JP2004237161A - Method for producing car body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a car body which can simply and effectively repair the hydrophilized defective part of the surface of the car body in the production of a car and can produce the car body excellent in glossiness. <P>SOLUTION: In the method for producing the car body excellent in glossiness, in a process for finishing the paint film of the car body coated with a surface hydrophilizing coating containing a hydrophilizing agent comprising a silicon compound and/or its condensate, a hydrophilized wax composition containing the hydrophilizing agent is applied to a surface hydrophilized defective part produced by polishing the defective part of the paint film and wiped off, the hydrolyzable group of the hydrophilizing agent is converted in situ in the presence of water into a hydrophilic group and condensed, and the hydrophilizing agent is polymerized, so that the hydrophilized wax composition layer is formed at least in the surface hydrophilized defective part, and its surface is hydrophilized and repaired. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００２０】
などがあげられるが、親水性、相溶性、密着性の点からＯＣＮ（ＣＨ_２）_３、ＣＨ_３Ｏ（ＣＨ_２ＣＨ_２Ｏ）_５（ＣＨ_２）_３が好ましい。
【００２１】
（３）また前記有機基Ｘは、たとえば酸素原子、チッ素原子、フッ素原子、塩素原子、ケイ素原子などを含んでいてもよい重合性の有機基があげられる。
【００２２】
これらの具体例は、たとえばＣＨ_２＝Ｃ（ＣＨ_３）ＣＯ_２（ＣＨ_２）_３、ＣＨ_２＝ＣＨ、ＣＨ_２＝ＣＨＣＨ_２、ＣＨ_２＝ＣＨＯ（ＣＨ_２）_３、ＣＨ_２＝ＣＨＯＣＯ（ＣＨ_２）_３、ＣＨ_２＝ＣＨＣ_６Ｈ_４、ＣＨ_２＝ＣＨＣＯ_２（ＣＨ_２）_３などがあげられるが、重合性、入手の容易さの点からＣＨ_２＝Ｃ（ＣＨ_３）ＣＯ_２（ＣＨ_２）_３、ＣＨ_２＝ＣＨＯ（ＣＨ_２）_３が好ましい。
【００２３】
なお、本発明においては、このような重合性の有機基を有する式（１）で示される化合物を重合または共重合して得られ、分子量が５００〜１００，０００、好ましくは１０００〜２０，０００の重合体または共重合体も好ましいものである。
【００２４】
前記Ｒ^１は、同じかまたは異なりいずれも酸素原子、チッ素原子、フッ素原子および／または塩素原子を含んでいてもよく、表面配向性、加水分解性、脱離性の点から炭素数１〜１０００の１価の有機基、シロキサン残基または水素原子であり、前記炭素数としては１〜１００であることが好ましく、１〜１６であることがさらに好ましい。
【００２５】
前記Ｒ^１のうちの１価の有機基は、たとえばＨ（ＣＨ_２）_ｍ、（ＣＨ_３）_２ＣＨ、Ｈ（ＣＨ_２）_ｍＣ＝Ｏ、Ｆ（ＣＦ_２）_ｎ（ＣＨ_２）_ｍ、（ＣＦ_３）_２ＣＨ、Ｈ（ＣＦ_２）_ｎ（ＣＨ_２）_ｍ、Ｆ（ＣＦ_２）_ｎ（ＣＨ_２）_ｍＣ＝Ｏ、Ｈ（ＣＦ_２）_ｎ（ＣＨ_２）_ｍＣ＝Ｏ、（Ｆ（ＣＦ_２）_ｎ（ＣＨ_２）_ｍ）_２Ｎ、（（ＣＦ_３）_２ＣＨ）_２Ｎ、（Ｈ（ＣＦ_２）_ｎ（ＣＨ_２）_ｍ）_２Ｎ、Ｆ（ＣＦ_２）_ｎＯ（ＣＦ（ＣＦ_３）ＣＦ_２Ｏ）_ｍＣＦ（ＣＦ_３）Ｃ＝Ｏ、（Ｆ（ＣＦ_２）_ｎ（ＣＨ_２）_ｍ）_２Ｃ＝Ｎ、（（ＣＦ_３）_２ＣＨ）_２Ｃ＝Ｎ、（Ｈ（ＣＦ_２）_ｎ（ＣＨ_２）_ｍ）_２Ｃ＝Ｎ、Ｆ（ＣＦ_２）_ｎ（ＣＨ_２）_ｍＣ＝ＯＮＲ^３、Ｈ（ＣＦ_２）_ｎ（ＣＨ_２）_ｍＣ＝ＯＮＲ^３、Ｆ（ＣＦ_２）_ｎ（ＣＨ_２）_ｍＣ＝ＣＨ_２、Ｈ（ＣＦ_２）_ｎ（ＣＨ_２）_ｍＣ＝ＣＨ_２、Ｆ（ＣＦ_２）_ｎ（ＣＨ_２）_ｍＣ＝ＣＦ_２、Ｈ（ＣＦ_２）_ｎ（ＣＨ_２）_ｍＣ＝ＣＦ_２（式中、ｍは０または１〜６の整数、ｎは１〜１０の整数、Ｒ^３は炭素数１〜６のアルキル基を表わし、アルキル基は直鎖でも分岐鎖でもよい）で示されるものが好ましい。
【００２６】
これらの有機基の具体例としては、たとえばＣＦ_３ＣＨ_２、ＣＦ_３ＣＦ_２ＣＨ_２、ＣＦ_３ＣＨＦＣＦ_２ＣＨ_２、ＣＦ_３（ＣＦ_２）_２ＣＨ_２、ＣＦ_３（ＣＦ_２）_３ＣＨ_２ＣＨ_２、（ＣＦ_３）_２ＣＨ、ＣＦ_３（ＣＦ_２）_７ＣＨ_２ＣＨ_２、Ｈ（ＣＦ_２）_２ＣＨ_２、Ｈ（ＣＦ_２）_３ＣＨ_２、Ｈ（ＣＦ_２）_４ＣＨ_２、ＣＦ_３Ｃ＝Ｏ、ＣＦ_３ＣＦ_２Ｃ＝Ｏ、ＣＦ_３（ＣＦ_２）_６Ｃ＝Ｏ、ＣＦ_３（ＣＦ_２）_７Ｃ＝Ｏなどがあげられるが、表面配向性、加水分解性、脱離性の点からＣＦ_３ＣＨ_２、ＣＦ_３ＣＦ_２ＣＨ_２、ＣＦ_３ＣＨＦＣＦ_２ＣＨ_２、ＣＦ_３（ＣＦ_２）_２ＣＨ_２、ＣＦ_３（ＣＦ_２）_３ＣＨ_２ＣＨ_２、ＣＦ_３Ｃ＝Ｏ、ＣＦ_３ＣＦ_２Ｃ＝Ｏが好ましくＣＦ_３ＣＨ_２、ＣＦ_３ＣＦ_２ＣＨ_２、ＣＦ_３ＣＨＦＣＦ_２ＣＨ_２がさらに好ましい。
【００２７】
前記Ｒ^１のうちのシロキサン残基は、たとえば（Ｓｉ（ＯＲ^１）_２Ｏ）_ｎＲ^１（式中、Ｒ^１は前記したＲ^１のうちの１価の有機基と同じ）などがあげられる。
【００２８】
前記Ｒ^２は、同じかまたは異なっていてもよく、フッ素原子および／または塩素原子を含んでいてもよいキレート化の能力を有しており、表面配向性、加水分解性、脱離性の点から炭素数が１〜２０であり、２〜１０であることが好ましい有機基である。
【００２９】
本発明においては、このようなキレート化の能力を有する有機基が結合しているケイ素化合物を用いることにより、貯蔵安定性、反応性、溶解性、相溶性により優れているという効果がえられる。
【００３０】
このようなキレート化の能力を有する有機基になりうる化合物としては、たとえば２，４−ペンタンジオン、２，４−ヘプタンジオンなどのβ−ジケトン類、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸ブチルなどのケトステル類、乳酸、乳酸メチル、乳酸エチル、乳酸アンモニウム塩、サリチル酸、サリチル酸メチル、サリチル酸エチル、リンゴ酸、リンゴ酸エチル、酒石酸、酒石酸エチルなどのヒドロキシカルボン酸類またはそのエステル、塩類、４−ヒドロキシ−４−メチル−２−ペンタノン、４−ヒドロキシ−２−ペンタノン、４−ヒドロキシ−２−ヘプタノン、４−ヒドロキシ−４−メチル−２−ヘプタノンなどのケトアルコール類、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ−メチルモノエタノールアミン、Ｎ−エチルモノエタノールアミン、Ｎ，Ｎ−ジメチルエタノールアミン、Ｎ，Ｎ−ジエチルエタノールアミンなどのアミノアルコール類、マロン酸ジエチル、メチロールメラミン、メチロール尿素、メチロールアクリルアミドなどのエノール性活性水素化合物類などが好ましく、これらの水素原子の全部または一部がフッ素原子および／または塩素原子で置換された化合物などが表面配向性の点からさらに好ましい。
【００３１】
本発明におけるケイ素化合物（１）のオリゴマーまたはコオリゴマーとしては、直鎖状、分岐鎖状、環状、三次元化などのオリゴマーまたはコオリゴマーがあげられる。
【００３２】
本発明におけるオリゴマーまたはコオリゴマーの重合度としては高分子量にはならない程度に縮合したものであり、２〜１００が好ましく、４〜２０であることがさらに好ましい。重合度が小さくなるとオリゴマーまたはコオリゴマーが低沸点となりやすく、塗装時に揮発しやすくなり、塗膜に取り込まれにくくなる。重合度が１００を超えると、合成時に重合度の制御が困難となったり、オリゴマーまたはコオリゴマーの粘度が高くなりやすく、作業性に劣る傾向がある。ただし、オリゴマーまたはコオリゴマーが、式（１）においてａが４、ｂが０でフッ素原子を有しているとき、その重合度は作業性、処理面の外観、貯蔵安定性などの点から４を超え３０以下であることが好ましい。
【００３３】
本発明で使用し得る他の親水化剤としては、たとえば
ＣＨ_３Ｏ（Ｓｉ（ＯＣＨ_３）（ＣＨ_３）Ｏ）_ｎＣＨ_３ （ｎ＝２０）、
Ｃ_２Ｈ_５Ｏ（Ｓｉ（ＯＣ_２Ｈ_５）_２Ｏ）_ｍＣ_２Ｈ_５ （ｍ＝８）
で示されるシリケートオリゴマ−などがあげられる。
【００３４】
かかる親水化剤を含む自動車ボディー塗装用の親水化塗料としては、塗料用樹脂、親水化剤、溶剤、他の添加剤からなるものがあげられる。塗料用樹脂としては、フッ素樹脂、アクリル樹脂、ポリエステル樹脂、メラミン樹脂、エポキシ樹脂、ポリウレタン樹脂などがあげられる。溶剤としては、芳香族炭化水素、脂肪族炭化水素、エーテル類、エステル類、エーテルエステル類、ケトン類，アルコール類などがあげられる。他の添加剤としては、紫外線吸収剤、光安定剤、酸化防止剤、粘性調整剤、表面調整剤、顔料などがあげられる。親水化塗料中の親水化剤の配合量は、樹脂１００重量部あたり０．１〜２０重量部、好ましくは１〜１０重量部である。
【００３５】
この親水化塗料を用いて自動車を塗装する方法としては従来公知の方法が採用される。たとえば、金属基材や樹脂基材などの被塗物に直接上塗として塗布する方法、あるいは下塗りした後中塗りし中塗り塗膜上に塗布する方法があげられる。また、塗装系としては単独での１コート塗装、ベースコートとの組み合わせでの２コート塗装、３コート塗装、あるいは上塗り上にオーバーコートとして塗装する方法が採用できる。
【００３６】
塗装によって形成された塗膜には、前述のとおり不可避的にブツなどの塗膜欠陥が生じているので、その部分を研磨して表面の仕上げを行なう。研磨方法としては特に限定されず、砥石で研磨する方法、耐水ペーパーで研磨する方法、コンパウンドで研磨する方法などが採用される。
【００３７】
研磨された自動車ボディーの表面塗膜には当然に親水化状態が損なわれた部分が生ずる。本発明ではかかる親水化不良部分を再度親水化するために前記親水化剤を含む親水化ワックスにより自動車ボディーの表面を処理する。
【００３８】
親水化ワックス処理は、親水化ワックス組成物を自動車ボディーの少なくとも研磨により生じた親水化不良部分に塗布して拭き取り、水分の存在下に前記親水化剤の加水分解性基をその場で親水性基に変換すると共に縮合して、前記親水化剤を高分子量化することにより、少なくとも該表面親水化不良部分に親水化ワックス組成物の層を形成してその表面を親水化して補修する処理である。
【００３９】
親水化ワックス組成物は、前記親水化剤のほかに、ワックス成分、さらに要すれば充填剤、有機溶媒からなるものである。
【００４０】
ワックス成分とは、炭素数が１０〜７０程度の脂肪族飽和炭化水素や脂肪酸とアルコールとのエステルなどの低分子量体（オリゴマー）が主な成分であり、塗料の造膜成分である樹脂のような高分子体（ポリマー）とは明確に区別されるものである。ワックスの特徴としては、常温で固体、または半固体の有機物であり、塗料で用いる樹脂のように塗布して乾燥後に塗膜（フィルム）を形成するものではなく、基材（塗膜）に塗り付けて拭き取る（圧力をかけて塗り広げる）ことにより、はじめて均一なワックス被覆層を形成し、かつ、艶を出す作用を有するものである。
【００４１】
使用するワックス成分としては特に制限はなく、従来公知のものを使用することができる。具体例としては、たとえばカルナバワックス（ロウ）、木ロウ、オウリキュリーロウ、エスパルロウなどの植物ロウ；蜜ロウ、昆虫ロウ、セラックロウ、鯨ロウなどの動物ロウ；パラフィンワックス、マイクロクリスタルワックス、ポリエチレンワックス、エステルワックス、酸化ワックスなどの石油ロウ；モンタンロウ、オゾケライト、セレシンなどの鉱物ロウなどのワックス類、さらに変性ワックス、グリセライド、合成ケトンアミンアマイド、水素化ワックスなどがあげられる。
【００４２】
そのほか、パルミチン酸、ステアリン酸、マルガリン酸、べへン酸などの高級脂肪酸；パルミチルアルコール、ステアリルアルコール、ベヘニルアルコール、マルガニルアルコール、ミリシルアルコール、エイコサノールなどの高級アルコール；パルミチン酸セチル、パルミチン酸ミリシル、ステアリン酸セチル、ステアリン酸ミリシルなどの高級脂肪酸エステル；アセトアミド、プロピオン酸アミド、パルミチン酸アミド、ステアリン酸アミド、アミドワックスなどのアミド類；ステアリルアミン、ベヘニルアミン、パルミチルアミンなどの高級アミン類などもワックス成分の一種としてあげられる。
【００４３】
これらのワックス成分は単独で、または２種以上を組合せて用いることができる。
【００４４】
好ましいワックス成分としては、パラフィンワックス、カルナバワックス、ポリエチレンワックスおよび各種アミドワックスがあげられ、特にパラフィンワックス、カルナバワックス、ポリエチレンワックスが、作業性が特に優れた艶出し剤を調製することができる点で好ましい。
【００４５】
本発明で用いるワックス組成物には、前記親水化剤およびワックス成分を分散または膨潤（場合によっては溶解）させ、作業性を向上させるために有機溶媒を配合してもよい。そうした有機溶媒としては石油系炭化水素類、アルコール類があげられる。
【００４６】
前記石油系炭化水素類としては特に制限はなく、たとえば石油ナフサ、ソルベントナフサ、石油エーテル、石油ベンジン、イソパラフィン、ノルマルパラフィン、デカリン、工業ガソリン、リグロイン、灯油などの１種または２種以上をあげることができる。これらの中でも好ましいのは、灯油、石油ナフサ、ソルベントナフサである。
【００４７】
アルコール類としては炭素数１〜２０のアルコールが好ましく、たとえばメチルアルコール、エチルアルコール、ｎ−プロピルアルコール、ｉｓｏ−プロピルアルコール、ｎ−ブチルアルコール、ｉｓｏ−ブチルアルコール、ｓｅｃ−ブチルアルコール、ｔｅｒｔ−ブチルアルコール、アリルアルコール、クロチルアルコールなどの一価アルコール類；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などの二価アルコール類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールジメチルエーテルなどのグリコールエーテル類などの１種または２種以上が例示できる。
【００４８】
ワックス組成物は塗布後拭き取ることにより艶が出てくるものであるが、この拭き取りを容易にするため充填剤を含有させてもよい。
【００４９】
充填剤としては従来から使用されている粉末状の充填剤を使用することができ、無機粉末および有機粉末のいずれも使用することができる。
【００５０】
無機粉末としては、たとえばカオリン、タルク、ケイ石、ケイ砂、珪藻土、無水珪酸、パーライト、炭酸カルシウム、ゼオライト、アルミナ、水酸化アルミニウム、含水珪酸、酸化クロム、酸化チタン、酸化亜鉛、酸化鉄、酸化ジルコニウム、酸化ケイ素、酸化セリウム、酸化マグネシウム、フッ化カルシウム、ベントナイト、モンモリロナイト、シラスバルーン、マイカ、雲母、珪酸カルシウム、珪酸ジルコニウム、ダイヤモンド、炭化ケイ素（カーボランダム）、ガラス、その他の各種セラミックスなどの粉末があげられる。
【００５１】
有機粉末としては、ポリエチレンなどのポリオレフィン、セルロース、ポリテトラフルオロエチレン、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、ポリフッ化ビニリデン、高級脂肪酸ビスアマイド、高級脂肪酸金属石鹸、不溶性シリコーン樹脂、ポリアミド、ポリスチレン、アクリル樹脂などの粉末やアミノ酸系粉末などがあげられる。
【００５２】
充填剤の粒径としては、通常１０μｍ以下であり、好ましくは１〜５μｍである。充填剤の粒径が前記範囲内にあると塗布し拭き取る際に対象物の表面を傷付けるおそれがない。
【００５３】
また、表面研磨を行なう場合は、必要に応じて公知の研磨剤を配合してもよい。研磨剤としては、上記の充填剤のうち、研磨作用を有する粒径の比較的大きい粉末が通常使用される。
【００５４】
本発明において、前記親水化剤はワックス成分１０重量部に対して５０重量部以上、好ましくは８０重量部以上で、５００重量部以下、好ましくは４００重量部以下含有されていることが好ましく、この範囲であれば特に親水化作用（防汚性）、拭き取り作業性および艶出し効果が共に良好である。
【００５５】
有機溶媒は、ワックス組成物の各成分を分散させ、かつワックス組成物の粘度を下げて塗布作業を容易にする作用をするものであり、そうした作用が奏される範囲の量で使用される。好ましくはワックス組成物全体の１０重量％以上、好ましくは３０重量％以上であり、９５重量％以下、好ましくは８５重量％以下である。前記含有量が９５重量％より多くなると、相対的に親水化剤、ワックス成分の含有量が少なくなるので親水化作用および艶出し効果が乏しくなる。一方、前記含有量が１０重量％より少なくなると粘度が高くなり、塗布や拭き取り時の作業性がわるくなる傾向にある。
【００５６】
充填剤は、ワックス成分１０重量部に対して２０重量部以上、好ましくは３０重量部以上で、２００重量部以下、好ましくは１００重量部以下である。充填剤が２０重量部よりも少ないと拭き取り作業性が低下し、２００重量部よりも多くなると親水化剤も拭き取られてしまい表面親水性が低下する傾向にある。
【００５７】
本発明の親水化ワックス組成物には、必要に応じてさらにシリコーンオイルを配合してもよい。
【００５８】
シリコーンオイルとしては特に制限はなく、たとえばジメチルシリコーン、フェニルシリコーン、アミノ変性シリコーン、アルキル変性シリコーン、ビニル変性シリコーン、メチルフェニルシリコーン、ポリエーテル変性シリコーンなどの１種または２種以上をあげることができ、表面親水化作用の邪魔になりにくい点からジメチルシリコーン、ポリエーテル変性シリコーンが特に好ましい。
【００５９】
シリコーンオイルの粘度としては、通常１〜１５０００ｃ／ｓであり、好ましくは２〜１００００ｃ／ｓである。
【００６０】
シリコーンオイルの含有量としては、ワックス成分１００重量部に対して通常０．１倍量以上、好ましくは０．３倍量以上で、５．０倍量以下、好ましくは４．０倍量以下である。シリコーンオイルの含有量が５．０倍倍量よりも多いと拭き取り性が低下し、本発明が目的とする表面親水化が低下することがある。
【００６１】
本発明においては、さらにその他の成分として防錆剤、低級多価アルコール、蛍光顔料、防塵剤、加水分解助剤、紫外線吸収剤、光安定剤などの適当量を必要に応じて添加することができる。
【００６２】
本発明のワックス組成物は、各成分を順次または一括して混合することによって調製することができる。
【００６３】
たとえば有機溶媒にワックス成分を分散または溶解させ、ついで親水化剤を加え、さらに充填剤を添加して攪拌混合し、均一に分散させればよい。
【００６４】
塗布方法は特に限定されず、ワックス組成物の形態（半固形状かペースト状か乳液状かなど）や粘度などにより、スポンジや布で擦りつける方法、刷毛などで塗布する方法、スプレーで噴霧する方法などの方法の中から適宜選択すればよい。
【００６５】
本発明の方法において、塗布後の拭き取りは必須の作業工程であるが、拭き取り作業自体は布で拭き取るなどの通常の方法で行なえばよい。この拭き取り作業によりワックス成分が擦れ、基材（塗膜）表面にしっかりと付着することとなり、艶のある親水化され得るワックス被覆層が形成される。
【００６６】
本発明における表面親水化は、前記親水化剤の加水分解性官能基が水分の存在（水洗時の水や雨など）により加水分解して水酸基となることによって発揮される。この際、親水化剤同士が縮合反応を起こして高分子量化したり、基材（塗膜）の官能基（水酸基など）と結合したりするため、長期に亘って基材（塗膜）に密着させることができる。
【００６７】
本発明の製造方法が適用され得る自動車ボディーとしては、自動車ボディーのほか、自動車ボディーを構成する部品であってもよく、たとえば自動車のボディーの外板部のほか、バンパーなどの外装品や車の外部部位で塗装されている部分全てが含まれる。そうした車の外部部位で塗装されている部分としては、たとえばスポイラー、ラジエータグリル、フードバルジ、外部ミラー（ドアミラーやフェンダーミラー）、外部ドアハンドル、プロテクトモール、サイドモール、ルーフモール、ルーフガーニッシュ、ピラーガーニッシュ、ルーフレール、リアガーニッシュ（ライセンスプレート、バックドア、トランクなど）などがあげられる。
【００６８】
【実施例】
つぎに本発明を実施例をあげて説明するが、本発明はかかる実施例のみに限定されるものではない。
【００６９】
実施例１〜９
以下の成分を使用し、表１に示す配合割合で混合して親水化塗料および親水化ワックス組成物を調製した。これらを用いて試験板を作製し、後述する特性を評価した。結果を表１に示す。
【００７０】
ケイ素化合物
Ａ−１：
ＲＯ（−Ｓｉ（ＯＲ）_２−Ｏ）_４−Ｒ
（式中、Ｒは−ＣＨ_３および−ＣＨ_２ＣＦ_３であり、−ＣＨ_３／−ＣＨ_２ＣＦ_３＝０．６である。）
Ａ−２：
ＲＯ（−Ｓｉ（ＯＲ）_２−Ｏ）_１０−Ｒ
（式中、Ｒは−ＣＨ_３および−ＣＨ_２ＣＦ_２ＣＦＨＣＦ_３であり、−ＣＨ_３／−ＣＨ_２ＣＦ_２ＣＦＨＣＦ_３＝０．３である。）
Ａ−３：
ＲＯ（−Ｓｉ（ＯＲ）_２−Ｏ）_４−Ｒ
（式中、Ｒは−ＣＨ_３および−ＣＨ_２Ｃ_２Ｆ_５であり、−ＣＨ_３／−ＣＨ_２Ｃ_２Ｆ_５＝０．５である。）
【００７１】
［試験板の作製および評価方法］
（基材の作製）
化成処理アルミニウム板（１００ｍｍ×１００ｍｍ×１ｍｍ）に、ＰＰ用プライマー（関西ペイント（株）製のソフレックス３５００、塩素化ポリオレフィン系樹脂塗料）をエアスプレー塗装し、８０℃で２０分間熱風乾燥して約１０μｍの下塗り塗膜を形成した。この上に１コートメタリック塗料（関西ペイント（株）製のソフレックス３００、２液ウレタン系樹脂塗料）をエアスプレー塗装し、１２０℃で３５分間熱風乾燥して約３０μｍの上塗り塗料を形成し、試験板作製用の基材を調製した。
【００７２】
（クリアー塗料の調製）
ダイキン工業（株）製のフッ素塗料用ワニス（ゼッフルＧＫ５５０。水酸基価９０、樹脂濃度６０重量％）１００重量部に、表１に示すケイ素化合物（親水化剤）６．０重量部（フッ素樹脂１００重量部に対しては１０重量部）添加し、タケネートＤ−１４０Ｎ（武田薬品工業（株）製のイソホロンジイソシアネート系硬化剤）３８．１重量部（ＮＣＯ／ＯＨ＝１．０）および酢酸ブチルを８０重量部加えて充分混合してクリアー塗料用組成物を調製した。
【００７３】
（親水化ワックス組成物の調製）
２００ｍｌのステンレススチール製の容器に有機溶剤（ノルマルパラフィン２３ｇと灯油２３ｇ）を入れ、これにワックス成分（カルバナワックス２ｇとパラフィンワックス２ｇ）を加え、７０〜８５℃にて溶解させた後、攪拌機で充分に混合した。ついで、表１に示すケイ素化合物を４０ｇ加え、攪拌機により充分に混合して分散させた。最後に充填剤（炭酸カルシウム５ｇと無水珪酸パウダー５ｇ）を加え、攪拌機で充分混合し、均一に分散したペースト状のワックス組成物を調製した。
【００７４】
（試験板の作製）
表１に示すクリアー塗料を上述の基材上にスプレー塗装し、１４０℃で１時間熱風乾燥して塗装膜厚約４０μｍの親水化塗膜を形成した。ついでその塗膜の全面積の２／３をコンパウンドで研磨し、研磨した領域の１／２に表１に示すペースト状のワックス組成物をスポンジで均一に塗布し、直ちにネルウエスで拭き取り、塗膜のみの領域部分、研磨された領域部分およびワックス被覆層を有する領域部分の３つの状態を有する試験板を作製した。
【００７５】
（曝露試験）
得られた試験板を大阪府下の３階建て建物の屋上にて南西方向に３０度傾斜させて設置し、１２カ月間外気に曝露した。曝露の前後における試験板表面の各部分の明度を色差計（ミノルタ（株）製のＣＲ−３００）にて測定し、その色差（ΔＬ）の経時変化で評価した。結果を表１に示す。
【００７６】
【表１】

【００７７】
【発明の効果】
本発明によれば、自動車の製造時における自動車ボディー表面の親水化不良部分を簡便かつ有効に補修でき、また艶に優れた自動車ボディーを製造することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for manufacturing an automobile having excellent gloss, which repairs coating defects of a hydrophilic coating film formed in a finishing step of manufacturing an automobile and forms a coating film excellent in hydrophilicity as a whole.
[0002]
[Prior art]
The exterior of the vehicle is usually protected by various coatings. However, since the outermost coating film is constantly exposed to various types of dirt, a coating film having an effect of preventing adhesion of dirt and removing dirt is formed.
[0003]
Such antifouling coatings include a water-repellent coating and a hydrophilic coating, each of which has its own characteristics. The water-repellent coating film is easy to remove dirt, but hydrophobic dirt such as oil is easily adhered.
[0004]
On the other hand, as a hydrophilic coating film, for example, a method is known in which a coating film of a hydrophilic coating containing a silicon compound having a hydrolyzable leaving group is formed on at least one outermost layer (for example, Patent Document 1).
[0005]
When such a hydrophilic coating film is formed on the outermost layer of an automobile, coating film defects such as bumps and unevenness occur inevitably. Therefore, in the finishing process of a coating film for an automobile body, such a defective portion of the coating film is polished and removed. As a result, the part that has been cut off becomes a part with poor surface hydrophilicity.Therefore, in order to compensate for the hydrophilicity, the only conventional method was to recoat the part that had been cut off with a hydrophilic coating. There are appearance defects such as steps or sagging, and paint dust remains. In order to eliminate such a portion, it is necessary to further polish, and as a result, there is a problem that a portion having poor surface hydrophilicity remains.
[0006]
[Patent Document 1]
JP-A-2000-229894
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a strong and durable surface hydrophilicity in a finishing process of an automobile body coating film without causing a step or sagging in a surface hydrophilic defective portion caused by polishing and appearance defects such as dust. It is an object of the present invention to provide a method of manufacturing an automobile, which can provide the following. That is, instead of a coating film, by treating with a thin film formed by applying and wiping a wax-like composition, a poorly hydrophilized portion caused by polishing is compensated for without impairing the appearance of the original coating film. Things.
[0008]
[Means for Solving the Problems]
That is, the present invention relates to formula (1):
X _b Si (OR ¹ ) _a (1)
[Wherein, a is an integer of 2 to 4, b is 0 or an integer of 1 to 2 (a + b = 4), and X is the same or different and each is an oxygen atom, a nitrogen atom, a fluorine atom and / or a chlorine atom. A monovalent organic group having 1 to 5000 carbon atoms or a hydrogen atom which may contain an atom, R ¹ Are the same or different, each of which is a monovalent organic group having 1 to 1000 carbon atoms which may contain an oxygen atom (excluding the terminal of a molecular chain), a nitrogen atom, a fluorine atom and / or a chlorine atom, and a siloxane residue. Group or a hydrogen atom (wherein at least one of R1 always contains a fluorine atom)], a surface-hydrophilizing paint containing a hydrophilizing agent comprising a silicon compound and / or a condensate thereof is applied. In the finishing step of the automobile body coating film, a hydrophilizing wax composition containing the above-mentioned hydrophilizing agent is applied to the poorly hydrophilized portion caused by polishing the defective portion of the coating film, and wiped off. By converting the hydrolyzable group of the hydrophilizing agent into a hydrophilic group in situ and condensing the hydrophilizing agent to have a high molecular weight, at least the surface hydrophilization defect occurs. Min to form a layer of hydrophilic wax composition characterized in that it repaired by hydrophilizing the surface, a method of manufacturing automobile bodies with excellent gloss.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
First, the hydrophilizing agent (1) used in the present invention is contained in both the hydrophilizing paint for car body coating and the hydrophilizing wax composition.
[0010]
The hydrophilizing agent (1) is a compound represented by the above formula (1), and may be an oligomer thereof or a co-oligomer of two or more thereof. A specific example is described in JP-A-2000-301054.
[0011]
Hereinafter, first, a preferred embodiment of the organometallic compound represented by the formula (1) as a whole viewed in the present invention will be described.
[0012]
The above a is 2 to 4 in terms of surface orientation (the property that the hydrolyzable group of the silicon compound is oriented toward the surface of the wax coating. This makes it easy to be hydrolyzed on the surface), hydrolyzability, and desorption properties. Is an integer.
[0013]
B is 0 or an integer of 1 to 2 from the viewpoint of surface orientation and hydrophilicity.
[0014]
X may be a hydrogen atom, and may have a carbon number of 1 to 5,000 which may contain an oxygen atom, a nitrogen atom, a fluorine atom and / or a chlorine atom as shown in the following (1) to (3). It is preferably a monovalent organic group.
[0015]
(1) The organic group X is, for example, H (CH ₂ ) _p , (CH ₃ ) ₂ CH, H (CH ₂ ) _p C = O, F (CF ₂ ) _q (CH ₂ ) _p , (CF ₃ ) ₂ CH, H (CF ₂ ) _q (CH ₂ ) _p (Wherein p is 0 or an integer of 1 to 6, q is an integer of 1 to 10, and part of the fluorine atoms may be substituted with chlorine atoms). However, it may be a branched chain.
[0016]
Specific examples of these are, for example, CH ₃ , CH ₃ CH ₂ , CH ₃ CH ₂ CH ₂ , (CH ₃ ) ₂ CH, CF ₃ CH ₂ , CF ₃ CF ₂ CH ₂ , (CF ₃ ) ₂ CH, F (CF ₂ ) ₄ CH ₂ CH ₂ , F (CF ₂ ) ₈ CH ₂ CH ₂ , H (CF ₂ ) ₄ CH ₂ And the like, but CF is preferred in terms of surface orientation, hydrolyzability, and desorption. ₃ CF ₂ CH ₂ , (CF ₃ ) ₂ CH is preferred.
[0017]
(2) The organic group X is, for example, NH ₂ , Secondary amino group, tertiary amino group, OH, NCO, CO ₂ H, CO ₂ Na, CO ₂ K, SO ₃ H, SO ₂ Na, SO ₃ K, epoxy group, oxyethylene group (CH ₂ CH ₂ Organic groups having a functional group such as O).
[0018]
Specific examples of these are, for example, H ₂ N (CH ₂ ) ₃ , OCN (CH ₂ ) ₃ , CH ₃ O (CH ₂ CH ₂ O) (CH ₂ ) ₃ , CH ₃ O (CH ₂ CH ₂ O) ₅ (CH ₂ ) ₃ , CH ₃ O (CH ₂ CH ₂ O) ₁₀ (CH ₂ ) ₃ ,
[0019]
Embedded image

[0020]
Etc., but OCN (CH ₂ ) ₃ , CH ₃ O (CH ₂ CH ₂ O) ₅ (CH ₂ ) ₃ Is preferred.
[0021]
(3) The organic group X is, for example, a polymerizable organic group which may contain an oxygen atom, a nitrogen atom, a fluorine atom, a chlorine atom, a silicon atom and the like.
[0022]
Specific examples of these are, for example, CH ₂ = C (CH ₃ ) CO ₂ (CH ₂ ) ₃ , CH ₂ = CH, CH ₂ = CHCH ₂ , CH ₂ = CHO (CH ₂ ) ₃ , CH ₂ = CHOCO (CH ₂ ) ₃ , CH ₂ = CHC ₆ H ₄ , CH ₂ = CHCO ₂ (CH ₂ ) ₃ And the like, but CH 4 is preferred from the viewpoint of polymerizability and availability. ₂ = C (CH ₃ ) CO ₂ (CH ₂ ) ₃ , CH ₂ = CHO (CH ₂ ) ₃ Is preferred.
[0023]
In the present invention, the compound represented by the formula (1) having such a polymerizable organic group is obtained by polymerization or copolymerization, and has a molecular weight of 500 to 100,000, preferably 1000 to 20,000. Polymers or copolymers of the above are also preferred.
[0024]
The R ¹ May be the same or different, and may each contain an oxygen atom, a nitrogen atom, a fluorine atom and / or a chlorine atom. It is a valent organic group, a siloxane residue or a hydrogen atom, and the number of carbon atoms is preferably 1 to 100, more preferably 1 to 16.
[0025]
The R ¹ Is a monovalent organic group such as H (CH ₂ ) _m , (CH ₃ ) ₂ CH, H (CH ₂ ) _m C = O, F (CF ₂ ) _n (CH ₂ ) _m , (CF ₃ ) ₂ CH, H (CF ₂ ) _n (CH ₂ ) _m , F (CF ₂ ) _n (CH ₂ ) _m C = O, H (CF ₂ ) _n (CH ₂ ) _m C = O, (F (CF ₂ ) _n (CH ₂ ) _m ) ₂ N, ((CF ₃ ) ₂ CH) ₂ N, (H (CF ₂ ) _n (CH ₂ ) _m ) ₂ N, F (CF ₂ ) _n O (CF (CF ₃ ) CF ₂ O) _m CF (CF ₃ ) C = O, (F (CF ₂ ) _n (CH ₂ ) _m ) ₂ C = N, ((CF ₃ ) ₂ CH) ₂ C = N, (H (CF ₂ ) _n (CH ₂ ) _m ) ₂ C = N, F (CF ₂ ) _n (CH ₂ ) _m C = ONR ³ , H (CF ₂ ) _n (CH ₂ ) _m C = ONR ³ , F (CF ₂ ) _n (CH ₂ ) _m C = CH ₂ , H (CF ₂ ) _n (CH ₂ ) _m C = CH ₂ , F (CF ₂ ) _n (CH ₂ ) _m C = CF ₂ , H (CF ₂ ) _n (CH ₂ ) _m C = CF ₂ (Wherein, m is 0 or an integer of 1 to 6, n is an integer of 1 to 10, R ³ Represents an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be linear or branched.
[0026]
Specific examples of these organic groups include, for example, CF ₃ CH ₂ , CF ₃ CF ₂ CH ₂ , CF ₃ CHFCF ₂ CH ₂ , CF ₃ (CF ₂ ) ₂ CH ₂ , CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ , (CF ₃ ) ₂ CH, CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ , H (CF ₂ ) ₂ CH ₂ , H (CF ₂ ) ₃ CH ₂ , H (CF ₂ ) ₄ CH ₂ , CF ₃ C = O, CF ₃ CF ₂ C = O, CF ₃ (CF ₂ ) ₆ C = O, CF ₃ (CF ₂ ) ₇ C ＝ O and the like, but CF is preferable in terms of surface orientation, hydrolyzability, and desorption. ₃ CH ₂ , CF ₃ CF ₂ CH ₂ , CF ₃ CHFCF ₂ CH ₂ , CF ₃ (CF ₂ ) ₂ CH ₂ , CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ , CF ₃ C = O, CF ₃ CF ₂ C = O is preferred and CF is preferred ₃ CH ₂ , CF ₃ CF ₂ CH ₂ , CF ₃ CHFCF ₂ CH ₂ Is more preferred.
[0027]
The R ¹ Of the siloxane residue is, for example, (Si (OR ¹ ) ₂ O) _n R ¹ (Where R ¹ Is R ¹ And the same as the monovalent organic group.
[0028]
The R ² May have the same or different chelating ability, which may contain a fluorine atom and / or a chlorine atom, and have a carbon number in terms of surface orientation, hydrolyzability, and elimination. Is 1 to 20, and preferably 2 to 10.
[0029]
In the present invention, by using such a silicon compound to which an organic group having a chelating ability is bonded, an effect that storage stability, reactivity, solubility, and compatibility are more excellent can be obtained.
[0030]
Examples of the compound which can be an organic group having such chelation ability include β-diketones such as 2,4-pentanedione and 2,4-heptanedione, methyl acetoacetate, ethyl acetoacetate, and butyl acetoacetate. Ketosters, lactic acid, methyl lactate, ethyl lactate, ammonium lactate, salicylic acid, methyl salicylate, ethyl salicylate, malic acid, ethyl malate, tartaric acid, hydroxytartrate such as ethyl tartrate, esters, salts, 4-hydroxy Keto alcohols such as -4-methyl-2-pentanone, 4-hydroxy-2-pentanone, 4-hydroxy-2-heptanone, 4-hydroxy-4-methyl-2-heptanone, monoethanolamine, diethanolamine, triethanol Amine, N-methyl monoe Amino alcohols such as nolamine, N-ethylmonoethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine; enol active hydrogen compounds such as diethyl malonate, methylolmelamine, methylolurea, and methylolacrylamide And the like, and a compound in which all or a part of these hydrogen atoms are substituted with a fluorine atom and / or a chlorine atom is more preferable from the viewpoint of surface orientation.
[0031]
Examples of the oligomer or cooligomer of the silicon compound (1) in the present invention include linear or branched, cyclic, and three-dimensional oligomers or cooligomer.
[0032]
The degree of polymerization of the oligomer or co-oligomer in the invention is such that the oligomer or co-oligomer is condensed to such an extent that the molecular weight does not become high, and is preferably 2 to 100, more preferably 4 to 20. When the degree of polymerization is small, the oligomer or co-oligomer tends to have a low boiling point, easily volatilize during coating, and is hardly taken into the coating film. When the degree of polymerization exceeds 100, it is difficult to control the degree of polymerization during synthesis, and the viscosity of the oligomer or co-oligomer tends to be high, resulting in poor workability. However, when the oligomer or co-oligomer has a fluorine atom in which a is 4 and b is 0 in the formula (1), the degree of polymerization is 4 from the viewpoint of workability, appearance of the treated surface, storage stability and the like. It is preferable to be more than 30 and 30 or less.
[0033]
Other hydrophilizing agents that can be used in the present invention include, for example,
CH ₃ O (Si (OCH ₃ ) (CH ₃ ) O) _n CH ₃ (N = 20),
C ₂ H ₅ O (Si (OC ₂ H ₅ ) ₂ O) _m C ₂ H ₅ (M = 8)
And the like.
[0034]
Examples of the hydrophilizing paint for automotive body coating containing such a hydrophilizing agent include those composed of a resin for a coating material, a hydrophilizing agent, a solvent, and other additives. Examples of the coating resin include a fluorine resin, an acrylic resin, a polyester resin, a melamine resin, an epoxy resin, and a polyurethane resin. Examples of the solvent include aromatic hydrocarbons, aliphatic hydrocarbons, ethers, esters, ether esters, ketones, and alcohols. Other additives include ultraviolet absorbers, light stabilizers, antioxidants, viscosity modifiers, surface modifiers, pigments and the like. The amount of the hydrophilic agent in the hydrophilic coating is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the resin.
[0035]
As a method of painting an automobile using the hydrophilic coating, a conventionally known method is employed. For example, there is a method in which the composition is applied directly to a substrate such as a metal base material or a resin base material as a top coat, or a method in which an undercoat is applied and then an intermediate coat is applied to the intermediate coat. Further, as a coating system, a method of applying one coat alone, two coats, three coats in combination with a base coat, or a method of applying an overcoat on a top coat can be adopted.
[0036]
As described above, the coating film formed by coating has inevitable coating defects such as bumps, and the surface is polished to finish the surface. The polishing method is not particularly limited, and a method of polishing with a grindstone, a method of polishing with water-resistant paper, a method of polishing with a compound, and the like are employed.
[0037]
Naturally, a portion of the polished surface coating of the automobile body in which the hydrophilic state is impaired occurs. In the present invention, the surface of the automobile body is treated with a hydrophilizing wax containing the hydrophilizing agent in order to hydrophilize the poorly hydrophilized portion again.
[0038]
The hydrophilizing wax treatment is performed by applying the hydrophilizing wax composition to at least the poorly hydrophilized portion of the automobile body caused by polishing and wiping off the hydrolyzable group of the hydrophilizing agent in the presence of moisture. By converting into a group and condensing to increase the molecular weight of the hydrophilizing agent, a layer of the hydrophilized wax composition is formed at least on the surface of the poorly hydrophilized portion, and the surface is hydrophilized to repair the surface. is there.
[0039]
The hydrophilized wax composition comprises, in addition to the hydrophilizing agent, a wax component, and if necessary, a filler and an organic solvent.
[0040]
The wax component is mainly composed of an aliphatic saturated hydrocarbon having about 10 to 70 carbon atoms or a low molecular weight substance (oligomer) such as an ester of a fatty acid and an alcohol. It is clearly distinguished from a high polymer. A characteristic of wax is that it is a solid or semi-solid organic substance at normal temperature. It does not form a coating film (film) after being applied and dried like a resin used in paint, but is applied to a substrate (coating film). By applying and wiping (spreading by applying pressure), a uniform wax coating layer is formed for the first time, and it has an effect of giving gloss.
[0041]
The wax component to be used is not particularly limited, and a conventionally known wax component can be used. Specific examples include, for example, vegetable waxes such as carnauba wax (wax), wood wax, ouriculi wax, and spal wax; animal waxes such as beeswax, insect wax, shellac wax, and whale wax; paraffin wax, microcrystal wax, polyethylene wax, Examples include waxes such as petroleum waxes such as ester waxes and oxidized waxes; mineral waxes such as montan wax, ozokerite and ceresin; modified waxes, glycerides, synthetic ketone amine amides, hydrogenated waxes and the like.
[0042]
In addition, higher fatty acids such as palmitic acid, stearic acid, margaric acid, and behenic acid; higher alcohols such as palmityl alcohol, stearyl alcohol, behenyl alcohol, marganyl alcohol, myricyl alcohol, and eicosanol; cetyl palmitate, myricyl palmitate Higher fatty acid esters such as, cetyl stearate and myricyl stearate; amides such as acetamide, propionamide, palmitic amide, stearic amide and amide wax; higher amines such as stearylamine, behenylamine and palmitylamine Is also one of the wax components.
[0043]
These wax components can be used alone or in combination of two or more.
[0044]
Preferred wax components include paraffin wax, carnauba wax, polyethylene wax and various amide waxes, and paraffin wax, carnauba wax and polyethylene wax are particularly preferred in that a polisher having particularly excellent workability can be prepared. preferable.
[0045]
In the wax composition used in the present invention, an organic solvent may be blended in order to disperse or swell (dissolve in some cases) the above-mentioned hydrophilizing agent and the wax component and to improve workability. Examples of such organic solvents include petroleum hydrocarbons and alcohols.
[0046]
The petroleum hydrocarbons are not particularly limited, and include, for example, one or more of petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzene, isoparaffin, normal paraffin, decalin, industrial gasoline, ligroin, kerosene, and the like. Can be. Among these, kerosene, petroleum naphtha and solvent naphtha are preferred.
[0047]
As the alcohols, alcohols having 1 to 20 carbon atoms are preferable. For example, methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol And monohydric alcohols such as allyl alcohol and crotyl alcohol; dihydric alcohols such as ethylene glycol, propylene glycol and diethylene glycol; glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and ethylene glycol dimethyl ether One or more kinds of ethers can be exemplified.
[0048]
The wax composition is lustrous when wiped off after application, and may contain a filler to facilitate the wiping.
[0049]
As the filler, conventionally used powdered fillers can be used, and both inorganic powders and organic powders can be used.
[0050]
Examples of the inorganic powder include kaolin, talc, quartzite, silica sand, diatomaceous earth, silicic acid, perlite, calcium carbonate, zeolite, alumina, aluminum hydroxide, hydrous silicate, chromium oxide, titanium oxide, zinc oxide, iron oxide, and oxide. Powders of zirconium, silicon oxide, cerium oxide, magnesium oxide, calcium fluoride, bentonite, montmorillonite, shirasu balloon, mica, mica, calcium silicate, zirconium silicate, diamond, silicon carbide (carborundum), glass and other ceramics Is raised.
[0051]
Organic powders include polyolefins such as polyethylene, cellulose, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, polyvinylidene fluoride, higher fatty acid bisamide, higher fatty acid metal soap, insoluble silicone resin, polyamide, polystyrene, acrylic Powders such as resins and amino acid-based powders are exemplified.
[0052]
The particle size of the filler is usually 10 μm or less, preferably 1 to 5 μm. When the particle size of the filler is within the above range, there is no possibility of damaging the surface of the object when applying and wiping.
[0053]
When the surface is polished, a known abrasive may be added as necessary. As the abrasive, among the above-mentioned fillers, powder having a relatively large particle size and having an abrasive action is usually used.
[0054]
In the present invention, the hydrophilizing agent is contained in an amount of 50 parts by weight or more, preferably 80 parts by weight or more, and 500 parts by weight or less, preferably 400 parts by weight or less based on 10 parts by weight of the wax component. If it is in the range, the hydrophilicity (antifouling property), the wiping workability, and the polishing effect are particularly good.
[0055]
The organic solvent serves to disperse the components of the wax composition and to reduce the viscosity of the wax composition to facilitate the coating operation. The organic solvent is used in such an amount that the action is exhibited. It is preferably at least 10% by weight, preferably at least 30% by weight, and at most 95% by weight, preferably at most 85% by weight of the whole wax composition. When the content is more than 95% by weight, the content of the hydrophilizing agent and the wax component is relatively reduced, so that the hydrophilizing effect and the polishing effect are poor. On the other hand, when the content is less than 10% by weight, the viscosity becomes high, and the workability at the time of application and wiping tends to deteriorate.
[0056]
The filler is used in an amount of 20 parts by weight or more, preferably 30 parts by weight or more, and 200 parts by weight or less, preferably 100 parts by weight or less based on 10 parts by weight of the wax component. If the amount of the filler is less than 20 parts by weight, the wiping workability is reduced. If the amount of the filler is more than 200 parts by weight, the hydrophilic agent is also wiped off and the surface hydrophilicity tends to be reduced.
[0057]
The hydrophilic wax composition of the present invention may further contain a silicone oil, if necessary.
[0058]
The silicone oil is not particularly limited, and examples thereof include one or more of dimethyl silicone, phenyl silicone, amino-modified silicone, alkyl-modified silicone, vinyl-modified silicone, methylphenyl silicone, and polyether-modified silicone. Dimethyl silicone and polyether-modified silicone are particularly preferable because they do not hinder the surface hydrophilicity.
[0059]
The viscosity of the silicone oil is generally 1 to 15000 c / s, preferably 2 to 10000 c / s.
[0060]
The content of the silicone oil is usually 0.1 times or more, preferably 0.3 times or more, and 5.0 times or less, preferably 4.0 times or less with respect to 100 parts by weight of the wax component. is there. When the content of the silicone oil is more than 5.0 times, the wiping property is reduced, and the surface hydrophilicity targeted by the present invention may be reduced.
[0061]
In the present invention, an appropriate amount of a rust preventive, a lower polyhydric alcohol, a fluorescent pigment, a dust preventive, a hydrolysis aid, an ultraviolet absorber, a light stabilizer and the like may be further added as necessary. it can.
[0062]
The wax composition of the present invention can be prepared by mixing the components sequentially or collectively.
[0063]
For example, a wax component may be dispersed or dissolved in an organic solvent, a hydrophilic agent is added, a filler is further added, and the mixture is stirred and mixed to uniformly disperse.
[0064]
The method of application is not particularly limited, and depending on the form (semi-solid, paste, emulsion, etc.) and viscosity of the wax composition, a method of rubbing with a sponge or cloth, a method of applying with a brush, etc., or spraying with a spray The method may be appropriately selected from methods such as a method.
[0065]
In the method of the present invention, wiping after application is an essential operation step, but the wiping operation itself may be performed by a usual method such as wiping with a cloth. By this wiping operation, the wax component is rubbed and firmly adheres to the surface of the base material (coating film), so that a glossy and hydrophilic wax coating layer is formed.
[0066]
The surface hydrophilization in the present invention is exerted when the hydrolyzable functional group of the hydrophilizing agent is hydrolyzed by the presence of moisture (such as water or rain during washing) to become a hydroxyl group. At this time, since the hydrophilizing agent causes a condensation reaction to increase the molecular weight or binds to a functional group (such as a hydroxyl group) of the substrate (coating film), the hydrophilicizing agent adheres to the substrate (coating) for a long time. Can be done.
[0067]
The car body to which the manufacturing method of the present invention can be applied may be a car body, or a part constituting the car body. For example, in addition to an outer plate portion of the car body, an exterior component such as a bumper or a car body. Includes all parts that are painted outside. The parts that are painted on the outer parts of such vehicles include, for example, spoilers, radiator grills, hood bulges, external mirrors (door mirrors and fender mirrors), external door handles, protect malls, side moldings, roof moldings, roof garnishes, pillar garnishes , Roof rails, rear garnish (license plate, back door, trunk, etc.).
[0068]
【Example】
Next, the present invention will be described with reference to examples, but the present invention is not limited to only these examples.
[0069]
Examples 1 to 9
The following components were used and mixed in the mixing ratio shown in Table 1 to prepare a hydrophilic coating material and a hydrophilic wax composition. Using these, a test plate was prepared, and characteristics described later were evaluated. Table 1 shows the results.
[0070]
Silicon compound
A-1:
RO (-Si (OR) ₂ -O) ₄ -R
(Wherein R is -CH ₃ And -CH ₂ CF ₃ And -CH ₃ / -CH ₂ CF ₃ = 0.6. )
A-2:
RO (-Si (OR) ₂ -O) ₁₀ -R
(Wherein R is -CH ₃ And -CH ₂ CF ₂ CFHCF ₃ And -CH ₃ / -CH ₂ CF ₂ CFHCF ₃ = 0.3. )
A-3:
RO (-Si (OR) ₂ -O) ₄ -R
(Wherein R is -CH ₃ And -CH ₂ C ₂ F ₅ And -CH ₃ / -CH ₂ C ₂ F ₅ = 0.5. )
[0071]
[Production and evaluation method of test plate]
(Preparation of base material)
A primer for PP (Soflex 3500 manufactured by Kansai Paint Co., Ltd., chlorinated polyolefin resin paint) is applied to a chemical conversion-treated aluminum plate (100 mm x 100 mm x 1 mm) by air spray coating, and dried with hot air at 80 ° C for 20 minutes. An undercoat film of about 10 μm was formed. A 1-coat metallic paint (Soflex 300 manufactured by Kansai Paint Co., Ltd., 2-component urethane resin paint) is applied by air spray coating, and dried with hot air at 120 ° C. for 35 minutes to form a top coat of about 30 μm. A substrate for preparing a test plate was prepared.
[0072]
(Preparation of clear paint)
6.0 parts by weight of a silicon compound (hydrophilizing agent) shown in Table 1 to 100 parts by weight of a varnish for fluorine paint (Zeffle GK550; hydroxyl value 90, resin concentration 60% by weight) manufactured by Daikin Industries, Ltd. 10 parts by weight with respect to parts by weight), and 38.1 parts by weight (NCO / OH = 1.0) of Takenate D-140N (an isophorone diisocyanate-based curing agent manufactured by Takeda Pharmaceutical Co., Ltd.) and butyl acetate. 80 parts by weight were added and mixed well to prepare a clear coating composition.
[0073]
(Preparation of hydrophilized wax composition)
An organic solvent (23 g of normal paraffin and 23 g of kerosene) is placed in a 200 ml stainless steel container, and a wax component (2 g of carbana wax and 2 g of paraffin wax) is added thereto and dissolved at 70 to 85 ° C., followed by a stirrer. And mixed well. Subsequently, 40 g of the silicon compound shown in Table 1 was added, and the mixture was sufficiently mixed and dispersed by a stirrer. Finally, a filler (5 g of calcium carbonate and 5 g of anhydrous silicate powder) was added, and the mixture was sufficiently mixed with a stirrer to prepare a uniformly dispersed paste-like wax composition.
[0074]
(Preparation of test plate)
The clear paint shown in Table 1 was spray-coated on the above-mentioned base material and dried with hot air at 140 ° C. for 1 hour to form a hydrophilic coating film having a coating thickness of about 40 μm. Then, 2/3 of the total area of the coating film was polished with a compound, and a half of the polished area was uniformly coated with a paste-like wax composition as shown in Table 1 using a sponge. A test plate was prepared having three states: a region having only a region, a region having a polished region, and a region having a wax coating layer.
[0075]
(Exposure test)
The obtained test plate was installed on the roof of a three-story building in Osaka Prefecture at an inclination of 30 degrees to the southwest, and was exposed to outside air for 12 months. The lightness of each part of the test plate surface before and after the exposure was measured with a color difference meter (CR-300 manufactured by Minolta Co., Ltd.), and the color difference (ΔL) was evaluated based on the change over time. Table 1 shows the results.
[0076]
[Table 1]

[0077]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the poor hydrophilic part of the surface of a motor vehicle body at the time of manufacture of a motor vehicle can be repaired easily and effectively, and the vehicle body excellent in gloss can be manufactured.

Claims (1)

Equation (1):
X _b Si (OR ¹ ) _a (1)
[Wherein, a is an integer of 2 to 4, b is 0 or an integer of 1 to 2 (a + b = 4), and X is the same or different and each is an oxygen atom, a nitrogen atom, a fluorine atom and / or a chlorine atom. A monovalent organic group having 1 to 5000 carbon atoms or a hydrogen atom, which may contain an atom, R ¹ may be the same or different, and each of them is an oxygen atom (however, excluding the terminal of a molecular chain), a nitrogen atom, a fluorine atom and And / or a monovalent organic group having 1 to 1000 carbon atoms which may contain a chlorine atom, a siloxane residue or a hydrogen atom (wherein at least one of R1 always contains a fluorine atom). A table formed by polishing a defective portion of a coating film in a finishing step of a coating film for an automobile body, which is coated with a surface-hydrophilizing coating material containing a hydrophilizing agent comprising a silicon compound and / or a condensate thereof. A hydrophilic wax composition containing the above-mentioned hydrophilizing agent is applied to the poorly hydrophilized portion and wiped off, and the hydrolyzable group of the hydrophilizing agent is converted into a hydrophilic group in situ and condensed in the presence of moisture. Then, by increasing the molecular weight of the hydrophilizing agent, a layer of a hydrophilized wax composition is formed on at least the surface hydrophilization defective portion, and the surface is hydrophilized to be repaired. Manufacturing method of excellent car body.