JPS642150B2 - - Google Patents
Info
- Publication number
- JPS642150B2 JPS642150B2 JP12536179A JP12536179A JPS642150B2 JP S642150 B2 JPS642150 B2 JP S642150B2 JP 12536179 A JP12536179 A JP 12536179A JP 12536179 A JP12536179 A JP 12536179A JP S642150 B2 JPS642150 B2 JP S642150B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- acrylic
- composition
- coating film
- 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
- 239000000203 mixture Substances 0.000 claims description 28
- 229920000098 polyolefin Polymers 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000008199 coating composition Substances 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 238000000576 coating method Methods 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 25
- 229920006243 acrylic copolymer Polymers 0.000 description 19
- 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 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 7
- -1 polypropylene Polymers 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920005672 polyolefin resin Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 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
- 239000000600 sorbitol Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali 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
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】
本発明は常温硬化あるいは低温硬化により、外
観のすぐれた、密着性良好な塗膜を与えるポリオ
レフイン系樹脂用被覆組成物に関するものであ
る。
近年、自動車部品や家庭用電化製品の材料に各
種プラスチツク類が使用されるようになり、こと
に自動車部品に関しては省エネルギーの面からプ
ラスチツク使用による軽量化がさけばれ、ますま
すこの傾向が拡大する模様である。現在各種のプ
ラスチツク類が多量に使用されているが、ポリオ
レフイン系樹脂は比較的安価にもかかわらず一部
使用にとどまつている。これはポリオレフイン系
樹脂用のよい被覆組成物がなく、特に被覆物が密
着しにくいというポリオレフインの性質が多分に
影響しており、ポリオレフイン樹脂への付着性が
良好な被覆用組成物の開発がおおいに期待されて
いる。これら要望のため、現在ポリオレフインに
対する付着性のある被覆組成物の種々の開発が進
められている。その1つとして、ポリオレフイン
用接着助剤として、塩素化ポリオレフインがポリ
オレフインによく付着するということを生かそう
という検討が進められている。
しかしながら、塩素化ポリオレフインを下塗り
に用い、さらに別の樹脂を上塗りする方法を別に
すると、塗料中に塩素化ポリオレフインを配合す
るワンコート仕上げのものについては、塩素化ポ
リオレフインと塗料用樹脂との相溶性が悪く、塗
膜外観の不良などの点で問題があり、塗膜外観を
良くしようと思えば、塩素化ポリオレフインの使
用量に制限があり、付着性に問題がある。
そこで、本発明者らは上記のごとき問題を解消
する目的で研究を重ねた結果、ワンコート仕上げ
で密着性が良好で、外観がすぐれ、耐ガソリン性
や耐溶剤性などの諸性能のすぐれた塗膜をつくる
組成物を見い出した。
すなわち本発明は、アクリル系単量体と塩素化
ポリオレフインの重量比が98/2〜30/70の範囲
で、該アクリル系単量体は100重量%の内容が
(1) 塩基性窒素含有アクリル系単量体0.2〜30重
量%
(2) アクリル酸あるいはメタクリル酸と脂肪族1
価アルコールとのエステルまたはそれらの混合
物 35〜99.8重量%
(3) その他共重合可能な単量体 0〜60重量%
からなるアクリル系単量体を塩素化ポリオレフイ
ンの存在下で重合して得られる共重合組成物
()および1分子当り2個以上のエポキシ基を
有する化合物または樹脂()からなる被覆組成
物である。
アクリル系共重合組成物()の成分(1)すなわ
ち塩基性含有アクリル系単量体()はと反応し
架橋させるためのものであり、ジメチルアミノエ
チルアクリレートまたはメタクリレート、ジエチ
ルアミノエチルアクリレートまたはメタクリレー
ト、t―ブチルアミノエチルアクリレートまたは
メタクリレート等が好ましく使用される。これら
の使用量は0.2〜30重量%であるが、好ましくは
0.5〜20重量%である。アクリル系共重合組成物
()成分(2)は、アクリル酸およびメタクリル酸
と1価の非環式もしくは環式の脂肪族1価アルコ
ールとのエステルが適し、特にメタノール、エタ
ノール、プロパノール、ブタノールなどとのエス
テルなど、およびそれらの混合物が好ましく、単
量体の35〜99.8重量%、好ましくは50〜80重量%
が使用される。アクリル系共重合組成物()の
成分(3)としてはスチレンと少量のアクリル酸およ
び/またはメタクリル酸が好ましく使用される
が、その他α―メチルスチレン、ビニルトルエ
ン、アクリロニトリル、酢酸ビニル、2―ヒドロ
キシエチルアクリレートまたはメタクリレート、
2―ヒドロキシプロピルアクリレートまたはメタ
クリレート、アクリルアミド、メタクリルアミ
ド、グリシジルアクリレートまたはメタクリレー
トなど(1)および(2)成分と共重合可能なものはすべ
て使用できる。この使用量は、スチレンなどは0
〜60重量%好ましくは10〜40重量%使用できる。
アクリル酸、メタクリル酸などは10%以下が好ま
しく、その他単量体は20%以下が好ましい。
塩素化ポリオレフインは、塩素化ポリプロピレ
ン、塩素化ポリエチレンなどが好ましく使用され
る。これらの使用量はアクリル系単量体と塩素化
ポリオレフインの重量比が98/2〜30/70であ
り、好ましくは90/10〜50/50の範囲である。上
記アクリル系共重合組成物()は塩素化ポリオ
レフイン存在下の溶液重合によつて重合される。
すなわちトルエンなどの芳香族系溶剤および/ま
たはイソブタノールなどのアルコール系溶剤およ
び/または酢酸エチルなどのエステル系溶剤の存
在下にアゾビス系および/または過酸化物系など
の重合開始剤を使用し、常法により重合される。
塩素化ポリオレフインの使用量にもよるが主とし
て芳香族系溶剤が好ましい。1分子当り2個以上
のエポキシ基を有する化合物または樹脂()と
しては多価アルコールのグリシジルエーテルが好
ましく使用される。すなわち、エチレングリコー
ルジグリシジルエーテル、グリセロールポリグリ
シジルエーテル、ソルビトールポリグリシジルエ
ーテルなどが好ましく使用されるが、これに限定
されるものではない。例えばグリシジルアクリレ
ートまたはメタクリレートを共重合したアクリル
系樹脂など、1分子当り2個以上のエポキシ基を
有する物質を含むものであれば何れも使用可能で
ある。アクリル系共重合組成物()とエポキシ
化合物あるいは樹脂()の配合比は
()中の塩基性窒素原子(グラム原子)/()中の
エポキシ基の酸素原子(グラム原子)
=0.3〜3.0程度が好ましいが、これに限定される
ものではない。
本発明の組成物は被塗物に塗布する直前にアク
リル系共重合組成物()とエポキシ化合物また
は樹脂()とを混合することが望ましい。必要
ならば顔料、添加剤、溶剤などを加えたアクリル
系共重合組成物()を含む組成物に必要ならば
溶剤、その他を加えたエポキシ化合物または樹脂
()を含む組成物を加えてかきまぜ、長時間放
置することなく、必要ならば溶剤、その他の添加
剤を加えて被塗物に塗布することが好ましい。ま
た、さらに必要ならば塩素化ポリオレフインが他
の樹脂を加えてもさしつかえない。塗布された塗
膜は常温で、または必要に応じて比較的低温で加
熱されることにより乾燥され、架橋反応により硬
化された塗膜が形成される。比較的低温で硬化
し、十分な性能が得られるが、高温で硬化させて
もなんらさしつかえない。
本発明の特徴はアクリル系樹脂の架橋反応にエ
ポキシ基を有する化合物または樹脂を架橋剤とし
て使用する塗膜形成方法において、塩素化ポリオ
レフインの存在下に特定のアクリル系単量体を重
合させることによつて得られるアクリル系共重合
組成物を使用する点にある。この方法によつて従
来相溶性が比較的不良であつたアクリル共重合体
と塩素化ポリオレフインが、塩素化ポリオレフイ
ンの一部にアクリル単量体あるいは共重合体が結
合すると考えられ、そのために塩素化ポリオレフ
インとアクリル重合体からなる組成物の親和性が
大幅に改良され、下記のような効果が現われるこ
とに特徴をもつものである。
本発明の組成物を用いれば特にポリオレフイン
系樹脂との密着性にすぐれた、表面状態良好な、
外観のすぐれた塗膜がワンコート仕上げで得られ
る。またこれら塗膜は自然乾燥型および本発明以
外の類似の方法で得られる塗膜よりも、耐ガソリ
ン性、耐溶剤性、耐アルカリ性などの諸性能がは
るかにすぐれる。すなわち、本発明の組成物を用
いれば、省資源で、イソシアネート類を使用する
系などにより毒性が少なく、特に基材との密着性
が良好で、外観と物理的性能および耐ガソリン
性、耐薬品性、耐水性などのすぐれた高性能塗膜
を得ることができる。
本発明の組成物はポリオレフイン系樹脂好まし
くはポリプロピレン樹脂の塗装に好ましく使用さ
れるほか、その他プラスチツク類や木材、コンク
リートなどの建材などの塗装にも使用できる。本
発明の効果を明らかにするため、その実施例を次
に示す。
実施例 1
冷却器、温度計、かくはん機を備えたフラスコ
中にトルエン70部、ハードレン―15LLB(東洋化
成株式会社製塩素化ポリプロピレン、固形分30
%)333部、ジメチルアミノエチルメタクリレー
ト12部、メチルメタクリレート35部、ブチルアク
リレート23部、スチレン30部、アゾビスイソブチ
ロニトリル1部を仕込み、80℃で2時間かきま
ぜ、その後2時間ごとに8回、アゾビスイソブチ
ロニトリル0.3部づつを加え、合計20時間で重合
を完了し、アクリル系共重合組成物()を得
た。組成物の不揮発分は39.9%であつた。このう
ちの100部にソルビトールポリグリシジルエーテ
ル(長瀬産業株式会社製のデナコールEX―611)
3部を加えてかきまぜ、トルエンで適当な粘度に
希釈した後、アプリケーターで市販のポリプロピ
レン樹脂板に塗布した。23℃で3日間放置後、塗
膜試験を行なつた。乾燥塗膜は透明均一で光沢が
あり、また付着性もきわめて良好であつた。
比較例 1
実施例1と同様のフラスコ中にトルエン100部、
ジメチルアミノエチルメタクリレート12部、メチ
ルメタクリレート35部、ブチルアクリレート23
部、スチレン30部、アゾビスイソブチロニトリル
1部を仕込み、80℃で2時間かきまぜ、その後2
時間ごとに8回アゾビスイソブチロニトリル0.3
部づつを加え、合計20時間で重合を完了し、アク
リル共重体樹脂溶液を得た。不揮発分は49.9%で
あつた。このうちの40部にハードレン―
15LLB67部、デナコールEX―611、3部を加え
てよくかきまぜ、トルエンで適当な粘度に希釈し
た後、実施例1と同様の方法で塗膜を作製し、試
験を行なつた。乾燥塗膜は不均一で平滑性にとぼ
しく、光沢がなく、付着性にはむらがあつた。
実施例 2
実施例1と同様のフラスコにトルエン100部、
ハードレン―15LLE83部、ジメチルアミノエチ
ルメタクリレート10部、メチルメタクリレート60
部、エチルアクリレート15部、n―ブチルメタク
リレート15部、アゾビスイソブチロニトリル1部
を仕込み、実施例1と同様の重合を行ない、不揮
発分44.0%のアクリル系共重合組成物()を得
た。このうちの55部にジグリセロールポリグリシ
ジルエーテル(長瀬産業株式会社製 デナコール
EX―421)2.5部を加えてかきまぜ、トルエンで
適当な粘度に希釈した後、実施例1と同様の方法
で塗膜を作製し、試験を行なつた。乾燥塗膜は均
一で平滑性にすぐれ、付着性も良好であつた。
比較例 2
実施例1と同様のフラスコ中にトルエン100部、
ジメチルアミノエチルメタクリレート10部、メチ
ルメタクリレート60部、エチルアクリレート15
部、n―ブチルメタクリレート15部、アゾビスイ
ソブチロニトリル1部を仕込み、塩素化ポリプロ
ピレンを含まない以外は実施例1と同様の重合を
行ない、不揮発分50.1%のアクリル共重合体樹脂
溶液を得た。このうちの40部に、デナコールEX
―421を2.5部加え、さらにハードレン―15LLBを
40部加えてよくかきまぜ、実施例1と同様の方法
で塗膜を作製し、試験を行なつた。乾燥塗膜は不
均一で平滑性にとぼしく、付着性にはむらがあつ
た。
実施例 3
実施例2で得られたアクリル系共重合組成物
()55部にデナコールEX―421を2.5部加え、さ
らにハードレン15―LLBを25部加えてよくかき
まぜ、実施例1と同様の方法で塗膜を作製し、試
験を行なつた。乾燥塗膜は平滑性にすぐれ、付着
性はきわめて良好であつた。
比較例 3
比較例2で得られたアクリル共重合体樹脂溶液
6部にトルエン10部、酸化チタン30部とサンドグ
ラインダ用ビーズを加えて振とうし、顔料を分散
した。これにアクリル共重合体樹脂溶液を100部、
デナコールEX―611を6部配合し、以下実施例4
と同様の方法で試験板を作製し、試験を行なつ
た。その結果満足な付着が得られなかつた。結果
を表―1に示す。
実施例 4
実施例2で得られたアクリル系共重合組成物
() 12部にトルエン10部、酸化チタン(石原
産業株式会社製 タイパー7R―930)30部とサン
ドグラインダー用ビーズを加えて振とうし、顔料
を分散した。これにアクリル系共重合組成物
()を138部、デナコールEX―611を6部配合
し、芳香族系シンナーで適当な粘度に希釈して市
販のポリプロピレン樹脂板にスプレー塗装した。
1時間静置後、70℃で30分間乾燥し、さらに23℃
で3日間乾燥後、塗膜の試験を行なつた。表面状
態、付着性、その他諸性能は良好であつた。結果
を表―1に示す。
比較例 4
比較例2で得られたアクリル共重合体樹脂溶液
6部にトルエン10部、酸化チタン30部とサンドグ
ラインダ用ビーズを加えて振とうし、顔料を分散
した。これにアクリル共重合体樹脂溶液を100部、
デナコールEX―611を6部、ハードレン15―
LLBを43g配合し、以下実施例4と同様の試験
を行なつた。その結果、光沢の低く、塗膜外観は
不良であつた。結果を表―1に示す。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a coating composition for polyolefin resins that provides a coating film with excellent appearance and good adhesion by curing at room temperature or low temperature. In recent years, various types of plastics have come to be used as materials for automobile parts and household electrical appliances, and in particular, the use of plastics to reduce the weight of automobile parts has been avoided in order to save energy, and this trend seems to be expanding. It is. Currently, various types of plastics are used in large quantities, but polyolefin resins are only partially used despite being relatively inexpensive. This is largely due to the lack of good coating compositions for polyolefin resins, and in particular the property of polyolefins, which makes it difficult for coatings to adhere.Therefore, the development of coating compositions that have good adhesion to polyolefin resins is greatly needed. It is expected. In response to these demands, various coating compositions that adhere to polyolefins are currently being developed. As one of these, studies are underway to utilize the fact that chlorinated polyolefin adheres well to polyolefin as an adhesive aid for polyolefin. However, apart from the method of using chlorinated polyolefin as an undercoat and then topcoating with another resin, the compatibility between the chlorinated polyolefin and the paint resin is limited for one-coat finishes that contain chlorinated polyolefin in the paint. There are problems in terms of poor coating film appearance, and if it is desired to improve the coating film appearance, there is a limit to the amount of chlorinated polyolefin that can be used, and there are problems with adhesion. Therefore, the inventors of the present invention have conducted repeated research with the aim of solving the above problems, and have found that a one-coat finish has good adhesion, an excellent appearance, and excellent performance such as gasoline resistance and solvent resistance. We have discovered a composition that forms a coating film. That is, in the present invention, the weight ratio of the acrylic monomer to the chlorinated polyolefin is in the range of 98/2 to 30/70, and the acrylic monomer contains 100% by weight of (1) basic nitrogen-containing acrylic; System monomer 0.2-30% by weight (2) Acrylic acid or methacrylic acid and aliphatic 1
Obtained by polymerizing an acrylic monomer consisting of 35 to 99.8% by weight of an ester with a alcohol or a mixture thereof (3) and 0 to 60% by weight of other copolymerizable monomers in the presence of a chlorinated polyolefin. A coating composition consisting of a copolymer composition () and a compound or resin () having two or more epoxy groups per molecule. Component (1) of the acrylic copolymer composition (), that is, the basic-containing acrylic monomer (), is for reacting with and crosslinking, dimethylaminoethyl acrylate or methacrylate, diethylaminoethyl acrylate or methacrylate, t. -Butylaminoethyl acrylate or methacrylate is preferably used. The amount used is 0.2-30% by weight, but preferably
It is 0.5-20% by weight. Component (2) of the acrylic copolymer composition (2) is preferably an ester of acrylic acid or methacrylic acid and a monovalent acyclic or cyclic aliphatic monohydric alcohol, particularly methanol, ethanol, propanol, butanol, etc. and mixtures thereof, preferably 35 to 99.8% by weight of the monomer, preferably 50 to 80% by weight of the monomer.
is used. As component (3) of the acrylic copolymer composition (), styrene and a small amount of acrylic acid and/or methacrylic acid are preferably used, but in addition, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, 2-hydroxy ethyl acrylate or methacrylate,
Anything that can be copolymerized with components (1) and (2), such as 2-hydroxypropyl acrylate or methacrylate, acrylamide, methacrylamide, glycidyl acrylate or methacrylate, can be used. This usage amount is 0 for styrene etc.
~60% by weight, preferably 10-40% by weight can be used.
The content of acrylic acid, methacrylic acid, etc. is preferably 10% or less, and the content of other monomers is preferably 20% or less. As the chlorinated polyolefin, chlorinated polypropylene, chlorinated polyethylene, etc. are preferably used. The weight ratio of the acrylic monomer to the chlorinated polyolefin is from 98/2 to 30/70, preferably from 90/10 to 50/50. The above acrylic copolymer composition () is polymerized by solution polymerization in the presence of chlorinated polyolefin.
That is, a polymerization initiator such as an azobis-based and/or peroxide-based initiator is used in the presence of an aromatic solvent such as toluene, an alcoholic solvent such as isobutanol, and/or an ester solvent such as ethyl acetate, Polymerization is carried out by conventional methods.
Although it depends on the amount of chlorinated polyolefin used, aromatic solvents are mainly preferred. As the compound or resin having two or more epoxy groups per molecule, glycidyl ether of polyhydric alcohol is preferably used. That is, ethylene glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, and the like are preferably used, but the present invention is not limited thereto. For example, any material containing a substance having two or more epoxy groups per molecule can be used, such as an acrylic resin copolymerized with glycidyl acrylate or methacrylate. The blending ratio of the acrylic copolymer composition () and the epoxy compound or resin () is
Basic nitrogen atom (gram atom) in parentheses/oxygen atom (gram atom) of epoxy group in parentheses is preferably about 0.3 to 3.0, but is not limited thereto. In the composition of the present invention, it is desirable to mix the acrylic copolymer composition (2) and the epoxy compound or resin (2) immediately before applying it to the object to be coated. If necessary, add a composition containing an epoxy compound or resin () to a composition containing an acrylic copolymer composition () to which pigments, additives, solvents, etc. are added, if necessary, and stir. It is preferable to apply the coating to the object without leaving it for a long time, adding a solvent and other additives if necessary. Furthermore, if necessary, other resins may be added to the chlorinated polyolefin. The applied coating film is dried at room temperature or, if necessary, by heating at a relatively low temperature, and a cured coating film is formed by a crosslinking reaction. It cures at a relatively low temperature and provides sufficient performance, but there is no problem even if it is cured at a high temperature. The feature of the present invention is that a specific acrylic monomer is polymerized in the presence of a chlorinated polyolefin in a coating film forming method that uses a compound or resin having an epoxy group as a crosslinking agent in the crosslinking reaction of an acrylic resin. The point is that the resulting acrylic copolymer composition is used. It is thought that by this method, the acrylic copolymer and chlorinated polyolefin, which had conventionally had relatively poor compatibility, are bonded to the acrylic monomer or copolymer to a part of the chlorinated polyolefin, and therefore chlorinated. It is characterized in that the affinity of the composition consisting of polyolefin and acrylic polymer is greatly improved, and the following effects appear. If the composition of the present invention is used, the composition will have excellent adhesion to polyolefin resins and a good surface condition.
A coating film with excellent appearance can be obtained with a one-coat finish. Furthermore, these coating films have much better performance, such as gasoline resistance, solvent resistance, and alkali resistance, than those obtained by air-drying or similar methods other than those of the present invention. In other words, if the composition of the present invention is used, it will save resources, have less toxicity due to the system using isocyanates, have particularly good adhesion to substrates, and improve appearance, physical performance, gasoline resistance, and chemical resistance. A high-performance coating film with excellent properties such as durability and water resistance can be obtained. The composition of the present invention is preferably used for coating polyolefin resins, preferably polypropylene resins, and can also be used for coating other building materials such as plastics, wood, and concrete. In order to clarify the effects of the present invention, examples thereof are shown below. Example 1 In a flask equipped with a condenser, a thermometer, and a stirrer, 70 parts of toluene and Hardene-15LLB (chlorinated polypropylene manufactured by Toyo Kasei Co., Ltd., solid content 30
%), 12 parts of dimethylaminoethyl methacrylate, 35 parts of methyl methacrylate, 23 parts of butyl acrylate, 30 parts of styrene, and 1 part of azobisisobutyronitrile, stirred at 80°C for 2 hours, and then stirred at 80°C every 2 hours. 0.3 parts of azobisisobutyronitrile was added twice, and the polymerization was completed in a total of 20 hours to obtain an acrylic copolymer composition (2). The nonvolatile content of the composition was 39.9%. 100 parts of sorbitol polyglycidyl ether (Denacol EX-611 manufactured by Nagase Sangyo Co., Ltd.)
After adding 3 parts and stirring, diluting with toluene to an appropriate viscosity, it was applied to a commercially available polypropylene resin plate using an applicator. After being left at 23°C for 3 days, a coating test was conducted. The dried coating film was transparent, uniform, and glossy, and had very good adhesion. Comparative Example 1 In a flask similar to Example 1, 100 parts of toluene,
12 parts of dimethylaminoethyl methacrylate, 35 parts of methyl methacrylate, 23 parts of butyl acrylate
1 part, 30 parts of styrene, and 1 part of azobisisobutyronitrile, stirred at 80℃ for 2 hours, then 2
Azobisisobutyronitrile 0.3 times per hour 8 times
The polymerization was completed in a total of 20 hours, and an acrylic copolymer resin solution was obtained. The nonvolatile content was 49.9%. 40 of these are hard-lenned.
After adding 67 parts of 15LLB and 3 parts of Denacol EX-611 and stirring well, diluting with toluene to an appropriate viscosity, a coating film was prepared in the same manner as in Example 1 and tested. The dried coating was uneven, had poor smoothness, lacked gloss, and had uneven adhesion. Example 2 100 parts of toluene was added to the same flask as in Example 1.
Hardren-15LLE83 parts, dimethylaminoethyl methacrylate 10 parts, methyl methacrylate 60 parts
15 parts of ethyl acrylate, 15 parts of n-butyl methacrylate, and 1 part of azobisisobutyronitrile, and polymerization was carried out in the same manner as in Example 1 to obtain an acrylic copolymer composition () with a nonvolatile content of 44.0%. Ta. Of this, 55 parts were added to diglycerol polyglycidyl ether (Denacol, manufactured by Nagase Sangyo Co., Ltd.).
After adding 2.5 parts of EX-421) and stirring and diluting with toluene to an appropriate viscosity, a coating film was prepared in the same manner as in Example 1 and tested. The dried coating film was uniform, had excellent smoothness, and had good adhesion. Comparative Example 2 In a flask similar to Example 1, 100 parts of toluene,
10 parts of dimethylaminoethyl methacrylate, 60 parts of methyl methacrylate, 15 parts of ethyl acrylate
Polymerization was carried out in the same manner as in Example 1 except that 15 parts of n-butyl methacrylate and 1 part of azobisisobutyronitrile were added, and chlorinated polypropylene was not included. Obtained. 40 of these include Denacol EX
-Add 2.5 parts of 421, and add Hardren-15LLB
After adding 40 parts and stirring well, a coating film was prepared in the same manner as in Example 1 and tested. The dried coating film was uneven and had poor smoothness, and its adhesion was uneven. Example 3 2.5 parts of Denacol EX-421 was added to 55 parts of the acrylic copolymer composition () obtained in Example 2, and further 25 parts of Hardren 15-LLB were added and stirred well, followed by the same method as in Example 1. A coating film was prepared and tested. The dried coating film had excellent smoothness and very good adhesion. Comparative Example 3 To 6 parts of the acrylic copolymer resin solution obtained in Comparative Example 2, 10 parts of toluene, 30 parts of titanium oxide, and sand grinder beads were added and shaken to disperse the pigment. Add 100 parts of acrylic copolymer resin solution to this,
6 parts of Denacol EX-611 was blended, Example 4 below.
A test plate was prepared and tested in the same manner as above. As a result, satisfactory adhesion could not be obtained. The results are shown in Table-1. Example 4 To 12 parts of the acrylic copolymer composition obtained in Example 2, 10 parts of toluene, 30 parts of titanium oxide (Typer 7R-930 manufactured by Ishihara Sangyo Co., Ltd.) and sand grinder beads were added and shaken. and dispersed the pigment. This was mixed with 138 parts of acrylic copolymer composition () and 6 parts of Denacol EX-611, diluted with aromatic thinner to an appropriate viscosity, and spray-painted onto a commercially available polypropylene resin board.
After standing for 1 hour, dry at 70℃ for 30 minutes, then dry at 23℃
After drying for 3 days, the coating was tested. The surface condition, adhesion, and other properties were good. The results are shown in Table-1. Comparative Example 4 To 6 parts of the acrylic copolymer resin solution obtained in Comparative Example 2, 10 parts of toluene, 30 parts of titanium oxide, and sand grinder beads were added and shaken to disperse the pigment. Add 100 parts of acrylic copolymer resin solution to this,
Denacol EX - 6 parts of 611, Hardren 15 -
43g of LLB was blended and the same test as in Example 4 was conducted. As a result, the gloss was low and the appearance of the coating film was poor. The results are shown in Table-1. 【table】
Claims (1)
重量比が98/2〜30/70の範囲で、該アクリル系
単量体100重量%の内容が (1) 塩基性窒素含有アクリル系単量体0.2〜30重
量% (2) アクリル酸あるいはメタクリル酸と脂肪族1
価アルコールとのエステルまたはそれらの混合
物35〜99.8重量% (3) その他共重合可能な単量体0〜60重量% からなるアクリル系単量体を塩素化ポリオレフイ
ンの存在下で重合して得られる共重合組成物
()および1分子当り2個以上のエポキシ基を
有する化合物または樹脂()からなる被覆組成
物。[Claims] 1. The weight ratio of the acrylic monomer to the chlorinated polyolefin is in the range of 98/2 to 30/70, and the content of 100% by weight of the acrylic monomer is (1) containing basic nitrogen; Acrylic monomer 0.2-30% by weight (2) Acrylic acid or methacrylic acid and aliphatic 1
Obtained by polymerizing an acrylic monomer consisting of 35 to 99.8% by weight of an ester with a alcohol or a mixture thereof (3) and 0 to 60% by weight of other copolymerizable monomers in the presence of a chlorinated polyolefin. A coating composition comprising a copolymer composition () and a compound or resin () having two or more epoxy groups per molecule.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12536179A JPS5650971A (en) | 1979-10-01 | 1979-10-01 | Coating composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12536179A JPS5650971A (en) | 1979-10-01 | 1979-10-01 | Coating composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5650971A JPS5650971A (en) | 1981-05-08 |
JPS642150B2 true JPS642150B2 (en) | 1989-01-13 |
Family
ID=14908226
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12536179A Granted JPS5650971A (en) | 1979-10-01 | 1979-10-01 | Coating composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5650971A (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5880356A (en) * | 1981-11-09 | 1983-05-14 | Toray Ind Inc | Coating composition |
JPS59138238A (en) * | 1983-01-27 | 1984-08-08 | Toray Ind Inc | Coating composition for undercoat |
JPH0742380B2 (en) * | 1984-10-13 | 1995-05-10 | 三井石油化学工業株式会社 | Paint composition |
JPS6311009U (en) * | 1986-07-04 | 1988-01-25 | ||
CA2075359A1 (en) * | 1992-02-13 | 1993-08-14 | Tatsuya Takenaka | Under-coating composition |
DE19547623C1 (en) * | 1995-12-20 | 1997-06-12 | Herberts Gmbh | Solvent-based coating compositions and their use |
CN108139118B (en) | 2015-10-08 | 2021-07-23 | 三菱电机株式会社 | Refrigeration cycle device |
-
1979
- 1979-10-01 JP JP12536179A patent/JPS5650971A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5650971A (en) | 1981-05-08 |
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