acrylic acid alkyl ester containing 5 to 50 parts by weight of a hard crosslinked resin (A) containing 80% by weight or more of methyl methacrylate units inside the particles, and in which the alkyl group has 1 to 8 carbon atoms. 69.9-89.9% by weight of at least one of
and 30 to 10% by weight of styrene alone or a mixture of styrene and its derivatives and copolymerizable with 1
A double structure in which the outer layer is composed of 95 to 50 parts by weight of a crosslinked acrylic ester copolymer (B) consisting of 0.1 to 10% by weight of a polyfunctional monomer having two or more carbon-carbon double bonds in the molecule. In the presence of 100 parts by weight of acrylic elastomer, 80 to 99.9% by weight of methyl methacrylate, 0 to 19.9% by weight of at least one acrylic acid alkyl ester having an alkyl group of 1 to 8 carbon atoms, and 0 to 10% by weight of other polymerizable vinyl monomers and a polyfunctional crosslinkable monomer having at least two or more carbon-carbon double bonds in one molecule, which is copolymerizable with this and has similar polymerization reactivity. 5 to 100 parts by weight of a crosslinkable monomer mixture (C) consisting of 0.1 to 10% by weight is polymerized, and then 80 to 100% by weight of methyl methacrylate,
0 to 20% by weight of at least one type of acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms and 0 to 10% by weight of other vinyl monomers copolymerizable therewith.
Non-crosslinkable monomer or monomer mixture (D)5 consisting of
~1000 parts by weight is added to the crosslinkable monomer mixture (C) in an amount such that the weight ratio [(D)/(C)] is 0.5 to 200, and polymerization is performed to improve impact resistance. A method for producing an excellent methacrylic resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7166880A JPS56167712A (en) | 1980-05-29 | 1980-05-29 | Production of methacryl resin composition having excellent impact resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7166880A JPS56167712A (en) | 1980-05-29 | 1980-05-29 | Production of methacryl resin composition having excellent impact resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56167712A JPS56167712A (en) | 1981-12-23 |
| JPS6245886B2 true JPS6245886B2 (en) | 1987-09-29 |
Family
ID=13467197
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7166880A Granted JPS56167712A (en) | 1980-05-29 | 1980-05-29 | Production of methacryl resin composition having excellent impact resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56167712A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02309699A (en) * | 1989-05-10 | 1990-12-25 | Telefonica De Espana Sa | Shilding mask having pulling-out and holding mechanism |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3300526A1 (en) * | 1983-01-10 | 1984-07-12 | Röhm GmbH, 6100 Darmstadt | IMPACT MODIFIER |
| JPS62230841A (en) * | 1985-11-29 | 1987-10-09 | Mitsubishi Rayon Co Ltd | Impact-resistant methacrylate resin composition |
-
1980
- 1980-05-29 JP JP7166880A patent/JPS56167712A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02309699A (en) * | 1989-05-10 | 1990-12-25 | Telefonica De Espana Sa | Shilding mask having pulling-out and holding mechanism |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56167712A (en) | 1981-12-23 |
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