JP4489905B2 - Multi-layer coating formation method - Google Patents
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- JP4489905B2 JP4489905B2 JP2000115088A JP2000115088A JP4489905B2 JP 4489905 B2 JP4489905 B2 JP 4489905B2 JP 2000115088 A JP2000115088 A JP 2000115088A JP 2000115088 A JP2000115088 A JP 2000115088A JP 4489905 B2 JP4489905 B2 JP 4489905B2
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Description
【0001】
【発明の属する技術分野】
本発明は、りん片状光輝性顔料を使用した新規なメタリック複層塗膜を形成する方法に関する。
【0002】
【従来の技術とその課題】
アルミニウムフレークなどの光輝性顔料を含有するメタリック塗料を塗装し、その塗膜を硬化させることなく、クリヤ塗料を塗装し、加熱してこれらの両塗膜を同時に硬化せしめて得られるメタリック複層塗膜は、キラキラとした光輝感があって意匠性にすぐれており、自動車車体の外板部の上塗り塗膜として広く採用されている。しかしながら、このメタリック塗料の単独塗膜は、主に樹脂成分、アルミニウムフレーク及び着色顔料で構成されており、このうちアルミニウムフレークは、その塗膜内において塗面に対して平行に配向していることが理想であるが、実際は不規則に配向することが多いために、アルミニウムフレークが本来的に有している白くかつ金属光沢感にすぐれ、しかもフリップフロップ性の強いメタリック塗膜を形成させることを困難にしている。
【0003】
【課題を解決するための手段】
本発明の目的は、りん片状光輝性顔料を使用したメタリック複層塗膜の形成方法に関し、特に、りん片状光輝性顔料を塗膜内において塗面に対して平行に配向せしめ、このりん片状光輝性顔料が本来的に有している白くかつ金属光沢感などの特性にすぐれ、しかもフリップフロップ性の強いメタリック塗膜を形成させる新規な方法を提供することである。その特徴は、水性塗料の未硬化塗面に、りん片状光輝性顔料及び有機溶剤を主成分とする光輝性塗料を塗装するところにある。
【0004】
しかして本発明によれば、水性塗料(A)の未硬化塗面に、りん片状光輝性顔料及び有機溶剤を主成分とする光輝性塗料(B)を塗装することを複層塗膜形成方法(以下、本方法という)が提供される。
【0005】
以下に、本方法について詳細に説明する。
【0006】
本方法による複層塗膜を形成させるための被塗物として金属製品及びプラスチック製品などがあげられ、これらの素材を用いて形成された乗用車、トラック、オートバイ、バスなどの自動車車体の外板部が特に好適である。これらの被塗物は、水性塗料(A)の塗装に先立って、あらかじめ表面処理などを行ない、さらに必要に応じてカチオン電着塗装及び中塗り塗装を行ない、これらの塗膜を硬化しておくことが好ましい。
【0007】
水性塗料(A)は、光輝性塗料(B)に先立って被塗物に塗装する塗料であり、水を主たる溶媒又は分散媒とする水性塗料であり、具体的には、ビニル樹脂及びポリエステル樹脂などの基体樹脂及び硬化剤を含有する熱硬化型水性塗料が好適に使用できる。
【0008】
ビニル樹脂として、それ自体既知のものが使用でき、例えば、カルボキシル基含有重合性単量体、水酸基含有重合性単量体及びその他の重合性単量体を共重合して得られる、数平均分子量約3000〜約40000、酸価約20〜約100、水酸基価約20〜約200のアクリル樹脂やビニル樹脂をあげることができる。
【0009】
カルボキシル基含有重合性単量体としては、(メタ)アクリル酸、マレイン酸、イタコン酸などのモノエチレン性不飽和カルボン酸類;水酸基含有重合性単量体としては、(メタ)アクリル酸2−ヒドロキシエチル、(メタ)アクリル酸2−ヒドロキシプロピルなどのモノエチレン性不飽和カルボン酸のヒドロキシアルキルエステル類などがあげられる。その他の重合性単量体としては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n−ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸デシルなどのモノエチレン性不飽和カルボン酸のアルキルエステル類、(メタ)アクリルアミド、N−メチロール(メタ)アクリルアミド、ジアセトンアクリルアミドなどのアクリルアミド誘導体、(メタ)アクリル酸グリシジルなどのモノエチレン性不飽和カルボン酸のグリシジルエステル類、酢酸ビニル、プロピオン酸ビニルなどの飽和カルボン酸のビニルエステル類、スチレン、α−メチルスチレン、ビニルトルエンなどの芳香族不飽和単量体をあげることができる。
【0010】
かくして得られるアクリル樹脂やビニル樹脂は、アンモニア又はトリエチルアミン、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、ジメチルアミノエタノールなどのアミン類、水酸化ナトリウムなどのアルカリ金属の水酸化物などの塩基性物質で中和することにより水性にすることができる。また、カルボキシル基含有重合性単量体を使用して、又は使用せずに、水酸基含有重合性単量体及びその他の重合性単量体を用いて共重合体を水中に分散せしめてなる水分散体も使用できる。
【0011】
水性ポリエステル樹脂としては、それ自体既知のものが使用でき、例えば、多価アルコールと多塩基酸とのエステル化反応により得られる、数平均分子量約1000〜約20000、酸価約20〜約100、水酸基価約20〜約200のポリエステル樹脂をあげることができる。多価アルコールとして、エチレングリコール、ジエチレングリコール、プロピレングリコール、ブタンジオール、ペンタンジオール、2,2−ジメチルプロパンジオール、グリセリン、トリメチロールプロパン、ペンタエリスリトールなど、多塩基酸として無水フタル酸、イソフタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、無水マレイン酸、無水コハク酸、アジピン酸、セバチン酸、無水トリメリット酸、無水ピロメリット酸などが使用でき、さらに必要に応じて安息香酸やt−ブチル安息香酸などの一塩基酸やヒマシ油、桐油、サフラワー油、大豆油、アマニ油、トール油、ヤシ油及びこれらの脂肪酸の油成分を用いることができる。
【0012】
かくしてポリエステル樹脂は、アンモニア又はトリエチルアミン、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、ジメチルアミノエタノールなどのアミン類、水酸化ナトリウムなどのアルカリ金属の水酸化物などの塩基性物質で中和することにより水性にすることができる。
【0013】
また、硬化剤として、メラミン樹脂、ベンゾグアナミン樹脂などが好適に使用でき、これらは、親水性及び疎水性のいずれでも差し支えなく使用できる。
【0014】
水性塗料(A)における、基体樹脂と硬化剤との比率は、両者の合計固形分重量を基準として、基体樹脂が約50〜約90重量%、好ましくは約60〜約85重量%、硬化剤が約10〜約50重量%、好ましくは約15〜約40重量%の範囲内で使用される。
【0015】
水性塗料(A)による単独塗膜は、無色透明、有色透明、着色不透明のいずれでも差支えない。着色はソリッドカラ−調の塗膜が適している。
【0016】
水性塗料(A)は、塗装時粘度をフォードカップ#4で約10〜約50秒(20℃)に調整し、エアスプレー塗装、エアレススプレー塗装、静電塗装などにより、上記の被塗物に塗装することができる。その膜厚は、硬化塗膜に基ずいて約5〜約30μm、特に約10〜約20μmが好ましい。
【0017】
本方法では、被塗物に塗装した水性塗料(A)の未硬化塗面に、りん片状光輝性顔料及び有機溶剤を主成分とする光輝性塗料(B)を塗装することを特徴としており、特に、光輝性塗料(B)を塗装する時点での水性塗料(A)の未硬化塗膜は、水分含有率50〜90重量%、特に60〜80重量%、粘度1000センチポイズ以上(20℃)、特に1300〜2000センチポイズ(20℃)で、ゲル分率10重量%以下あることが好ましい。水性塗料(A)の未硬化塗膜の水分含有率、粘度及びゲル分率を上記の範囲に調整するために、被塗物に塗装された水性塗料(A)の未硬化塗膜を室温乃至100℃で1〜30分放置することが好ましい。
【0018】
水性塗料(A)の「未硬化塗膜」の粘度は、その塗料をガラス板に実際に即した条件で塗装し、所定の時間放置してから、ガラスビンに捕集し、それをコーンアンドプレート型粘時計でズリ速度10sec-1における粘度を読み取ることにより測定した。水分含有率は同様にして捕集した塗料約2gを100℃で3時間加熱して、加熱前との減量率を測定した。ゲル分率は、同様にして捕集した塗料をアセトンで3時間還流温度で抽出した後の残存率を測定した(顔料は除いて計算した)。
【0019】
本方法において、光輝性塗料(B)は、水分含有率、粘度及びゲル分率を上記範囲に調整された、水性塗料(A)の未硬化塗膜の塗面に塗装する塗料であり、りん片状光輝性顔料及び有機溶剤を主成分とする光輝性塗料である。
【0020】
光輝性塗料(B)はりん片状光輝性顔料及び有機溶剤を含有する光輝性塗料であり、さらに必要に応じて塗料用樹脂組成物、沈降防止剤、静電助剤などを適宜配合することは可能である。
【0021】
りん片状光輝性顔料は、キラキラとした金属光沢感又は光干渉感を示すフレーク状の顔料が使用でき、具体的には、アルミニウム(リーフィング、ノンリーフィング)、蒸着アルミニウム、塩化オキシビスマス、アルミナ(酸化アウミニウム)、雲母、グラファイト、雲母状酸化鉄、酸化チタン被服雲母、酸化鉄被覆雲母などがあげられる。これらの形状はいずれもりん片状であって、長手方向の大きさが2〜50μm、厚さが0.001〜2μmであることが好ましい。また、有機溶剤として、通常の塗料に使用されている炭化水素系、エステル系、エーテル系、アルコール系、ケトン系などの溶剤が使用できる。
【0022】
りん片状光輝性顔料と有機溶剤との比率は、これらの両成分の合計重量を基準に、りん片状光輝性顔料は1〜60重量%、特に2〜10重量%、有機溶剤は99〜40重量%、特に98〜90重量%の範囲内が適している。
【0023】
光輝性塗料(B)において、上記の両成分に加えて、必要に応じて含有せしめることが可能な塗料用樹脂組成物として、水酸基などの官能基を有するアクリル樹脂、ポリエステル樹脂、アルキド樹脂、ウレタン樹脂などの基体樹脂とメラミン樹脂、(ブロック)ポリイソシアネート化合物などの硬化剤からなる組成物があげられる。これらの塗料用樹脂組成物の配合量は、りん片状光輝性顔料100重量部あたり、300重量部以下、特に0.1〜100重量部の範囲内が適している。沈降防止剤として、例えば、脂肪酸アマイドワックス、酸化ポリエチレンなどがあげられ、これらの配合量は、りん片状光輝性顔料100重量部あたり、50重量部以下、特に0.1〜30重量部の範囲内が適している。
【0024】
本方法は、水性塗料(A)の未硬化塗面に、光輝性塗料(B)を、塗装時粘度をフォードカップ#4で約10〜約50秒(20℃)に調整し、エアスプレー塗装、エアレススプレー塗装、静電塗装などにより、塗装することができる。その膜厚は、一般に、硬化塗膜(りん片状光輝性顔料のみ、又は塗料用樹脂などが併存することもある)として、約0.5〜約5μm、特に約0.8〜約2μmが好ましい。
【0025】
水性塗料(A)の未硬化塗面に、有機溶剤系光輝性塗料(B)を塗装すると、水面に油をを流したように、光輝性塗料(B)が未硬化塗面に速やかにかつ均一に延展し、その結果、りん片状光輝性顔料が均一かつち密に未硬化塗面に平行に配向し、りん片状光輝性顔料が本来的に有しているそれぞれの特性、例えば、りん片状アルミニウムでは白くかつ金属光沢感にすぐれ、しかもフリップフロップ性の強いメタリック塗膜を形成させることができる。
【0026】
本方法では、水性塗料(A)の未硬化塗面に光輝性塗料(B)を塗装した後、室温で放置し、又はさらに50〜100℃で1〜30分程度強制乾燥して、100〜170℃で10〜40分程度加熱して、水性塗料(A)の塗膜、さらに光輝性塗料(B)の塗膜を同時に硬化することにより本発明の目的とするメタリック複層塗膜を形成することができる。
【0027】
さらに、本方法では、水性塗料(A)及び光輝性塗料(B)を上記のように塗装し、必要に応じてこれらの塗膜を加熱硬化してから、光輝性塗料(B)の塗面にクリヤ塗料(C)を塗装することができる。
【0028】
クリヤ塗料(C)は、無色透明又は有色透明の塗膜を形成する塗料であり、複層塗膜の美化粧、仕上り外観、耐候性、耐薬品性、耐水性、耐湿性などをより一層向上させることができる。具体的には、水酸基、カルボキシル基、シラノール基、エポキシ基などの官能基を有するアクリル樹脂、ポリエステル樹脂、アルキド樹脂、フッ素樹脂、ウレタン樹脂、シリコン含有樹脂などの基体樹脂に、メラミン樹脂、(ブロック)ポリイソシアネート化合物、エポキシ樹脂又は化合物、カルボキシル基含有樹脂又は化合物、酸無水物、アルコキシシラン基含有樹脂又は化合物などの架橋剤とからなる熱硬化性樹脂組成物をビヒクル成分とする有機溶剤型又は非水分散液型の塗料が挙げられる。これらのクリヤ塗料には、紫外線吸収剤、着色剤などを適宜配合することもできる。
【0029】
クリヤ塗料(C)は、公害防止、省資源の観点から、高固形分型であることが好ましく、具体的には、塗装時の不揮発分濃度を約35重量%以上、好ましくは約40〜約80重量%、更に好ましくは約45〜約80重量%に調整したものが望ましい。
【0030】
クリヤ塗料(C)は、エアスプレー塗装、エアレススプレー塗装、静電塗装などにより塗装することができ、硬化塗膜に基ずいて約5〜約50μmの膜厚に塗装することが好ましい。
【0031】
本方法による複層塗膜は、上記した水性塗料(A)及び光輝性塗料(B)、さらに必要に応じてクリヤ塗料(C)を塗装することにより形成することができる。
【0032】
【発明の効果】
水性塗料(A)の未硬化塗膜面に有機溶剤系光輝性塗料(B)を塗装すると、水面に油を浮かべたように、塗料(A)の塗面に塗料(B)が薄く均一に延展しやすく、しかも塗料(B)は主に有機溶剤とりん片状光輝性顔料とからなっているので、りん片状光輝性顔料は未硬化塗面に全体に均一かつその塗面に対して平行方向に配向しやすく、その結果、従来のメタリック塗料を塗装したものと比べて、アルミニウムフレークの場合は、白く、金属光沢感にすぐれ、しかもフリップフロップ性の強いメタリック塗膜を形成することが可能になった。
【0033】
【実施例】
以下に本発明に関する実施例及び比較例について説明する。部及び%はいずれも重量を基準ににしており、塗膜の膜厚は硬化塗膜についてである。
1.試料の調製
1)被塗物
りん酸亜鉛化成処理を施した厚さ0.8mmのダル鋼板に、熱硬化性エポキシ樹脂系カチオン電着塗料(「エレクロン9600」、関西ペイント社製、商品名)を膜厚20μmになるように電着塗装し、170℃で30分間加熱し塗膜を硬化させてから、自動車用中塗り塗料(「TP−37プライマーサーフェーサー」、関西ペイント社製、商品名、熱硬化性ポリエステル樹脂・メラミン樹脂有機溶剤系)を膜厚25μmになるようにエアスプレー塗装し、140℃で30分間加熱し塗膜を硬化させて被塗物とした。
2)水性塗料(A)
a):重合体(イ)(注1)25部、重合体(ロ)(注2)60部、「サイメル327」(サイテック社製、商品名、メラミン樹脂)15部、チタン白顔料80部を混合し、水を加えて粘度40秒/フォードカップ#4/20℃に調整し水性塗料(A)(a)を得た。(配合比率は固形分比である)
(注1)重合体(イ):スチレン15部、メチルメタクリレート20部、エチルアクリレート25部、n−ブチルアクリレート20部、ヒドロキシエチルアクリレート15部及びアクリル酸5部からなる重合体(水酸基価72、酸価39、数平均分子量12000)をジメチルエタノールアミンで中和したもの。
(注2)重合体(ロ):スチレン15部、メチルメタクリレート20部、エチルアクリレート25部、n−ブチルアクリレート25部、アクリル酸5部及びジアセトンアクリルアミド10部からなる重合体(水酸基価0、酸価39、カルボニル価0.6mmol/g/固形分、数平均分子量12000)をジメチルエタノールアミンで中和したもの。
b):重合体(ハ)(注3)80部及び「サイメル327」20部を混合し、水を加えて粘度40秒/フォードカップ#4/20℃に調整した。(配合比率は固形分比である)
(注3)重合体(ハ):スチレン15部、メチルメタクリレート20部、エチルアクリレート25部、n−ブチルアクリレート15部、ヒドロキシエチルアクリレート15部、アクリル酸5部及びジアセトンアクリルアミド5部からなる重合体(水酸基価72、酸価39、カルボニル価0.3mmol/g/固形分、数平均分子量12000)をジメチルエタノールアミンで中和したもの。
【0034】
3)光輝性塗料(B)
a):ノンリーフィングアルニウムフレーク(注4)5部及び「スワゾール1000」95部からなる混合物。
(注4)ノンリーフィングアルニウムフレーク:「アルペースト7680NS」(東洋アルミニウム社製、商品名、長手寸法13μm、厚さ0.1〜2μm)
b):ノンリーフィングアルニウムフレーク(注4)5部、樹脂組成物(注5)2部及び「スワゾール1000」93部からなる混合物。
(注5)樹脂組成物:水酸基価100、数平均分子量15000のアクリル樹脂/ブチルエーテル化メラミン樹脂=75/25(重量比)からなる混合物。
c)ノンリーフィングアルニウムフレーク(注4)1部、樹脂組成物(注5)6部及び「スワゾール1000」93部からなる混合物。
【0035】
2.実施例及び比較例
実施例 1
被塗物に水性塗料(A)(a)を膜厚25μmになるように塗装し、室温で15分間放置してから(この未硬化塗膜の粘度は1500センチポイズ、水分含有率は65%、ゲル分率は0%であった)、光輝性塗料(B)(a)を膜厚1μmに塗装し、室温で3分間放置してから、「マジクロンクリヤ」(関西ペイント社製、商品名、有機溶剤型熱硬化性アクリル樹脂系クリヤ塗料)を膜厚40μmに塗装し、室温で3分間放置してから、140℃で30分間加熱してこれらの複層塗膜を同時に硬化せしめた。
【0036】
水性塗料(A)(a)の未硬化塗面に光輝性塗料(B)(a)を塗装すると、水面に油を浮かべたように、塗料(A)(a)の塗面に塗料(B)(a)が薄く均一に延展し、しかも塗料(B)(a)は主に有機溶剤とりん片状アルミニウム顔料とからなっているので、りん片状アルミニウム顔料は未硬化塗面に全体に均一かつその塗面に対して平行方向に配向しており、その結果、比較例1に比べ、白く、金属光沢感にすぐれ、しかもフリップフロップ性の強いメタリック塗膜を形成することができた。
【0037】
実施例 2
被塗物に水性塗料(A)(b)を膜厚25μmになるように塗装し、室温で15分間放置してから(この未硬化塗膜の粘度は1500センチポイズ、水分含有率は65%、ゲル分率は0%であった)、光輝性塗料(B)(b)を膜厚1μmに塗装し、室温で3分間放置してから、「マジクロンクリヤ」(関西ペイント社製、商品名、有機溶剤型熱硬化性アクリル樹脂系クリヤ塗料)を膜厚40μmに塗装し、室温で3分間放置してから、140℃で30分間加熱してこれらの複層塗膜を同時に硬化せしめた。
【0038】
水性塗料(A)(b)の未硬化塗面に光輝性塗料(B)(b)を塗装すると、水面に油を浮かべたように、塗料(A)(b)の塗面に塗料(B)(b)が薄く均一に延展し、しかも塗料(B)(b)は主に有機溶剤とりん片状アルミニウム顔料とからなっているので、りん片状アルミニウム顔料は未硬化塗面に全体に均一かつその塗面に対して平行方向に配向しており、その結果、比較例1に比べ、白く、金属光沢感にすぐれ、しかもフリップフロップ性の強いメタリック塗膜を形成することができた。
【0039】
比較例 1
被塗物に水性塗料(A)(a)を膜厚25μmになるように塗装し、室温で15分間放置してから(この未硬化塗膜の粘度は1500センチポイズ、水分含有率は65%、ゲル分率は0%であった)、光輝性塗料(B)(c)を膜厚1μmに塗装し、室温で3分間放置してから、「マジクロンクリヤ」(関西ペイント社製、商品名、有機溶剤型熱硬化性アクリル樹脂系クリヤ塗料)を膜厚40μmに塗装し、室温で3分間放置してから、140℃で30分間加熱してこれらの複層塗膜を同時に硬化せしめた。
【0040】
水性塗料(A)(a)の未硬化塗面に光輝性塗料(B)(c)を塗装すると、塗料(A)(a)の塗面に塗料(B)(c)が薄く均一に延展せず、しかも塗料(B)(c)は塗料用樹脂が多量含有しているので、りん片状アルミニウム顔料を未硬化塗面に全体に均一かつその塗面に対して平行方向に配向させることは困難であり、その結果、実施例1、2に比べ、白さが劣り、金属光沢感も十分でなく、しかもフリップフロップ性も弱かった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for forming a novel metallic multilayer coating film using a flake-like glitter pigment.
[0002]
[Prior art and its problems]
Applying a metallic paint containing bright pigments such as aluminum flakes, applying a clear paint without curing the paint film, and heating to cure both paint films at the same time. The film has a brilliant glitter and excellent design, and is widely used as an overcoat film on the outer plate of an automobile body. However, the single paint film of this metallic paint is mainly composed of resin components, aluminum flakes and color pigments, and aluminum flakes are oriented parallel to the paint surface in the paint film. Is ideal, but in fact, it is often irregularly oriented, so it is possible to form a metallic coating film with excellent white and metallic luster inherent in aluminum flakes and strong flip-flop properties. Making it difficult.
[0003]
[Means for Solving the Problems]
The object of the present invention relates to a method for forming a metallic multilayer coating film using a flake-like glitter pigment, and in particular, the flake-like glitter pigment is oriented parallel to the coating surface in the paint film. It is an object of the present invention to provide a novel method for forming a metallic coating film which is excellent in properties such as white and metallic luster which are inherently possessed by flake-like glittering pigments and which has a strong flip-flop property. Its feature is that a bright paint mainly composed of a flake-like bright pigment and an organic solvent is applied to an uncured coating surface of an aqueous paint.
[0004]
Thus, according to the present invention, the multi-layer coating is formed by coating the uncured coating surface of the water-based paint (A) with the glitter paint (B) mainly composed of a scaly glitter pigment and an organic solvent. A method (hereinafter referred to as the present method) is provided.
[0005]
Below, this method is demonstrated in detail.
[0006]
Examples of the objects to be coated to form a multilayer coating film by this method include metal products and plastic products, and the outer plate portion of automobile bodies such as passenger cars, trucks, motorcycles and buses formed using these materials. Is particularly preferred. Prior to the application of the water-based paint (A), these objects are subjected to surface treatment and the like, and if necessary, cationic electrodeposition coating and intermediate coating are performed to cure these coating films. It is preferable.
[0007]
The water-based paint (A) is a paint that is applied to an object prior to the glittering paint (B), and is a water-based paint using water as a main solvent or dispersion medium, specifically, a vinyl resin and a polyester resin. A thermosetting water-based paint containing a base resin and a curing agent such as can be suitably used.
[0008]
As the vinyl resin, those known per se can be used, for example, a number average molecular weight obtained by copolymerizing a carboxyl group-containing polymerizable monomer, a hydroxyl group-containing polymerizable monomer, and other polymerizable monomers. Examples thereof include acrylic resins and vinyl resins having about 3000 to about 40,000, an acid value of about 20 to about 100, and a hydroxyl value of about 20 to about 200.
[0009]
As the carboxyl group-containing polymerizable monomer, monoethylenically unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid and itaconic acid; as the hydroxyl group-containing polymerizable monomer, (meth) acrylic acid 2-hydroxy Examples thereof include hydroxyalkyl esters of monoethylenically unsaturated carboxylic acids such as ethyl and 2-hydroxypropyl (meth) acrylate. Examples of other polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( Alkyl esters of monoethylenically unsaturated carboxylic acids such as methacrylic lauryl acrylate, decyl methacrylic acid, acrylamide derivatives such as (meth) acrylamide, N-methylol (meth) acrylamide, diacetone acrylamide, (meth) Glycidyl esters of monoethylenically unsaturated carboxylic acids such as glycidyl acrylate, vinyl esters of saturated carboxylic acids such as vinyl acetate and vinyl propionate, and aromatic unsaturated units such as styrene, α-methylstyrene and vinyltoluene I can raise my body.
[0010]
The acrylic resin and vinyl resin thus obtained are basic substances such as ammonia or amines such as triethylamine, monoethanolamine, diethanolamine, triethanolamine and dimethylaminoethanol, and alkali metal hydroxides such as sodium hydroxide. It can be made aqueous by summing. Further, water obtained by dispersing a copolymer in water using a hydroxyl group-containing polymerizable monomer and other polymerizable monomers with or without using a carboxyl group-containing polymerizable monomer. Dispersions can also be used.
[0011]
As the aqueous polyester resin, those known per se can be used. For example, the number average molecular weight obtained by esterification reaction of polyhydric alcohol and polybasic acid is about 1000 to about 20000, the acid value is about 20 to about 100, A polyester resin having a hydroxyl value of about 20 to about 200 can be mentioned. Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol, 2,2-dimethylpropanediol, glycerin, trimethylolpropane, pentaerythritol, etc. Polybasic acids such as phthalic anhydride, isophthalic acid, tetrahydroanhydride Phthalic acid, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, adipic acid, sebacic acid, trimellitic anhydride, pyromellitic anhydride, etc. can be used, and benzoic acid and t-butylbenzoic acid as necessary Monobasic acid, castor oil, tung oil, safflower oil, soybean oil, linseed oil, tall oil, coconut oil and oil components of these fatty acids can be used.
[0012]
Thus, the polyester resin is aqueous by neutralizing with basic substances such as ammonia or amines such as triethylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, and alkali metal hydroxides such as sodium hydroxide. Can be.
[0013]
Moreover, a melamine resin, a benzoguanamine resin, etc. can be used conveniently as a hardening | curing agent, These can use any of hydrophilicity and hydrophobicity.
[0014]
In the water-based paint (A), the ratio of the base resin to the curing agent is about 50 to about 90% by weight, preferably about 60 to about 85% by weight, based on the total solid weight of both. Is used in the range of about 10 to about 50% by weight, preferably about 15 to about 40% by weight.
[0015]
The single coating film with the water-based paint (A) may be any of colorless and transparent, colored and transparent, or colored and opaque. A solid color film is suitable for coloring.
[0016]
The water-based paint (A) is adjusted to about 10 to about 50 seconds (20 ° C.) with a Ford Cup # 4, and applied to the above-mentioned object by air spray painting, airless spray painting, electrostatic painting, etc. Can be painted. The film thickness is preferably about 5 to about 30 μm, particularly about 10 to about 20 μm, based on the cured coating film.
[0017]
This method is characterized in that a bright paint (B) mainly composed of a flake-like bright pigment and an organic solvent is applied to an uncured coating surface of a water-based paint (A) coated on an object. In particular, the uncured coating film of the water-based paint (A) at the time of applying the glitter paint (B) has a water content of 50 to 90% by weight, particularly 60 to 80% by weight, and a viscosity of 1000 centipoise or more (20 ° C. ), Preferably 1300 to 2000 centipoise (20 ° C.) and a gel fraction of 10% by weight or less. In order to adjust the water content, viscosity, and gel fraction of the uncured coating film of the water-based paint (A) to the above ranges, the uncured coating film of the water-based paint (A) coated on the object to be coated is used at room temperature to It is preferable to leave at 100 ° C. for 1 to 30 minutes.
[0018]
The viscosity of the “uncured coating film” of the water-based paint (A) is such that the paint is applied to a glass plate under conditions that are practical, left for a predetermined time, and then collected in a glass bottle. The viscosity was measured by reading the viscosity at a shear rate of 10 sec −1 with a model viscoclock. The water content was measured by heating about 2 g of the collected paint in the same manner at 100 ° C. for 3 hours, and measuring the weight loss rate before heating. The gel fraction was determined by measuring the residual ratio after extracting the paint collected in the same manner with acetone at reflux temperature for 3 hours (excluding the pigment).
[0019]
In this method, the glittering paint (B) is a paint that is applied to the surface of the uncured coating film of the water-based paint (A), whose water content, viscosity, and gel fraction are adjusted to the above ranges. It is a glittering paint mainly composed of a flake-like glittering pigment and an organic solvent.
[0020]
The glitter paint (B) is a glitter paint containing a flake-like glitter pigment and an organic solvent, and if necessary, a resin composition for paint, an anti-settling agent, an electrostatic assistant, and the like are appropriately blended. Is possible.
[0021]
The flake-like glittering pigment can be a flake-like pigment exhibiting a brilliant metallic luster or optical interference. Specifically, aluminum (leafing, non-leafing), vapor-deposited aluminum, oxybismuth chloride, alumina ( Aluminium oxide), mica, graphite, mica-like iron oxide, titanium oxide-coated mica, iron oxide-coated mica, and the like. These shapes are all in the form of flakes, preferably having a longitudinal size of 2 to 50 μm and a thickness of 0.001 to 2 μm. Further, as the organic solvent, hydrocarbon-based, ester-based, ether-based, alcohol-based, and ketone-based solvents used in ordinary paints can be used.
[0022]
The ratio between the flake-like glitter pigment and the organic solvent is 1-60 wt% for the flake glitter pigment, particularly 2-10 wt%, and 99-99 for the organic solvent, based on the total weight of these two components. A range of 40% by weight, in particular 98 to 90% by weight, is suitable.
[0023]
In the glitter paint (B), in addition to the above two components, as a paint resin composition that can be incorporated as required, acrylic resin having a functional group such as hydroxyl group, polyester resin, alkyd resin, urethane Examples thereof include a composition comprising a base resin such as a resin and a curing agent such as a melamine resin or a (block) polyisocyanate compound. The blending amount of these coating resin compositions is suitably 300 parts by weight or less, particularly 0.1 to 100 parts by weight per 100 parts by weight of the flake-like glitter pigment. Examples of the anti-settling agent include fatty acid amide wax, polyethylene oxide and the like, and the blending amount thereof is 50 parts by weight or less, particularly 0.1 to 30 parts by weight per 100 parts by weight of the flake-like glitter pigment. The inside is suitable.
[0024]
In this method, the glitter paint (B) is applied to the uncured coating surface of the water-based paint (A), the viscosity at the time of painting is adjusted to about 10 to about 50 seconds (20 ° C.) with Ford Cup # 4, and air spray coating is performed. Can be painted by airless spray painting, electrostatic painting, etc. The film thickness is generally from about 0.5 to about 5 μm, particularly from about 0.8 to about 2 μm, as a cured coating film (only a flake-like glittering pigment or a coating resin may coexist). preferable.
[0025]
When the organic solvent-based glitter paint (B) is applied to the uncured coating surface of the water-based paint (A), the glitter paint (B) is quickly applied to the uncured paint surface as if oil was poured on the water surface. As a result, the flake-like glittering pigment is uniformly and densely oriented parallel to the uncured coating surface, and each characteristic inherent in the flake-like glittering pigment, for example, phosphorous In the case of flake aluminum, it is possible to form a metallic coating film which is white and excellent in metallic luster and has a strong flip-flop property.
[0026]
In this method, after the glitter paint (B) is applied to the uncured coating surface of the water-based paint (A), it is allowed to stand at room temperature or forcibly dried at 50 to 100 ° C. for about 1 to 30 minutes. By heating at 170 ° C for about 10 to 40 minutes and simultaneously curing the paint film of the water-based paint (A) and further the paint film of the glitter paint (B), the metallic multilayer paint film intended for the present invention is formed. can do.
[0027]
Further, in this method, the water-based paint (A) and the glitter paint (B) are applied as described above, and these coating films are heated and cured as necessary, and then the paint surface of the glitter paint (B) is applied. A clear paint (C) can be applied to the surface.
[0028]
Clear paint (C) is a paint that forms a colorless transparent or colored transparent coating, and further improves the beauty, finish, weather resistance, chemical resistance, water resistance, moisture resistance, etc. of the multilayer coating. Can be made. Specifically, a base resin such as an acrylic resin having a functional group such as a hydroxyl group, a carboxyl group, a silanol group, or an epoxy group, a polyester resin, an alkyd resin, a fluororesin, a urethane resin, or a silicon-containing resin, a melamine resin, (block ) Organic solvent type using a thermosetting resin composition comprising a polyisocyanate compound, an epoxy resin or compound, a carboxyl group-containing resin or compound, an acid anhydride, an alkoxysilane group-containing resin or compound as a vehicle component, or Non-aqueous dispersion type paints may be mentioned. These clear paints can be appropriately mixed with an ultraviolet absorber, a colorant and the like.
[0029]
The clear paint (C) is preferably a high solid content type from the viewpoint of pollution prevention and resource saving. Specifically, the concentration of the non-volatile content during coating is about 35% by weight or more, preferably about 40 to about Those adjusted to 80% by weight, more preferably about 45 to about 80% by weight are desirable.
[0030]
The clear paint (C) can be applied by air spray coating, airless spray coating, electrostatic coating or the like, and is preferably applied to a film thickness of about 5 to about 50 μm based on the cured coating film.
[0031]
The multilayer coating film by this method can be formed by applying the above-mentioned water-based paint (A) and glitter paint (B) and, if necessary, clear paint (C).
[0032]
【The invention's effect】
When the organic solvent-based glitter paint (B) is applied to the uncured paint film surface of the water-based paint (A), the paint (B) is thinly and evenly applied to the paint surface of the paint (A) as if the oil floated on the water surface. Since the paint (B) is mainly composed of an organic solvent and a flake-like glitter pigment, the flake-like glitter pigment is uniformly uniform on the uncured painted surface. As a result, aluminum flakes can form a white, excellent metallic luster, and a strong flip-flop metallic coating compared to conventional metallic paints. It became possible.
[0033]
【Example】
Examples and comparative examples relating to the present invention will be described below. Both parts and% are based on weight, and the film thickness of the coating is for the cured coating.
1. Preparation of sample 1) Thermosetting epoxy resin cationic electrodeposition paint ("Electron 9600", manufactured by Kansai Paint Co., Ltd., trade name) on a 0.8 mm-thick dull steel plate subjected to zinc phosphate conversion treatment After coating the film with a film thickness of 20 μm and heating at 170 ° C. for 30 minutes to cure the coating film, an automotive intermediate coating (“TP-37 Primer Surfacer”, manufactured by Kansai Paint Co., Ltd., trade name, A thermosetting polyester resin / melamine resin organic solvent system) was applied by air spray so as to have a film thickness of 25 μm, and heated at 140 ° C. for 30 minutes to cure the coating film to obtain an article to be coated.
2) Water-based paint (A)
a): 25 parts of polymer (ii) (Note 1), 60 parts of polymer (b) (Note 2), 15 parts of “Cymel 327” (trade name, melamine resin, manufactured by Cytec), 80 parts of titanium white pigment And water was added to adjust the viscosity to 40 seconds / Ford Cup # 4/20 ° C. to obtain an aqueous paint (A) (a). (The blending ratio is the solid content ratio)
(Note 1) Polymer (I): Polymer comprising 15 parts of styrene, 20 parts of methyl methacrylate, 25 parts of ethyl acrylate, 20 parts of n-butyl acrylate, 15 parts of hydroxyethyl acrylate and 5 parts of acrylic acid (hydroxyl value 72, Acid value 39, number average molecular weight 12000) neutralized with dimethylethanolamine.
(Note 2) Polymer (b): A polymer comprising 15 parts of styrene, 20 parts of methyl methacrylate, 25 parts of ethyl acrylate, 25 parts of n-butyl acrylate, 5 parts of acrylic acid and 10 parts of diacetone acrylamide (hydroxyl value 0, Acid value 39, carbonyl value 0.6 mmol / g / solid content, number average molecular weight 12000) neutralized with dimethylethanolamine.
b): 80 parts of polymer (c) (Note 3) and 20 parts of “Cymel 327” were mixed, and water was added to adjust the viscosity to 40 seconds / Ford Cup # 4/20 ° C. (The blending ratio is the solid content ratio)
(Note 3) Polymer (C): A polymer consisting of 15 parts of styrene, 20 parts of methyl methacrylate, 25 parts of ethyl acrylate, 15 parts of n-butyl acrylate, 15 parts of hydroxyethyl acrylate, 5 parts of acrylic acid and 5 parts of diacetone acrylamide. A compound (hydroxyl value 72, acid value 39, carbonyl value 0.3 mmol / g / solid, number average molecular weight 12000) neutralized with dimethylethanolamine.
[0034]
3) Bright paint (B)
a): A mixture comprising 5 parts of non-leafing aluminum flakes (Note 4) and 95 parts of “Swazole 1000”.
(Note 4) Non-leafing Arnium Flakes: “Alpaste 7680NS” (trade name, longitudinal dimension 13 μm, thickness 0.1-2 μm, manufactured by Toyo Aluminum Co., Ltd.)
b): A mixture comprising 5 parts of non-leafing aluminum flakes (Note 4), 2 parts of a resin composition (Note 5) and 93 parts of “Swazole 1000”.
(Note 5) Resin composition: A mixture of acrylic resin / butyl etherified melamine resin having a hydroxyl value of 100 and a number average molecular weight of 15000 = 75/25 (weight ratio).
c) A mixture comprising 1 part of non-leafing aluminum flakes (Note 4), 6 parts of a resin composition (Note 5) and 93 parts of “Swazole 1000”.
[0035]
2. Examples and Comparative Examples Example 1
Apply the water-based paint (A) (a) to the object to be coated to a film thickness of 25 μm and leave it at room temperature for 15 minutes (the viscosity of this uncured coating film is 1500 centipoise, the moisture content is 65%, The gel fraction was 0%), and the glitter paint (B) (a) was applied to a film thickness of 1 μm and allowed to stand at room temperature for 3 minutes, then “Majikuron Kuriya” (trade name, manufactured by Kansai Paint Co., Ltd.) The organic solvent type thermosetting acrylic resin-based clear paint) was applied to a film thickness of 40 μm, left at room temperature for 3 minutes, and then heated at 140 ° C. for 30 minutes to simultaneously cure these multilayer coating films.
[0036]
When the glitter paint (B) (a) is applied to the uncured paint surface of the water-based paint (A) (a), the paint (B) is applied to the paint surface of the paint (A) (a) as if oil is floated on the water surface. ) (A) is thin and evenly spread, and the paint (B) (a) is mainly composed of an organic solvent and scaly aluminum pigment, so that the scaly aluminum pigment is entirely applied to the uncured coating surface. Uniform and oriented in the direction parallel to the coating surface. As a result, it was possible to form a metallic coating film that was whiter, superior in metallic luster, and strong in flip-flop properties as compared with Comparative Example 1.
[0037]
Example 2
A water-based paint (A) (b) is applied to the object to be coated to a film thickness of 25 μm and left at room temperature for 15 minutes (the viscosity of this uncured coating film is 1500 centipoise, the water content is 65%, The gel fraction was 0%), and the glitter paint (B) (b) was applied to a film thickness of 1 μm and allowed to stand at room temperature for 3 minutes, and then “Majicron Kuriya” (trade name, manufactured by Kansai Paint Co., Ltd.) The organic solvent type thermosetting acrylic resin-based clear paint) was applied to a film thickness of 40 μm, left at room temperature for 3 minutes, and then heated at 140 ° C. for 30 minutes to simultaneously cure these multilayer coating films.
[0038]
When the glitter paint (B) (b) is applied to the uncured paint surface of the water-based paint (A) (b), the paint (B) is applied to the paint surface of the paint (A) (b) as if oil is floated on the water surface. ) (B) spreads thinly and uniformly, and the paint (B) (b) is mainly composed of an organic solvent and scaly aluminum pigment. Uniform and oriented in the direction parallel to the coating surface. As a result, it was possible to form a metallic coating film that was whiter, superior in metallic luster, and strong in flip-flop properties as compared with Comparative Example 1.
[0039]
Comparative Example 1
Apply the water-based paint (A) (a) to the object to be coated to a film thickness of 25 μm and leave it at room temperature for 15 minutes (the viscosity of this uncured coating film is 1500 centipoise, the moisture content is 65%, The gel fraction was 0%), and the glitter paint (B) (c) was applied to a film thickness of 1 μm and allowed to stand at room temperature for 3 minutes, then “Majikuron Kuriya” (trade name, manufactured by Kansai Paint Co., Ltd.) The organic solvent type thermosetting acrylic resin-based clear paint) was applied to a film thickness of 40 μm, left at room temperature for 3 minutes, and then heated at 140 ° C. for 30 minutes to simultaneously cure these multilayer coating films.
[0040]
When the glitter paint (B) (c) is applied to the uncured paint surface of the water-based paint (A) (a), the paint (B) (c) is thinly and uniformly spread on the paint surface of the paint (A) (a). In addition, since paints (B) and (c) contain a large amount of resin for paints, the flake-like aluminum pigment should be uniformly oriented on the entire surface of the uncured coating and parallel to the coating surface. As a result, as compared with Examples 1 and 2, the whiteness was inferior, the metallic luster was not sufficient, and the flip-flop property was also weak.
Claims (1)
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JP2000115088A JP4489905B2 (en) | 2000-04-17 | 2000-04-17 | Multi-layer coating formation method |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6121761A (en) * | 1984-07-11 | 1986-01-30 | Kansai Paint Co Ltd | Metallic finishing method |
JPH0292974A (en) * | 1988-09-30 | 1990-04-03 | Kansai Paint Co Ltd | Water-dispersible paint and method for forming coating film using the paint |
JPH09187722A (en) * | 1996-01-12 | 1997-07-22 | Kansai Paint Co Ltd | Method for forming coating film |
JPH10296171A (en) * | 1997-04-28 | 1998-11-10 | Nippon B Chem Kk | Method for coating plastic base material |
JPH10328615A (en) * | 1997-05-29 | 1998-12-15 | Kansai Paint Co Ltd | Compound layer film forming method |
JPH1157605A (en) * | 1997-08-26 | 1999-03-02 | Kansai Paint Co Ltd | Metallic coating method |
JPH1190318A (en) * | 1997-07-25 | 1999-04-06 | Kansai Paint Co Ltd | Formation of metallic coating film |
JP2000000517A (en) * | 1998-06-15 | 2000-01-07 | Kansai Paint Co Ltd | Method for repairing multi layered coating |
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2000
- 2000-04-17 JP JP2000115088A patent/JP4489905B2/en not_active Expired - Lifetime
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6121761A (en) * | 1984-07-11 | 1986-01-30 | Kansai Paint Co Ltd | Metallic finishing method |
JPH0292974A (en) * | 1988-09-30 | 1990-04-03 | Kansai Paint Co Ltd | Water-dispersible paint and method for forming coating film using the paint |
JPH09187722A (en) * | 1996-01-12 | 1997-07-22 | Kansai Paint Co Ltd | Method for forming coating film |
JPH10296171A (en) * | 1997-04-28 | 1998-11-10 | Nippon B Chem Kk | Method for coating plastic base material |
JPH10328615A (en) * | 1997-05-29 | 1998-12-15 | Kansai Paint Co Ltd | Compound layer film forming method |
JPH1190318A (en) * | 1997-07-25 | 1999-04-06 | Kansai Paint Co Ltd | Formation of metallic coating film |
JPH1157605A (en) * | 1997-08-26 | 1999-03-02 | Kansai Paint Co Ltd | Metallic coating method |
JP2000000517A (en) * | 1998-06-15 | 2000-01-07 | Kansai Paint Co Ltd | Method for repairing multi layered coating |
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JP2001293428A (en) | 2001-10-23 |
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