JP2004075893A - Undercoat composition for plastic member - Google Patents

Undercoat composition for plastic member Download PDF

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JP2004075893A
JP2004075893A JP2002239384A JP2002239384A JP2004075893A JP 2004075893 A JP2004075893 A JP 2004075893A JP 2002239384 A JP2002239384 A JP 2002239384A JP 2002239384 A JP2002239384 A JP 2002239384A JP 2004075893 A JP2004075893 A JP 2004075893A
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resin
component
content
parts
weight
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JP4410460B2 (en
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Shinji Tomita
冨田 真司
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an undercoat composition for plastic members which can be directly applied to the plastic members such as bumpers and door mirror covers without using any exclusive primer and is especially used as a putty or a primer surfacer for automobile repair, etc. <P>SOLUTION: The composition comprises (A) a normal temperature-dried resin composition, (B) a chlorinated polyolefin resin, (C) a pigment and (D) a resin fine particle. Here, the content of component (C) is 100-500 pts.wt. based on 100 pts.wt. resin solid content of component (A), and the content of component (D) is 0.1-35 wt.% in terms of solid content based on the content of component (C). <P>COPYRIGHT: (C)2004,JPO

Description

【0001】
【発明の属する技術分野】
本発明は、専用プライマーを使用せずとも、バンパーやドアミラーカバーなどのプラスチック部材に直接塗着可能なプラスチック部材用下地塗料組成物に関する。
【0002】
【従来技術及びその課題】
バンパーやドアミラーカバー等の自動車用部品は、現在、ポリプロピレンなどのポリオレフィン系樹脂を素材とするものが主流である。ポリオレフィン樹脂素材は、成型性、耐薬品性に優れるものの、その表面に塗装する場合には、付着性が非常に悪い。そのため該ポリオレフィン樹脂素材によるバンパー面損傷部の補修塗装は、素地が露出した場合、該素材と付着性の良い塩素化ポリオレフィン樹脂を配合してなる専用プライマーを塗装した後、パテやプライマーサーフェーサーを塗装するのが一般的である。
【0003】
しかしながら上記専用プライマーであっても、補修塗装分野で使用される常温乾燥タイプの基体樹脂成分と塩素化ポリオレフィン樹脂との相溶性が悪く、付着性が不十分であったり、専用プライマー塗装工程よる工程増もコスト的に不利であり問題であった。
【0004】
本発明の目的は、専用プライマーを使用せずとも、ポリオレフィン素材によるプラスチック部材に直接塗着可能な、パテやプライマーサーフェーサーとして使用できるプラスチック部材用下地塗料組成物を提供することにある。
【0005】
【課題を解決するための手段】
本発明者らは、上記問題を解決すべく鋭意検討した結果、パテやプラサフ用に用いられる樹脂組成物に塩素化ポリオレフィンを配合し、さらに樹脂微粒子を特定量配合することによって、塩素化ポリオレフィンを塗料中に均一に分散でき、ポリオレフィン素材によるプラスチック部材に対して優れた付着性を有する塗膜を形成できることを見出し本発明を完成するに至った。
【0006】
即ち本発明は、
1.(A)常温乾燥型樹脂組成物、(B)塩素化ポリオレフィン系樹脂、(C)顔料及び(D)樹脂微粒子を含有する下地塗料組成物であって、該(C)成分の含有量が(A)成分の樹脂固形分100重量部に対し100〜500重量部で、且つ該(D)成分の含有量が(C)成分の含有重量に対してに対して固形分で0.1〜35重量%であることを特徴とするプラスチック部材用下地塗料組成物、
2.常温乾燥型樹脂組成物(A)が、アクリル樹脂系又はアルキド樹脂系、及び繊維素誘導体系を含むものである1項記載の下地塗料組成物、
3.(B)成分の含有量が(A)成分の樹脂固形分100重量部に対して固形分で5〜25重量部である1項記載の下地塗料組成物、
4.プラスチック部材面に、1ないし3のいずれか1項記載の下地塗料組成物を塗布した後、さらに上塗り塗装を行なうことを特徴とする補修塗装方法、
を提供するものである。
【0007】
【発明の実施の形態】
本発明において常温乾燥型樹脂組成物(A)としては、従来公知の鈑金パテや樹脂パテ、プラサフ用の低粘度の樹脂組成物が適用可能であり、例えば繊維素誘導体系、不飽和ポリエステル樹脂系、エポキシアクリレ−ト樹脂系、エポキシ樹脂系、アクリル樹脂系、アルキド樹脂系、ウレタン樹脂系などが挙げられる。これらのうち特に、不飽和ポリエステル樹脂及び重合性不飽和モノマーを含む樹脂組成物(A−1)や、アクリル樹脂系又はアルキド樹脂系、及び繊維素誘導体系を含む樹脂組成物(A−2)が好適に使用できる。
【0008】
上記樹脂組成物(A−1)において使用される不飽和ポリエステル樹脂としては、従来パテ用に用いられているものであれば特に制限なく適用でき、例えばマレイン酸、無水マレイン酸、フマル酸、イタコン酸等の不飽和多塩基酸と、エチレングリコール、プロピレングリコール、ジエチレングリコール、水素添加ビスフェノールAなどの多価アルコールとの縮合によって得られるものが挙げられ、またこれらを、アリルグリシジルエーテル、アリルグリコール等のアリル化合物やアマニ油、脱水ヒマシ油等の油脂もしくはその脂肪酸の共存下で縮合して得られるものも挙げられる。さらに上記不飽和多塩基酸には、必要に応じてアジピン酸、無水フタル酸等の飽和多塩基酸を併用してもよい。
【0009】
上記樹脂組成物(A−1)において使用される重合性不飽和モノマーとしては、例えばスチレン、α−メチルスチレン、ビニルトルエン;エチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート等の(メタ)アクリル酸のアルキルエステル;2−ヒドロキシエチル(メタ)アクリレート等の(メタ)アクリル酸のヒドロキシアルキルエステル;酢酸ビニル、アクリロニトリルなどが挙げられ、これらは1種又は2種以上併用して用いることができる。上記不飽和ポリエステル樹脂と該重合性不飽和モノマーとの使用(重量)比は、90/10〜50/50の範囲内が好適である。
【0010】
上記樹脂組成物(A−1)には、硬化触媒として、例えばメチルエチルケトンパーオキサイド、ベンゾイルパーオキサイド、クメンハイドロパーオキサイド、シクロヘキサノンパーオキサイド等の有機過酸化物を配合することができる。該硬化触媒は、通常、可塑剤等に溶解し、必要に応じて後述の(B)及び(C)成分などと混合したペーストとして貯蔵し、使用直前に不飽和ポリエステル樹脂や重合性不飽和モノマーと混合される。
【0011】
また上記樹脂組成物(A−1)の不飽和ポリエステル樹脂の代わりに、エポキシ樹脂にアクリル酸やマレイン酸などの不飽和カルボン酸を反応させて得られるエポキシアクリレート等のエポキシエステル樹脂を用いることもできる。
【0012】
上記エポキシ樹脂としては、例えばビスフェノールA型エポキシ樹脂などのグリシジルエーテル型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、その他のグリシジルエーテル型エポキシ樹脂、脂環族エポキシ樹脂、及びこれらのエポキシ樹脂をアルキルフェノール又は/及び脂肪酸によって変性してなる変性エポキシ樹脂、あるいはアルキルフェノール又はアルキルフェノールノボラック型樹脂とエピクロルヒドリンとを反応させてなるエポキシ基導入アルキルフェノール又はアルキルフェノールノボラック型樹脂などの低粘度のエポキシ樹脂を挙げることができる。
【0013】
上記樹脂組成物(A−2)において使用されるアクリル樹脂系やアルキド樹脂系としては、従来ラッカータイプのプラサフ用に用いられているものであれば特に制限なく適用でき、アクリル樹脂系としては、例えばスチレン及び/又はスチレン誘導体や、アクリル酸又はメタクリル酸のアルキル又はシクロアルキルエステル類とをそれ自体公知の方法によって重合せしめてなる、分子量20,000〜100,000程度のアクリル樹脂を用いることができる。アルキド樹脂系としては、多塩基酸成分、多価アルコール成分及び油脂肪酸をそれ自体既知の方法によってエステル化してなる樹脂を用いることができる。
【0014】
上記樹脂組成物(A−2)において使用される繊維素誘導体系としては、例えばセルロースアセテートブチレート、セルロースアセテート、セルロースアセテートプロピオネート及びニトロセルロース(硝酸セルロース)等が挙げられ、これらは1種又は2種以上併用して用いることができる。また上記樹脂組成物(A−2)には可塑剤を配合してもよい。
【0015】
本発明において常温乾燥型樹脂組成物(A)としては、特に樹脂組成物(A−2)が好適である。
【0016】
上記常温乾燥型樹脂組成物(A)は、低粘度の樹脂組成物であり、好適には25℃における粘度が5Pa・s(パスカル・秒)、好ましくは1〜3Pa・sで、降伏値が50Pa以下、好ましくは5〜8Pa程度であることが望ましい。これらの範囲外では、塗料組成物を作成したときに、へら付けなどの塗布がしにくくなる恐れがあるので望ましくない。ここで、粘度は、25℃において「レオメーターMR−300」(レオロジー(株)製)を用いて、ずり速度100sec−1の条件で測定された値であり、降伏値は、同装置を用いて、ずり速度を変化させてずり応力を測定し「CASSONの式」から求められる値である。
【0017】
本発明において塩素化ポリオレフィン系樹脂(B)は、主に、ポリオレフィン類又はこれを(無水)不飽和カルボン酸等で変性してなる変性体を、塩素化してなるものである。
【0018】
ポリオレフィン類としては、例えばエチレン、プロピレン、ブテン、3−メチル−1−ブテン、3−メチル−1−ヘプテン等から選ばれたオレフィン類の単独重合体又は共重合体、及び該オレフィン類と酢酸ビニル、ブタジエン、アクリル酸エステル、メタクリル酸エステル等との共重合体があげられる。具体的には、塩素化ポリエチレン、塩素化ポリプロピレン、塩素化エチレン−プロピレン共重合体、塩素化エチレン−酢酸ビニル共重合体等が好適である。
【0019】
これらポリオレフィン類の変性体としては、上記ポリオレフィン類に(無水)不飽和カルボン酸を付加させてなる変性体や、上記ポリオレフィン類に(無水)不飽和カルボン酸及び活性水素化合物を反応させてなる変性体などが好適に使用できる。該(無水)不飽和カルボン酸としては、例えば(無水)マレイン酸、フマル酸、(無水)イタコン酸、(メタ)アクリル酸などが挙げられる。該変性体は、通常、ポリオレフィン類と(無水)不飽和カルボン酸とを有機過酸化物等の存在下で反応させることによって得られる。
【0020】
上記ポリオレフィン又はその変性体の塩素化は、通常、塩素化率が50%以下、好ましくは10〜45%、さらに好ましくは20〜40%となるように、例えば四塩化炭素などの塩素系溶剤にポリオレフィンもしくはその変性体を加熱溶解し、50〜120℃の温度で塩素ガスを吹き込み反応させるなどして得ることができる。
【0021】
塩素化ポリオレフィン系樹脂(B)としては、上記ポリオレフィン類又はこれを(無水)不飽和カルボン酸等で変性してなる変性体を塩素化してなるものに、アクリル樹脂をグラフト化反応せしめてなるアクリル変性の塩素化ポリオレフィンを用いても良い。
【0022】
該アクリル変性の塩素化ポリオレフィンは、通常、ポリオレフィン又はその変性体の塩素化物の存在下で、アクリル樹脂を形成する重合性不飽和モノマー混合物を滴下し、グラフト化反応させることによって得られる。該反応は、有機溶剤中で、通常、60〜100℃程度の重合温度で、ベンゾイルパーオキサイドやアゾイソブチロニトリルなどのラジカル重合開始剤の存在下、それ自体既知の重合方法、例えば溶液重合等によって行われる。
【0023】
グラフト重合時に滴下させる重合性不飽和モノマーとしては、例えばメチル(メタ)アクリレート、エチル(メタ)アクリレート、n−、i−プロピル(メタ)アクリレート、n−、i−、t−ブチル(メタ)アクリレート、2−エチルヘキシルアクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、トリデシル(メタ)アクリレート、ステアリル(メタ)アクリレート等のアクリル酸又はメタクリル酸のアルキル(炭素数1〜20)エステル;2−ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、4−ヒドロキシブチル(メタ)アクリレート等の、多価アルコールとアクリル酸又はメタクリル酸とのモノエステル化物:アクリル酸、メタクリル酸、マレイン酸、フマル酸等の重合性不飽和カルボン酸;グリシジル(メタ)アクリレート、アクリロニトリル、メタクリロニトリル、酢酸ビニル、スチレン、ビニルトルエン、α−メチルスチレン等が挙げられ、これらは1種又は2種以上併用して使用できる。
【0024】
上記塩素化ポリオレフィン系樹脂(B)の重量平均分子量は、通常、2,000〜300,000程度、特に5,000〜100,000程度であることが好ましい。
【0025】
上記塩素化ポリオレフィン系樹脂(B)の含有量は、(A)成分の樹脂固形分100重量部に対して固形分で5〜25重量部、好ましくは7.5〜22重量部であることが、プラスチック部材に対する付着性と、塗料組成物の貯蔵安定性の点から望ましい。該含有量が5重量部未満ではプラスチック部材に対する付着性が確保できず、25重量部を越えると塗料粘度が低くタレ易くニス分かれが発生する恐れがあるので望ましくない。
【0026】
本発明において顔料(C)としては、例えばタルク、マイカ、硫酸バリウム、カオリン、炭酸カルシウム、クレ−、シリカ、石英、ガラスなどの体質顔料、チタン白、ベンガラ、カ−ボンブラック、鉄黒などの着色顔料が挙げられ、さらにガラスバルーン、プラスチックバルーンなども含むことができる。該顔料(C)の含有量は、樹脂固形分100重量部に対し100〜500重量部の範囲内である。該含有量が100重量部未満では、研磨作業性が劣り、一方500重量部を超えると上塗り塗装後の仕上り性が低下するので好ましくない。該顔料(C)の分散には、顔料分散剤を用いることが望ましく、特に3級アミノ基含有分散剤が分散ペーストの低粘度化の点から好適に使用できる。
【0027】
本発明において樹脂微粒子(D)としては、従来公知のポリマ−ビ−ズなどの樹脂粒子や前記モノマ−類の重合物を微細に粉砕したもの、さらにゲル化重合体微粒子(例えば、特開昭51−126287号公報、特開昭53−133233号公報、特開昭53−133236号公報、特開昭56−76447号公報、特開昭58−129065号公報参照)などが挙げられ、特に分子内に少なくとも2個のラジカル重合可能な不飽和基を有する重合性モノマー及びその他のラジカル重合性不飽和モノマーを、分子内にアリル基を含有する反応性乳化剤の存在下で、乳化重合せしめて得られるゲル化重合体微粒子(例えば、特開平3−66770号公報参照)が(A)、(B)及び(C)成分に対する分散性に優れるので好適に使用できる。
【0028】
該ゲル化重合体微粒子の製造に用いられる分子内に少なくとも2個のラジカル重合可能な不飽和基を有する重合性モノマーとしては、例えばエチレングリコ−ルジ(メタ)アクリレ−ト、1,6−ヘキサンジオ−ルジアクリレ−トなどが挙げられ、その他のラジカル重合性不飽和モノマ−としては、例えば(メタ)アクリル酸アルキルエステル、水酸基含有モノマ−、スチレンなどの従来公知の重合性不飽和モノマ−が挙げられ適宜選択されるものである。また乳化重合時の重合開始剤として水溶性アゾアミド化合物などを用いることができる。
【0029】
上記樹脂微粒子(D)の粒径は、特に制限なく適宜選択できるが、通常30μm以下、、好ましくは0.05〜10μmの範囲内が適当である。粒径の調整は、従来公知の方法で行え、例えば上記ゲル化重合体微粒子であれば反応性乳化剤の種類や量を調整することで可能である。
【0030】
樹脂微粒子(D)は、上記(C)成分の含有重量に対して固形分で0.1〜35重量%、好ましくは1〜30重量%となるように配合される。該樹脂微粒子(D)の含有率が35重量%を越えて多いと、塗料粘度が高くなり過ぎてヘラ付けなどの塗布が不可能となり、一方0.1重量%未満では塗料粘度が低くヘラ付けが困難となるので好ましくない。該樹脂微粒子(D)の配合量によって、各種のパテやプラサフに必要な粘性挙動に制御することが可能である。
【0031】
本発明の塗料組成物には、必要に応じて可塑剤、硬化促進剤、硬化遅延剤、消泡剤、有機溶剤などの添加剤や、変性ヒマシ油系、有機アミド系などのレオロジー添加剤を配合することができる。
【0032】
上記の通り得られる本発明の塗料組成物は、25℃における粘度が25Pa・s以下、好ましくは20Pa・s以下、降伏値が80Pa以上、より好ましくは100Pa以上であることが好適である。粘度が25Pa・sを超えるとへら付けなどの塗布がしにくくなり、降伏値が80Pa未満の場合は、垂直面に塗布したときにタレが発生するので望ましくない。ここで、粘度は、25℃において「レオメーターMR−300」(レオロジー(株)製)を用いて、ずり速度100sec−1の条件で測定された値であり、降伏値は、同装置を用いて、ずり速度を変化させてずり応力を測定し「CASSONの式」から求められる値である。
【0033】
本発明では、上記の通り得られる下地塗料組成物を用いて補修塗装を行なうことで、プラスチック部材面に該下地塗料組成物を直接塗布することができ、該下地塗装後に、さらに上塗り塗装を行なうことができる。
【0034】
上記組成物を用いた補修塗装時の下地処理方法としては、まず、塗膜の損傷部分を必要に応じて脱脂し、次いで該部分に本発明の塗料組成物をパテとして直接充填する。パテの充填はヘラを用いるなどにより、それ自体既知の方法で行える。パテの塗布面が乾燥したら、必要に応じて研磨することができる。またパテ面の素穴をうめる最終仕上げ段階のグレーチングパテとしても上記塗料組成物を用いることができる。その場合には該塗料組成物を有機溶剤で攪拌しながら適宜希釈することによって使用可能である。使用する有機溶剤の割合は所望の粘度、降伏値の如何によって適宜選択でき、特に25℃における粘度が5〜10Pa・s、降伏値が400〜700Paの範囲内となるように調整することがグレーチングパテとして好適である。
【0035】
【実施例】
以下、実施例を挙げて本発明をさらに詳細に説明する。尚、「部」及び「%」はそれぞれ「重量部」及び「重量%」を示す。
【0036】
樹脂微粒子の製造
攪拌装置、温度計、冷却管及び加熱マントルを備えた1リットルフラスコに、脱イオン水3547.5部と「ラテムルS−120A」(花王社製、スルホコハク酸系アリル基含有アニオン性反応性乳化剤、50%水溶液)40部を加えて攪拌しながら90℃まで昇温した。次いでこの中に「VA−086」(和光純薬工業社製、水溶性アゾアミド重合開始剤)12.5部を脱イオン水500部に溶解した水溶液の20%を加えた。15分後にスチレン300部、メチルメタクリレ−ト400部、n−ブチルアクリレ−ト200部、1,6−ヘキサンジオ−ルジアクリレ−ト100部からなるモノマ−混合物の5%を加え、30分間攪拌した。その後、さらに残りのモノマ−混合物及び重合開始剤水溶液の滴下を開始し、モノマ−混合物の滴下は3時間で、重合開始剤水溶液の滴下は3.5時間かけてそれぞれ行ない、その間90℃に保持した。重合開始剤水溶液の滴下終了後、さらに30分間90℃に保持してから室温に冷却し、濾布を用いて取り出し、固形分20%の水性ゲル化微粒子重合体水分散液を得た。その粒径は72nmであった。これをステンレスパット上で乾燥させ樹脂微粒子Gを得た。
【0037】
塗料組成物の作成
実施例1
固形分60%のアルキド樹脂溶液(注1)18.7部、ジブチルフタレート1.1部、ニトロセルロース(注2)7.5部及びキシレン35.8部の混合液に、水和酸化鉄(オキサイドエロー)0.3部、ベンガラ2.8部、カーボンブラック0.2部、チタン白8.4部、タルク9.3部、炭酸カルシウム9.3部、上記で得た樹脂微粒子Gを6.5部、及び固形分20%の塩素化ポリオレフィン系樹脂溶液(注3)20部を順次配合して混合・攪拌し、30分間分散処理して塗料組成物を得た。この塗料組成物の25℃における粘度及び降伏値を、「レオメーターMR−300」(レオロジー(株)製)を用いて測定した。
【0038】
また得られた塗料組成物をパテとして直ちに脱脂処理した軟鋼板を垂直に立てて、その板面上にヘラにて厚さ約2mmとなるように盛り付けた。へら付け時のパテの伸び(◎:非常に良く伸びる、○:良く伸び、塗り易い、△:あまり伸びない、×:全く伸びない)と、垂直面からのパテのタレ具合(◎:全くタレない、○:ほぼタレない、△:少しタレる、×:筋状にタレる)を夫々評価した。
【0039】
さらにポリプロピレン板(研磨剤入洗剤とスポンジを使って、素材表面の足付けと脱脂を行なったもの)に、上記で得た塗料組成物をヘラにて厚さ約2mmとなるように盛り付けて室温で放置乾燥後、耐水ペーパー#400で研磨してから、その塗面に2液型アクリルウレタン樹脂系上塗り塗料(「レタンPGハイブリッド」、関西ペイント社製)を乾燥膜厚が約30μmになるようにスプレー塗装を行ない、80℃で30分間加熱して硬化させて試験塗板を作成した。この試験塗板について初期の付着性と、20℃で7日間の没水試験後の付着性を次の通り評価した。塗膜面に素地に達するようにカッターで切り込み線を入れ、大きさ2mm×2mmのマス目を100個作り、その表面に粘着セロハンテープを貼着し、20℃においてそれを急激に剥離した後のマス目の残存塗膜数を調べた(○は100個残存、△は99〜95個残存、×は94個以下残存を示す)。結果を表2に示す。
【0040】
(注1)アルキド樹脂溶液:「R−540FT」、関西ペイント社製、固形分60%のキシレン/トルエン溶液
(注2)ニトロセルロース:「ショウカメンRS−1/2MW」、ダイセル化学工業社製
(注3)塩素化ポリプロピレン系樹脂溶液:「スーパークロン851L」、日本製紙社製、固形分20%有機溶剤溶液
【0041】
実施例2〜3比較例1〜4
実施例1において、表1の配合組成とする以外は実施例1と同様の操作で各塗料組成物を得た。各塗料組成物の粘度及び降伏値を測定し、またへら付け時のパテの伸びと、垂直面からのパテのタレ具合、塗膜の付着性を夫々評価した。結果を表2に示す。また各塗料組成物を室温にて1ヶ月貯蔵したところ、比較例4の塗料組成物が塩素化ポリプロピレンの分離を起こしていた。
【0042】
表1中の(注4)〜(注6)は下記の通りである。
(注4)アクリル樹脂溶液:「KH130」、関西ペイント社製、固形分55%のキシレン溶液
(注5)「CAB 381−0.5」、イーストマンケミカルズ社製、セルロースアセテートブチレート
(注6)「CAB 381−0.1」、イーストマンケミカルズ社製、セルロースアセテートブチレート
【0043】
【表1】

Figure 2004075893
【0044】
【表2】
Figure 2004075893
【0045】
【発明の効果】
本発明の下地塗料組成物によれば、専用プライマーを使用せずとも、バンパーやドアミラーカバーなどのプラスチック部材に直接塗着可能であり、特に自動車補修用等のパテやプライマーサーフェーサーとして好適に使用できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a base coating composition for a plastic member that can be directly applied to a plastic member such as a bumper or a door mirror cover without using a dedicated primer.
[0002]
[Prior art and its problems]
Currently, automotive parts such as bumpers and door mirror covers are mainly made of polyolefin resin such as polypropylene. Polyolefin resin materials are excellent in moldability and chemical resistance, but have very poor adhesion when coated on the surface. For this reason, when the base material is exposed, the polyolefin resin material is used to repair the damaged part of the bumper surface. After applying a special primer composed of the chlorinated polyolefin resin with good adhesion to the material, paint the putty and primer surfacer. It is common to do.
[0003]
However, even with the above-mentioned dedicated primer, the compatibility between the room temperature drying type base resin component used in the field of repair coating and the chlorinated polyolefin resin is poor, the adhesion is insufficient, or the process by the dedicated primer coating process The increase was also disadvantageous and problematic.
[0004]
An object of the present invention is to provide a base coating composition for a plastic member that can be directly applied to a plastic member made of a polyolefin material without using a dedicated primer and can be used as a putty or a primer surfacer.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors blended a chlorinated polyolefin into a resin composition used for putty and prassaf, and further blended a specific amount of resin fine particles to obtain a chlorinated polyolefin. The inventors have found that a coating film that can be uniformly dispersed in a paint and has excellent adhesion to a plastic member made of a polyolefin material can be formed, and the present invention has been completed.
[0006]
That is, the present invention
1. (A) A room temperature drying resin composition, (B) a chlorinated polyolefin resin, (C) a pigment and (D) a base coating composition containing fine resin particles, wherein the content of the component (C) is ( The component (A) is 100 to 500 parts by weight with respect to 100 parts by weight of the resin solid content, and the content of the component (D) is 0.1 to 35 with solid content with respect to the content of the component (C). A base coating composition for plastic members, characterized in that it is by weight%,
2. 2. The base coating composition according to 1, wherein the room temperature drying resin composition (A) comprises an acrylic resin or alkyd resin system, and a fiber derivative system;
3. The base coating composition according to 1, wherein the content of the component (B) is 5 to 25 parts by weight in solid content with respect to 100 parts by weight of the resin solid content of the component (A),
4). A repair coating method comprising applying a base coating composition according to any one of 1 to 3 to a plastic member surface, and further performing a top coating.
Is to provide.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, as the room-temperature drying resin composition (A), conventionally known plating patties, resin patties, and low-viscosity resin compositions for Prasaf are applicable. For example, a fiber derivative system, an unsaturated polyester resin system , Epoxy acrylate resin, epoxy resin, acrylic resin, alkyd resin, urethane resin, and the like. Among these, in particular, a resin composition (A-1) containing an unsaturated polyester resin and a polymerizable unsaturated monomer, and a resin composition (A-2) containing an acrylic resin or alkyd resin and a fiber derivative system Can be suitably used.
[0008]
The unsaturated polyester resin used in the resin composition (A-1) is not particularly limited as long as it is conventionally used for putty. For example, maleic acid, maleic anhydride, fumaric acid, itacone Examples thereof include those obtained by condensation of unsaturated polybasic acids such as acids and polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, and hydrogenated bisphenol A. These are also exemplified by allyl glycidyl ether and allyl glycol. Examples thereof include oils such as allyl compounds, linseed oil, dehydrated castor oil, and the like obtained by condensation in the presence of fatty acids thereof. Furthermore, you may use together with the said unsaturated polybasic acid saturated polybasic acids, such as adipic acid and a phthalic anhydride, as needed.
[0009]
Examples of the polymerizable unsaturated monomer used in the resin composition (A-1) include styrene, α-methylstyrene, vinyltoluene; (meth) such as ethyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. Alkyl ester of acrylic acid; hydroxyalkyl ester of (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate; vinyl acetate, acrylonitrile, and the like. These may be used alone or in combination of two or more. . The use (weight) ratio of the unsaturated polyester resin to the polymerizable unsaturated monomer is preferably in the range of 90/10 to 50/50.
[0010]
An organic peroxide such as methyl ethyl ketone peroxide, benzoyl peroxide, cumene hydroperoxide, or cyclohexanone peroxide can be blended with the resin composition (A-1) as a curing catalyst. The curing catalyst is usually dissolved in a plasticizer or the like and stored as a paste mixed with the components (B) and (C) described below as necessary, and immediately before use, an unsaturated polyester resin or a polymerizable unsaturated monomer. Mixed with.
[0011]
Further, instead of the unsaturated polyester resin of the resin composition (A-1), an epoxy ester resin such as epoxy acrylate obtained by reacting an epoxy resin with an unsaturated carboxylic acid such as acrylic acid or maleic acid may be used. it can.
[0012]
Examples of the epoxy resins include glycidyl ether type epoxy resins such as bisphenol A type epoxy resins, glycidyl ester type epoxy resins, other glycidyl ether type epoxy resins, alicyclic epoxy resins, and these epoxy resins as alkylphenols and / or Examples thereof include low-viscosity epoxy resins such as modified epoxy resins modified with fatty acids, or epoxy group-introduced alkylphenols or alkylphenol novolac resins obtained by reacting alkylphenols or alkylphenol novolac resins with epichlorohydrin.
[0013]
The acrylic resin and alkyd resin used in the resin composition (A-2) can be applied without particular limitation as long as they are conventionally used for lacquer-type Prasaf. For example, use of an acrylic resin having a molecular weight of about 20,000 to 100,000, which is obtained by polymerizing styrene and / or a styrene derivative or an alkyl or cycloalkyl ester of acrylic acid or methacrylic acid by a method known per se. it can. As the alkyd resin system, a resin obtained by esterifying a polybasic acid component, a polyhydric alcohol component, and an oil fatty acid by a method known per se can be used.
[0014]
Examples of the fiber derivative system used in the resin composition (A-2) include cellulose acetate butyrate, cellulose acetate, cellulose acetate propionate, and nitrocellulose (cellulose nitrate). Or it can use in combination of 2 or more types. Moreover, you may mix | blend a plasticizer with the said resin composition (A-2).
[0015]
In the present invention, the resin composition (A-2) is particularly preferable as the room temperature dry resin composition (A).
[0016]
The room temperature dry resin composition (A) is a low-viscosity resin composition, and preferably has a viscosity at 25 ° C. of 5 Pa · s (pascal · second), preferably 1 to 3 Pa · s, and a yield value. The pressure is 50 Pa or less, preferably about 5 to 8 Pa. Outside these ranges, when a coating composition is prepared, it may be difficult to apply spatula or the like, which is not desirable. Here, the viscosity is a value measured using a “Rheometer MR-300” (manufactured by Rheology Co., Ltd.) at 25 ° C. under the condition of a shear rate of 100 sec −1. The shear stress is measured by changing the shear rate, and the value is obtained from the “CASSON formula”.
[0017]
In the present invention, the chlorinated polyolefin resin (B) is mainly formed by chlorinating a polyolefin or a modified product obtained by modifying it with (anhydrous) unsaturated carboxylic acid or the like.
[0018]
Examples of polyolefins include homopolymers or copolymers of olefins selected from, for example, ethylene, propylene, butene, 3-methyl-1-butene, 3-methyl-1-heptene, and the olefins and vinyl acetate. , Butadiene, acrylic acid ester, methacrylic acid ester and the like. Specifically, chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene-propylene copolymer, chlorinated ethylene-vinyl acetate copolymer and the like are preferable.
[0019]
Examples of modified products of these polyolefins include modified products obtained by adding (anhydrous) unsaturated carboxylic acids to the above polyolefins, and modified products obtained by reacting (anhydrous) unsaturated carboxylic acids and active hydrogen compounds with the above polyolefins. A body etc. can be used conveniently. Examples of the (anhydrous) unsaturated carboxylic acid include (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, (meth) acrylic acid and the like. The modified product is usually obtained by reacting polyolefins with (anhydrous) unsaturated carboxylic acid in the presence of an organic peroxide or the like.
[0020]
Chlorination of the polyolefin or a modified product thereof is usually carried out in a chlorinated solvent such as carbon tetrachloride so that the chlorination rate is 50% or less, preferably 10 to 45%, more preferably 20 to 40%. It can be obtained by heating and dissolving polyolefin or a modified product thereof and blowing and reacting with chlorine gas at a temperature of 50 to 120 ° C.
[0021]
As the chlorinated polyolefin resin (B), an acrylic resin obtained by grafting an acrylic resin to a product obtained by chlorinating a modified product obtained by modifying the above polyolefins or this with an (anhydrous) unsaturated carboxylic acid or the like. A modified chlorinated polyolefin may be used.
[0022]
The acrylic-modified chlorinated polyolefin is usually obtained by dropping a polymerizable unsaturated monomer mixture that forms an acrylic resin in the presence of a polyolefin or a chlorinated product of a modified product thereof and causing a grafting reaction. The reaction is carried out in an organic solvent, usually at a polymerization temperature of about 60 to 100 ° C., in the presence of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile, for example, a polymerization method known per se. Etc.
[0023]
Examples of the polymerizable unsaturated monomer dropped during the graft polymerization include methyl (meth) acrylate, ethyl (meth) acrylate, n-, i-propyl (meth) acrylate, n-, i-, and t-butyl (meth) acrylate. Alkyl (carbon number 1 to 20) esters of acrylic acid or methacrylic acid such as 2-ethylhexyl acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate; Monoesterified product of polyhydric alcohol and acrylic acid or methacrylic acid such as ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate: acrylic acid, methacrylic acid, maleic acid, Polymerizable unsaturated carboxylic acids such as phosphoric acid; glycidyl (meth) acrylate, acrylonitrile, methacrylonitrile, vinyl acetate, styrene, vinyltoluene, α-methylstyrene, and the like. These may be used alone or in combination of two or more. Can be used.
[0024]
The weight average molecular weight of the chlorinated polyolefin resin (B) is usually about 2,000 to 300,000, particularly preferably about 5,000 to 100,000.
[0025]
The content of the chlorinated polyolefin resin (B) is 5 to 25 parts by weight, preferably 7.5 to 22 parts by weight, based on 100 parts by weight of the resin solid content of the component (A). From the viewpoint of adhesion to a plastic member and storage stability of the coating composition. If the content is less than 5 parts by weight, adhesion to a plastic member cannot be ensured, and if it exceeds 25 parts by weight, the viscosity of the paint is low and the varnish may be easily separated.
[0026]
In the present invention, examples of the pigment (C) include extender pigments such as talc, mica, barium sulfate, kaolin, calcium carbonate, clay, silica, quartz, and glass, titanium white, bengara, carbon black, and iron black. Examples of the color pigment include glass balloons and plastic balloons. Content of this pigment (C) exists in the range of 100-500 weight part with respect to 100 weight part of resin solid content. If the content is less than 100 parts by weight, the polishing workability is inferior. On the other hand, if it exceeds 500 parts by weight, the finish after the top coating is lowered, which is not preferable. For dispersing the pigment (C), it is desirable to use a pigment dispersant, and in particular, a tertiary amino group-containing dispersant can be suitably used from the viewpoint of reducing the viscosity of the dispersion paste.
[0027]
In the present invention, the resin fine particles (D) include finely pulverized resin particles such as conventionally known polymer beads and polymers of the aforementioned monomers, and gelled polymer fine particles (for example, JP-A 51-126287, JP-A-53-133233, JP-A-53-133236, JP-A-56-76447, JP-A-58-129065) and the like. Obtained by emulsion polymerization of a polymerizable monomer having at least two radically polymerizable unsaturated groups and other radically polymerizable unsaturated monomers in the presence of a reactive emulsifier containing an allyl group in the molecule. The resulting gelled polymer fine particles (see, for example, JP-A-3-66770) are excellent in dispersibility with respect to the components (A), (B) and (C) and can be preferably used.
[0028]
Examples of the polymerizable monomer having at least two radically polymerizable unsaturated groups in the molecule used for the production of the gelled polymer fine particles include ethylene glycol di (meth) acrylate and 1,6-hexanediol. -Other examples of the radically polymerizable unsaturated monomer include conventionally known polymerizable unsaturated monomers such as (meth) acrylic acid alkyl ester, hydroxyl group-containing monomer, styrene and the like. It is appropriately selected. Moreover, a water-soluble azoamide compound etc. can be used as a polymerization initiator at the time of emulsion polymerization.
[0029]
The particle diameter of the resin fine particles (D) can be appropriately selected without particular limitation, but is usually 30 μm or less, preferably 0.05 to 10 μm. The particle diameter can be adjusted by a conventionally known method. For example, the gelled polymer fine particles can be adjusted by adjusting the type and amount of the reactive emulsifier.
[0030]
The resin fine particles (D) are blended so that the solid content is 0.1 to 35% by weight, preferably 1 to 30% by weight, based on the content of the component (C). If the content of the resin fine particles (D) exceeds 35% by weight, the viscosity of the coating becomes too high and application such as spatula is impossible. On the other hand, if the content is less than 0.1% by weight, the viscosity of the coating is low. Is not preferable because it becomes difficult. It is possible to control the viscous behavior required for various putties and prassuffs depending on the blending amount of the resin fine particles (D).
[0031]
In the coating composition of the present invention, additives such as a plasticizer, a curing accelerator, a curing retarder, an antifoaming agent, and an organic solvent, and a rheological additive such as a modified castor oil type and an organic amide type are added as necessary. Can be blended.
[0032]
The coating composition of the present invention obtained as described above preferably has a viscosity at 25 ° C. of 25 Pa · s or less, preferably 20 Pa · s or less, and a yield value of 80 Pa or more, more preferably 100 Pa or more. When the viscosity exceeds 25 Pa · s, application such as spatula is difficult, and when the yield value is less than 80 Pa, sagging occurs when applied to a vertical surface, which is not desirable. Here, the viscosity is a value measured using a “Rheometer MR-300” (manufactured by Rheology Co., Ltd.) at 25 ° C. under the condition of a shear rate of 100 sec −1. The shear stress is measured by changing the shear rate, and the value is obtained from the “CASSON formula”.
[0033]
In the present invention, by performing repair coating using the base coating composition obtained as described above, the base coating composition can be directly applied to the plastic member surface, and after the base coating, further top coating is performed. be able to.
[0034]
As a ground treatment method for repair coating using the above composition, first, a damaged portion of the coating film is degreased as necessary, and then the coating composition of the present invention is directly filled in the portion as a putty. The putty can be filled by a method known per se by using a spatula. Once the putty application surface is dry, it can be polished if necessary. The coating composition can also be used as a grating putty in the final finishing stage in which the hole on the putty surface is filled. In that case, the coating composition can be used by appropriately diluting it with stirring with an organic solvent. The ratio of the organic solvent to be used can be appropriately selected depending on the desired viscosity and yield value. In particular, the grating is adjusted so that the viscosity at 25 ° C. is in the range of 5 to 10 Pa · s and the yield value is in the range of 400 to 700 Pa. Suitable as putty.
[0035]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. “Parts” and “%” indicate “parts by weight” and “% by weight”, respectively.
[0036]
Production of resin fine particles In a 1 liter flask equipped with a stirrer, a thermometer, a cooling tube and a heating mantle, 3547.5 parts of deionized water and "Latemul S-120A" (manufactured by Kao Corporation, sulfosuccinic acid-based allyl) 40 parts of a group-containing anionic reactive emulsifier, 50% aqueous solution) was added and the temperature was raised to 90 ° C. with stirring. Next, 20% of an aqueous solution obtained by dissolving 12.5 parts of “VA-086” (manufactured by Wako Pure Chemical Industries, Ltd., water-soluble azoamide polymerization initiator) in 500 parts of deionized water was added thereto. After 15 minutes, 5% of a monomer mixture comprising 300 parts of styrene, 400 parts of methyl methacrylate, 200 parts of n-butyl acrylate and 100 parts of 1,6-hexanediol diacrylate was added and stirred for 30 minutes. Thereafter, the dropping of the remaining monomer mixture and the polymerization initiator aqueous solution was started, the monomer mixture was dropped for 3 hours, and the polymerization initiator aqueous solution was dropped for 3.5 hours, and maintained at 90 ° C. during that time. did. After completion of the dropwise addition of the polymerization initiator aqueous solution, the mixture was kept at 90 ° C. for 30 minutes, cooled to room temperature, and taken out using a filter cloth to obtain an aqueous gelled fine particle polymer aqueous dispersion having a solid content of 20%. Its particle size was 72 nm. This was dried on a stainless steel pad to obtain resin fine particles G.
[0037]
Creating coating compositions <br/> Example 1
To a mixed liquid of 18.7 parts of an alkyd resin solution (Note 1) having a solid content of 60%, 1.1 parts of dibutyl phthalate, 7.5 parts of nitrocellulose (Note 2) and 35.8 parts of xylene, hydrated iron oxide ( Oxide Yellow) 0.3 parts, 2.8 parts Bengala, 0.2 parts carbon black, 8.4 parts titanium white, 9.3 parts talc, 9.3 parts calcium carbonate, 6 resin fine particles G obtained above .5 parts and 20 parts of a 20% solid content chlorinated polyolefin resin solution (Note 3) were sequentially blended, mixed and stirred, and dispersed for 30 minutes to obtain a coating composition. The viscosity and yield value of this coating composition at 25 ° C. were measured using “Rheometer MR-300” (manufactured by Rheology Co., Ltd.).
[0038]
Further, a mild steel plate immediately degreased using the obtained coating composition as a putty was set up vertically and placed on the plate surface with a spatula to a thickness of about 2 mm. Elongation of putty during spatula (◎: stretches very well, ○: stretches well, easy to apply, △: does not stretch very much, x: does not stretch at all) and sagging state of putty from vertical surface (◎: completely sagging) No, o: almost no sagging, Δ: sagging a little, x: sagging in a streak).
[0039]
In addition, the coating composition obtained above is placed on a polypropylene plate (with a detergent and a sponge containing an abrasive and the surface of the material is added and degreased) with a spatula to a thickness of about 2 mm. After being left to dry, and then polished with water-resistant paper # 400, a two-component acrylic urethane resin-based top coating (“Letane PG Hybrid”, manufactured by Kansai Paint Co., Ltd.) is applied to the coated surface so that the dry film thickness is about 30 μm. Spray coating was performed, and the test coating plate was prepared by heating at 80 ° C. for 30 minutes to cure. The initial adhesion and the adhesion after a submersion test for 7 days at 20 ° C. were evaluated as follows. After making a cut line with a cutter to reach the substrate on the coating surface, making 100 squares with a size of 2 mm x 2 mm, sticking adhesive cellophane tape on the surface, and peeling it off rapidly at 20 ° C The number of remaining coatings in the squares was examined (◯ indicates 100 remaining, Δ indicates 99 to 95, and × indicates 94 or less remaining). The results are shown in Table 2.
[0040]
(Note 1) Alkyd resin solution: “R-540FT”, manufactured by Kansai Paint, 60% solids xylene / toluene solution (Note 2) Nitrocellulose: “Shokamen RS-1 / 2MW”, manufactured by Daicel Chemical Industries, Ltd. ( Note 3) Chlorinated polypropylene resin solution: “Super Clon 851L”, manufactured by Nippon Paper Industries Co., Ltd., 20% solid content organic solvent solution
Examples 2-3 Comparative Examples 1-4
In Example 1, each coating composition was obtained in the same manner as in Example 1 except that the composition shown in Table 1 was used. The viscosity and yield value of each coating composition were measured, and the putty elongation at the time of spatulating, the sagging condition of the putty from the vertical surface, and the adhesion of the coating film were evaluated. The results are shown in Table 2. Moreover, when each coating composition was stored at room temperature for one month, the coating composition of Comparative Example 4 caused separation of chlorinated polypropylene.
[0042]
(Note 4) to (Note 6) in Table 1 are as follows.
(Note 4) Acrylic resin solution: “KH130”, manufactured by Kansai Paint, xylene solution with a solid content of 55% (Note 5) “CAB 381-0.5”, manufactured by Eastman Chemicals, cellulose acetate butyrate (Note 6) ) "CAB 381-0.1", manufactured by Eastman Chemicals, cellulose acetate butyrate
[Table 1]
Figure 2004075893
[0044]
[Table 2]
Figure 2004075893
[0045]
【The invention's effect】
According to the base coating composition of the present invention, it can be directly applied to a plastic member such as a bumper or a door mirror cover without using a dedicated primer, and can be suitably used as a putty or primer surfacer for repairing automobiles. .

Claims (4)

(A)常温乾燥型樹脂組成物、(B)塩素化ポリオレフィン系樹脂、(C)顔料及び(D)樹脂微粒子を含有する下地塗料組成物であって、該(C)成分の含有量が(A)成分の樹脂固形分100重量部に対し100〜500重量部で、且つ該(D)成分の含有量が(C)成分の含有重量に対してに対して固形分で0.1〜35重量%であることを特徴とするプラスチック部材用下地塗料組成物。(A) A room temperature drying resin composition, (B) a chlorinated polyolefin resin, (C) a pigment, and (D) a base coating composition containing fine resin particles, wherein the content of the component (C) is ( The component (A) is 100 to 500 parts by weight with respect to 100 parts by weight of the resin solid content, and the content of the component (D) is 0.1 to 35 with solid content with respect to the content of the component (C) An undercoating composition for plastic members, characterized in that it is in weight percent. 常温乾燥型樹脂組成物(A)が、アクリル樹脂系又はアルキド樹脂系、及び繊維素誘導体系を含むものである請求項1記載の下地塗料組成物。The base coating composition according to claim 1, wherein the room temperature dry resin composition (A) comprises an acrylic resin or alkyd resin system and a fiber derivative system. (B)成分の含有量が、(A)成分の樹脂固形分100重量部に対して固形分で5〜25重量部である請求項1記載の下地塗料組成物。The base coating composition according to claim 1, wherein the content of the component (B) is 5 to 25 parts by weight in solid content with respect to 100 parts by weight of the resin solid content of the component (A). プラスチック部材面に、請求項1ないし3のいずれか1項記載の下地塗料組成物を塗布した後、さらに上塗り塗装を行なうことを特徴とする補修塗装方法。A repair coating method comprising applying a base coating composition according to any one of claims 1 to 3 to a plastic member surface, and further performing a top coating.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101286840B1 (en) 2006-07-20 2013-07-17 현대모비스 주식회사 Coating composition for plastic and eletro deposition coating of automobile
JP2015134331A (en) * 2014-01-17 2015-07-27 株式会社コバテクノロジー Repair method for vehicle components
CN106221448A (en) * 2016-07-28 2016-12-14 上海维凯光电新材料有限公司 Low VOC easy offset printing cold wave releasing layer coating and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101286840B1 (en) 2006-07-20 2013-07-17 현대모비스 주식회사 Coating composition for plastic and eletro deposition coating of automobile
JP2015134331A (en) * 2014-01-17 2015-07-27 株式会社コバテクノロジー Repair method for vehicle components
CN106221448A (en) * 2016-07-28 2016-12-14 上海维凯光电新材料有限公司 Low VOC easy offset printing cold wave releasing layer coating and preparation method thereof

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