JP2004300380A - Water-dispersed powdery slurry coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide powdery slurry coating by using a surfactant and giving a coated film excellent in water resistance, acid rain resistance and film strength. <P>SOLUTION: This water-dispersed powdery slurry coating is provided by containing (A) fine particles consisting of (a) a resin having an active hydrogen which may be an acrylic resin, a polyester resin, a polyurethane resin or an epoxy resin, (C) a curing agent, and preferably containing (B) a reactive surfactant consisting of (b3) an addition reaction product consisting of (b1) preferably a monohydric phenol or monohydric aromatic alcohol with (b2) a vinyl monomer, or (b4) its alkylene oxide adduct. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００６５】
メラミン樹脂（Ｃ４）としては、通常、メラミンとアルデヒドとからなる混合物及びこれらの一部重縮物が使用できる。
メラミンとしては、例えば、メラミン、メチロールメラミン、メチル化メチロールメラミン及びブチル化メチロールメラミン等が挙げられる。
アルデヒドとしては、例えば、ホルムアルデヒド、アセトアルデヒド、ブチルアルデヒド、アクロレイン及びフルフラール等が挙げられる。
【００６６】
（ヘミ）アセタール基含有化合物（Ｃ５）としては、例えば、ベンズアルデヒドジエチルアセタール、ベンズアルデヒドブチルアセタール、ベンズアルデヒドアミルアセタール、ベンズアルデヒドベンジルアセタール、プロピオンアルデヒドブチルアセタール、プロピオンアルデヒドアミルアセタール、プロピオンアルデヒドベンジルアセタール等が挙げられる。
【００６７】
活性水素含有樹脂（ａ）と硬化剤（Ｃ）の比率は、上記樹脂（ａ）の活性水素基と上記硬化剤（Ｃ）の活性水素と反応し得る官能基のモル比として、好ましくは１／１以上２／１以下、より好ましくは１．２／１以上１．８／１以下、さらに好ましくは１．３／１以上１．６／１以下である。１／１以上のモル比で反応させることにより、過剰な硬化剤官能基の副反応により塗膜の表面形状が悪化することを防ぐことができる。また、２／１以下のモル比で反応させることにより、活性水素含有樹脂の活性水素が十分に反応することができ、強度、平滑性等の塗膜性能にすぐれた塗膜を得ることができる。
【００６８】
本発明の水分散粉体スラリー塗料において、反応性界面活性剤（Ｂ）の含有量は、微粒子（Ａ）および反応性界面活性剤（Ｂ）の合計重量に対して好ましくは０．１〜１０重量％、さらに好ましくは０．５〜８重量％、最も好ましくは１〜５重量％である。
【００６９】
本発明の方法により得られる水分散粉体スラリー塗料中の樹脂分は、好ましくは２０〜７５重量％、さらに好ましくは２０〜６０重量％である。樹脂分はＪＩＳ Ｋ５４００−１９７９（塗料一般試験方法）により測定される値である。
本発明の水分散粉体スラリー塗料の２５℃における粘度は好ましくは１０〜１００，０００ｍＰａ・ｓ、さらに好ましくは５０〜５，０００ｍＰａ・ｓである。また、該スラリー塗料中の微粒子（Ａ）の平均粒径は、０．１〜５０μｍ、好ましくは０．５〜２０μｍ、さらに好ましくは１．０〜１０μｍである。粒径の測定法は電子顕微鏡測定、沈降法、エレクトロゾーン法、動的光散乱法等があるが、測定粒度範囲の適合性より、動的光散乱法での測定が好ましい。
本発明のスラリー塗料において、微粒子（Ａ）の粒子形状は不定形であっても球状であっても良いが、塗膜の平滑性、均一性の点で球状の方が好ましい。ここで球状というのは粒子の長径／短径の比率が１．０〜１．５の範囲にあるものを指す。微粒子（Ａ）は、平均の長径／短径比率が１．０〜１．５の球形であり、好ましくは１．０〜１．２である。
長径／短径比率は光学顕微鏡を用いて粒子を観察し、Ｈｅｙｗｏｏｄの定義により、粒子の平面図について輪郭に接する二つの平行線の最短距離を短径、それに直角方向の平行線の最大距離を長径とし、測定される値の長径と短径の比率を計算して求める。
樹脂分が２０〜７５重量％であるとき、微粒子（Ａ）の水中での分散性は良好となり、分散体粘度が１０〜１００，０００ｍＰａ・ｓであるとき、塗料としての取り扱いが容易となる。微粒子（Ａ）の平均粒径が０．１〜５０μｍであるとき、水中での粒子の沈降は無く、焼付け時の水分揮発および粘度調整が容易となる。また、長径／短径比率が１．０〜１．５の範囲にある時、平滑性、均一性に優れた塗膜を得ることができる。
【００７０】
なお、本発明の効果を阻害しない範囲において、反応性界面活性剤（Ｂ）とともに必要により公知の他の乳化剤または界面活性剤（ノニオン性乳化剤および界面活性剤、アニオン乳化剤および界面活性剤、カチオン乳化剤および界面活性剤、ブロックイソシアネート基、カルボン酸基、エポキシ基、ビニル基、酸無水物等を導入した、本発明におけるもの以外の各種反応性乳化剤および界面活性剤等）等を併用することができる。併用する場合の該他の乳化剤および界面活性剤の使用量は、乳化剤または界面活性剤の全量に対して好ましくは４４重量％以下、より好ましくは３７重量％以下である。
【００７１】
本発明の方法で得られる水分散粉体スラリー塗料には、目的とする用途に応じて必要により公知の添加剤（Ｄ）（たとえば粘弾性調整剤、動的表面張力調整剤、反応促進剤、充填剤、増粘剤、耐熱もしくは耐候安定剤、レベリング剤、消泡剤、防腐剤、着色料など）を任意に含有させることができる。
【００７２】
粘弾性調整剤としては、たとえばポリカルボン酸系、ポリスルホン酸系、ポリエーテル変性カルボン酸系、ポリエーテル系等の高分子型粘弾性調整剤、ウレタン変性ポリエーテル系等の会合型粘弾性調整剤が挙げられる。配合量は水分散粉体スラリー塗料に対して好ましくは１０．０％以下、より好ましくは０．１以上５％以下である。
【００７３】
動的表面張力調整剤としては、たとえばアセチレングリコール系動的表面張力調整剤、フッ素系動的表面張力調整剤やシリコーン系動的表面張力調整剤等が挙げられる。配合量はスラリー塗料に対して好ましくは０．０５％以上２０．０％以下、より好ましくは０．１以上１０％以下である。
【００７４】
反応促進剤としては、たとえばジアザビシクロオクタン、１，８−ジアザビシクロ（５，４，０）−ウンデセン−７などのアミン化合物、ジブチル錫ジラウレート、オクチル酸ジルコニウムなどの金属含有化合物が挙げられる。配合量は水分散粉体スラリー塗料に対して好ましくは５．００％以下、より好ましくは０．１％以上３％以下である。
【００７５】
耐候安定剤としては、たとえばフェニルサリシレート、ｐ−ｔｅｒｔ−ブチルフェニルサリシレート等のサリチル酸系紫外線吸収剤、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン等のベンゾフェノン系紫外線吸収剤、２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール等のベンゾトリアゾール系紫外線吸収剤、２−エチルヘキシル−２−シアノ−３，３’−ジフェニルアクリレート等のシアノアクリレート系紫外線吸収剤、オクチル化ジフェニルアミン、イソオクチル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェノール）プロピオネート等のヒンダードアミン系光安定剤が挙げられる。配合量は水分散粉体スラリー塗料に対して好ましくは１０％以下、より好ましくは０．５％以上３％以下である。
【００７６】
レベリング剤としては特に限定されないが、たとえば低分子ポリエチレン、低分子ポリプロピレンなどのオレフィン系樹脂、エチレン−アクリル共重合体、エチレン−メタクリル共重合体などのオレフィン共重合体、（メタ）アクリル共重合体、ポリビニルピロリドンなどが挙げられる。配合量は水分散粉体スラリー塗料に対して好ましくは６％以下、より好ましくは０．５％以上３％以下である。
【００７７】
必要により用いる着色料としては特に限定されないが、たとえば無機顔料、有機顔料、染料などが挙げられる。無機顔料としてはたとえば、酸化チタン、カーボンブラック、酸化クロム、フェライト等が挙げられる。有機顔料としてはアゾレーキ系、モノアゾ系、ジスアゾ系、キレートアゾ系等のアゾ顔料、ベンズイミダゾロン系、フタロシアニン系、キナクリドン系、ジオキサジン系、イソインドリノン系、チオインジゴ系、ペリレン系、キノフタロン系、アンスラキノン系等の多環式顔料が挙げられる。染料としてはニグロシン系、アニリン系が挙げられる。配合量としては着色料の種類によって異なるが、水分散粉体スラリー塗料に対して好ましくは３０％以下、より好ましくは１．０％以上１０％以下である。
【００７８】
本発明の水分散粉体スラリー塗料を製造する方法としては、下記の方法が例示できるが、これらに限定されない。
▲１▼脱溶剤法［反応性界面活性剤（Ｂ）を含む水性媒体中（水、またはメタノール、イソプロパノール等のアルコールやアセトン等のケトン溶剤の水混和性溶媒と水との混合溶媒；必要により各種添加剤（Ｄ）を混合）に、上記樹脂（ａ）および硬化剤（Ｃ）、各種添加剤（Ｄ）を上記記載の有機系溶剤に溶解させ、ホモミキサー等で反応容器に分散させ、必要により最高１００℃まで加熱しながら、０．１〜１５Ｔｏｒｒまで減圧して、水を残存させるよう、上記の水混和性溶媒及び有機系溶剤だけを主に脱溶剤し、平均粒径０．１μｍ〜５０μｍとした樹脂粒子を水中に分散させる方法］；
▲２▼粉砕粒子分散法［上記樹脂（ａ）、および硬化剤（Ｃ）、各種添加剤（Ｄ）を溶融混練し、冷却、粉砕し、平均粒径０．１〜５０μｍとした樹脂粒子を、反応性界面活性剤（Ｂ）及び必要により各種添加剤（Ｄ）を含む水性媒体と、ディスパーサー等で反応容器に分散させる方法］。
上記▲１▼による製造における上記樹脂（ａ）、および硬化剤（Ｃ）の、有機系溶剤中での濃度は好ましくは２０〜７５重量％、より好ましくは４０〜６０重量％である。
また、樹脂水性分散体における系内温度は好ましくは−５〜１００℃、より好ましくは３０〜８０℃、脱溶剤は好ましくは０．１〜５０時間、より好ましくは２〜１０時間である。
【００７９】
上記の樹脂水性分散体を製造する方法で用いる分散機としては、例えば、ホモミキサー、高圧ホモミキサー、ディスパーサー、高圧ホモジナイザー、スタティックミキサー、膜乳化機、フィルミックス、超音波分散機等が挙げられる。このうち好ましいのはホモミキサーである。
【００８０】
本発明において、反応性界面活性剤（Ｂ）は、良好な界面活性能と分散安定性を示す。それとともに、本発明の水分散粉体スラリー塗料を塗布後、焼き付けを行うことによって、該界面活性剤（Ｂ）が硬化剤（Ｃ）と化学結合を起こし、皮膜中に取り込まれ、優れた耐水性と強度を示す。
【００８１】
本発明の水分散粉体スラリー塗料は、従来の水性塗料用塗装設備、または溶剤塗料用塗装設備であるスプレー塗装機を使用して塗装することができ、新規の設備を必要としない。
塗膜形成方法は、被塗装物に対して、該水分散粉体スラリー塗料を、ウェット膜厚を好ましくは１０μｍ以上２００μｍ以下、より好ましくは１０μｍ以上１００μｍ以下となるようにスプレー塗布する。塗料がスプレーノズルから被塗装物まで浮遊する間に、塗料中の水分が揮発して樹脂分が増加する。被塗装物に塗着時の塗料樹脂分（重量％）は、塗着塗料量と加熱後の塗膜重量との差を塗着塗料量で除した値と１００との差で表すことができ、好ましくは５０重量％以上９５重量％以下、さらに好ましくは６０重量％以上９０重量％以下であり、塗着した塗料中の樹脂分が５０重量％以上であると、塗料のタレが発生せず、平滑な塗膜が作成できる。
塗装された被塗装物を、好ましくは１００℃以上２００℃以下、さらに好ましくは１２０℃以上１８０℃以下の温度で、好ましくは５分以上６０分以下、さらに好ましくは５分以上３０分以下、特に好ましくは５分以上２０分以下の時間加熱することで塗膜を形成することができる。
本発明の塗料を塗布し、焼き付けることによって得られる塗膜の被塗装物の膜厚は好ましくは１０μｍ以上１５０μｍ以下、より好ましくは１５μｍ以上５０μｍ以下である。
【００８２】
本発明の方法で得られるスラリー塗料は、特に自動車用トップコートとして、あるいは建築物や家電製品等、種々の製品の塗装に用いることができる。
【００８３】
【実施例】
以下、製造例及び実施例により本発明を更に詳細に説明するが、本発明はこれに限定されるものではない。以下において「部」は重量部、「％」は重量％を示す。
【００８４】
製造例１
攪拌機、滴下ロート、窒素ガス導入管、温度計、還流冷却器を備えた反応容器に４−α−クミルフェノール２３部およびルイス酸触媒（水澤化学工業社製、ＧａｌｌｅｏｎＥａｒｔｈ）０．３５部を仕込み、攪拌下、系内を窒素ガスで置換し、１１０℃に昇温した。同温度にてスチレン７７部を３時間かけて滴下し、さらに同温度にて５時間反応させた。これを３０℃に冷却後、触媒を濾別することにより、スチレン７モルを４−α−クミルフェノール１モルに付加したもの（数平均分子量９００）（Ｂ０−１）を９５部を得た。上記（Ｂ０−１）５５部にＥＯ４５部を付加させ、オキシエチレン単位含量５５重量％、重量平均分子量２，４００の反応性界面活性剤［Ｂ−１］１００部を得た。
【００８５】
製造例２
製造例１と同様のフリーデルクラフツ反応にて得られたヒドロキシル基含有炭化水素［スチレン２モルとα−メチルスチレン５モルを４−α−クミルフェノール１モルに付加したもの；数平均分子量１，１００］５５部にＥＯ４５部を付加させ、オキシエチレン単位含量５５重量％、重量平均分子量２，６００の反応性界面活性剤［Ｂ−２］１００部を得た。
【００８６】
製造例３
製造例１と同様のフリーデルクラフツ反応にて得られたヒドロキシル基含有炭化水素［スチレン２モルとα−メチルスチレン１モルをフェノール１モルに付加したもの；数平均分子量４００］３５部にＥＯ６５部を付加させ、オキシエチレン単位含量６５重量％、重量平均分子量２，０００の反応性界面活性剤［Ｂ−３］１００部を得た。
【００８７】
製造例４
製造例１で得られた反応性界面活性剤［Ｂ−１］２３．７部、ポリエチレングリコール（数平均分子量６，０００）７３．２部およびヘキサメチレンジイソシアネート（以下ＨＤＩと略記）３．０部を８０℃で３時間反応させ、オキシエチレン単位含量８３重量％、重量平均分子量１０，０００の反応性界面活性剤［Ｂ−４］１００部を得た。
【００８８】
製造例５
ドデシルベンジルアルコールアミン８８．３部を塩酸１１．７部で中和し、数平均分子量３１２．５の反応性界面活性剤［Ｂ−５］１００部を得た。
【００８９】
製造例６
ラウリン酸４８．８部、ジエタノールアミン５１．２部を窒素気流下にかきまぜながら加熱し脱水縮合させ、数平均分子量３９２の反応性界面活性剤［Ｂ−６］１００部を得た。
【００９０】
製造例７
ステアリルアミン１５．４部、エチレンオキサイド８４．６部を窒素気流下にかきまぜながら加熱しエチレンオキサイド付加反応をおこない重量平均分子量１，３００、オキシエチレン単位８４．６重量％の反応性界面活性剤［Ｂ−７］１００部を得た。
【００９１】
アクリル系ヒドロキシ官能性樹脂の調製
キシレンの２５０部を反応器に入れ、加熱して１００℃とし、ついで、次に示されるような割合の混合物を約３時間滴下した。その間の反応は、窒素雰囲気下にて行った。この滴下終了後、２時間のあいだ、１００℃に保持して、反応を続行した。
（１）スチレン ２３ 部
（２）メチルメタクリレート ２３ 部
（３）アクリル酸ブチル ２０ 部
（４）アクリル酸ヒドロキシエチル ３３ 部
（５）パーオキシＤ（日本油脂製、過酸化物） １ 部
反応終了後、減圧蒸留によって有機溶剤および残存モノマーを除去し、その後、真空乾燥させることにより、水酸基当量４２０、重量平均分子量３２，０００のアクリル系ヒドロキシ官能性樹脂［アクリル樹脂１］を得た。
上記で得られた［アクリル樹脂１］５９部とＭＥＫオキシムブロックされたＨＤＩトリマー（旭化成製、ジュラネート）４１部を１００℃で加熱ニーダーを用いて混練後、５μｍ程度に粉砕し、平均粒径７μｍ、長径／短径比１．２の［アクリル樹脂２］を得た。
【００９２】
ポリエステル系樹脂の調製
反応器にネオペンチルグリコール２００部、エチレングリコール９３部、テレフタル酸３５５部を投入し、２３０℃に加熱し生成する水を留去しながら２時間反応を進めた。その後０．２部のジブチルチンオキサイドを添加し、酸価が０．５以下になるまで反応を続けることで、本発明の塗膜に用いる、両末端に水酸基を有する、重量平均分子量１２，０００、水酸基価１６．５ｍｇＫＯＨ／ｇのポリエステル樹脂［ポリエステル樹脂１］を得た。
上記で得られた［ポリエステル樹脂１］９３部とＭＥＫオキシムブロックされたＨＤＩトリマー（旭化成製、ジュラネート）７部を１００℃で加熱ニーダーを用いて混練後、５μｍ程度に粉砕し、平均粒径７μｍ、長径／短径比１．２の ［ポリエステル樹脂２］を得た。
【００９３】
エポキシ系樹脂の調整
反応器にキシレン４００部を仕込み、窒素雰囲気下、８０℃に昇温した。そこへ、ビスフェノールＡジグリシジルエーテル６７部とアジピン酸３３部からなる混合物を６時間にわたって滴下した。滴下終了後、同温度にて５時間保持して反応をおこない、反応終了後、有機溶剤を減圧蒸留し、重量平均分子量８，０００、水酸基価１２０ｍｇＫＯＨ／ｇのエポキシ樹脂［エポキシ樹脂１］を得た。
上記で得られた［エポキシ樹脂１］５７部とＭＥＫオキシムブロックされたＨＤＩトリマー（旭化成製、ジュラネート）４３部を１００℃で加熱ニーダーを用いて混練後、５μｍ程度に粉砕し、平均粒径７μｍ、長径／短径比１．２のエポキシ樹脂［エポキシ樹脂２］を得た。
【００９４】
分散液の調製例
製造例１〜７により得られた反応性界面活性剤［Ｂ−１］〜［Ｂ−７］、および非反応性界面活性剤としてラウリン酸ナトリウム［Ｂ’−８］、ラウリルアミン塩酸塩［Ｂ’−９］のそれぞれ３部を水１００部に分散し、分散液を得た。これを［分散液１］〜［分散液９］とする。
【００９５】
実施例１〜７、比較例１〜２
ビーカー内に、［アクリル樹脂１］５９部、ＭＥＫオキシムブロックされたＨＤＩトリマー（旭化成製、ジュラネート）４１部、およびテトラヒドロフラン１００部を混合しておき、これを［分散液１］〜［分散液９］１００部に添加した後、ウルトラディスパーサー（ヤマト科学製）を使用して、回転数９，０００ｒｐｍで１分間混合し、平均粒径を５μｍとした。混合後、攪拌棒および温度計をセットした４つ口フラスコにこの混合液を投入し、２５℃、減圧下で１０時間脱溶剤した。次いでウレタン化触媒［「ＴＥＤＡ」、東ソー製］０．１部、耐光安定剤［「ＤＩＣ−ＴＢＳ」、大日本インキ化学工業製］０．１部、粘弾性付与剤［「ＳＮシックナー−６５１」、サンノプコ社製］３．０部をそれぞれ加え、平均粒径、長径／短径比率及び粘度が表１に示すような樹脂水性分散塗料を得た。
【００９６】
実施例８〜１４、比較例３〜４
分散液の調製例により得られた［分散液１］〜［分散液９］１００部中に、上記で得られたアクリル系ヒドロキシ官能性樹脂微粉［アクリル樹脂２］１００部を加え、ウルトラディスパーサー（ヤマト科学製）を使用し、回転数９，０００ｒｐｍで１分間混合した。次いでウレタン化触媒［「ＴＥＤＡ」、東ソー製］０．１部、耐光安定剤［「ＤＩＣ−ＴＢＳ」、大日本インキ化学工業製］０．１部をそれぞれ加え、平均粒径、長径／短径比率及び粘度が表２に示すような樹脂水性分散塗料を得た。
【００９７】
実施例１５〜２１、比較例５〜６
ビーカー内に、［ポリエステル樹脂１］９３部、ＭＥＫオキシムブロックされたＨＤＩトリマー（旭化成製、ジュラネート）７部、およびテトラヒドロフラン１００部を混合しておき、これを［分散液１］〜［分散液９］１００部に添加した後、ウルトラディスパーサー（ヤマト科学製）を使用して、回転数９，０００ｒｐｍで１分間混合し、平均粒径を５μｍとした。混合後、攪拌棒および温度計をセットした４つ口フラスコにこの混合液を投入し、２５℃、減圧下で１０時間脱溶剤した。次いでウレタン化触媒［「ＴＥＤＡ」、東ソー製］０．１部、耐光安定剤［「ＤＩＣ−ＴＢＳ」、大日本インキ化学工業製］０．１部、粘弾性付与剤［「ＳＮシックナー−６５１」、サンノプコ社製］３．０部をそれぞれ加え、平均粒径、長径／短径比率及び粘度が表３に示すような樹脂水性分散塗料を得た。
【００９８】
実施例２２〜２８、比較例７〜８
分散液の調製例により得られた［分散液１］〜［分散液９］１００部中に、上記で得られたポリエステル系ヒドロキシ官能性樹脂微粉［ポリエステル樹脂２］１００部を加え、ウルトラディスパーサー（ヤマト科学製）を使用し、回転数９，０００ｒｐｍで１分間混合した。次いでウレタン化触媒［「ＴＥＤＡ」、東ソー製］０．１部、耐光安定剤［「ＤＩＣ−ＴＢＳ」、大日本インキ化学工業製］０．１部をそれぞれ加え、平均粒径、長径／短径比率及び粘度が表４に示すような樹脂水性分散塗料を得た。
【００９９】
実施例２９〜３５、比較例９〜１０
ビーカー内に、エポキシ樹脂［エポキシ樹脂１］５７部、ＭＥＫオキシムブロックされたＨＤＩトリマー（旭化成製、ジュラネート）４３部、ベンゾイン２部（脱ガス剤）、ＫＰ３２２（信越化学製レベリング剤）１部をおよびメチルエチルケトン１００部を混合しておき、これを［分散液１］〜［分散液９］１００部に添加した後、ウルトラディスパーサー（ヤマト科学製）を使用して、回転数９，０００ｒｐｍで１分間混合し、平均粒径を５μｍとした。混合後、攪拌棒および温度計をセットした４つ口フラスコにこの混合液を投入し、２５℃、減圧下で１０時間脱溶剤した。次いで、ウレタン化触媒［「ＴＥＤＡ」、東ソー製］０．１部、耐光安定剤［「ＤＩＣ−ＴＢＳ」、大日本インキ化学工業製］０．１部、粘弾性付与剤［「ＳＮシックナー−６５１」、サンノプコ社製］３．０部をそれぞれ加え、平均粒径、長径／短径比率及び粘度が表５に示すような樹脂水性分散塗料を得た。
【０１００】
実施例３６〜４２、比較例１１〜１２
分散液の調製例により得られた［分散液１］〜［分散液９］１００部中に、上記で得られたエポキシ系樹脂微粉［エポキシ樹脂２］１００部を加え、ウルトラディスパーサー（ヤマト科学製）を使用し、回転数９，０００ｒｐｍで１分間混合した。次いで、耐光安定剤［「ＤＩＣ−ＴＢＳ」、大日本インキ化学工業製］０．１部をそれぞれ加え、平均粒径、長径／短径比率及び粘度が表６に示すような樹脂水性分散塗料を得た。
【０１０１】
上記方法で得られた各樹脂水性分散体について、下記試験方法により評価を行った。その結果を表１〜表６に示す。
【０１０２】
（試験片の作成）
得られた樹脂水性分散塗料をリン酸亜鉛処理鋼板にスプレー塗布し、８０℃で１０分間前焼付けした後、１５０℃で２０分間焼付け乾燥して、膜厚０．０３ｍｍの塗膜を得た。
（試験方法）
吸水率の測定：上記で得られた塗膜を水に２５℃で１時間浸漬し、重量増加率を測定し吸水率とした。
抽出物含量比：上記で得られた加熱硬化後の塗膜１０．０ｇをエタノールを使用しソックスレー抽出器を使用して７８℃で２時間抽出を行ったときの抽出物含量を加熱硬化前の塗膜の抽出物含量で徐した値。
耐酸性雨性の評価：３０％の硫酸水溶液０．４ｇを上記で得られた塗膜に滴下し、循風乾燥機にて８０℃で３０分間加熱した後水洗し、塗面を目視評価した。
○：塗面に変化が全く認められない。
△：滴下跡が少し認められる。
×：滴下跡にシミ、白化又はフクレが著しく認められる
塗膜強度の測定：上記で得られた塗膜を、フィッシャー硬度計（フィッシャー・インストルメンツ製フィッシャースコープＨ１００Ｖ）で表面硬さを測定した。（加重０．４〜１００ｍＮ、押し込み深さ５μｍ）この試験方法は塗料の皮膜硬さを高精度で数値化できるうえ、一回の試験で押し込み硬さ、ヤング率等、多くの塗膜強度の要素を評価できるものである。この表面硬さを測定することにより塗膜強度を評価することができる。硬度値が大きいほど、塗膜強度は大きいと判断される。
【０１０３】
【表１】

【０１０４】
【表２】

【０１０５】
【表３】

【０１０６】
【表４】

【０１０７】
【表５】

【０１０８】
【表６】

【０１０９】
【発明の効果】
本発明の水分散粉体スラリー塗料は、分散剤として使用している反応性界面活性剤が分子内に活性水素を有しているため、硬化塗膜中に組み込まれる。そのため、硬化させた塗膜は優れた耐水性、耐酸性雨性、硬度を有する。
上記効果を奏することから、本発明の水分散粉体スラリー塗料は、例えば、自動車、建築物、産業機械等の塗料用特に自動車上塗り塗料用にきわめて有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a powder slurry coating composition. More specifically, the present invention relates to a powder slurry coating composition having excellent dispersibility of a resin dispersed in water and excellent strength, water resistance and acid rain resistance of a cured coating film after baking.
[0002]
[Prior art]
Powder slurry paints have a form in which resin microparticles are dispersed in water.When used, surface active agents are used to suppress coalescence and sedimentation of particles and to stably disperse resin microparticles in water. An agent is used (for example, see Patent Document 1).
[0003]
[Patent Document 1]
JP-A-7-196953 (pages 2-3)
[0004]
[Problems to be solved by the invention]
However, when the powder slurry is actually used as a coating material using a surfactant, the surfactant remaining after evaporating and drying the aqueous medium deteriorates the water resistance of the coating film. In addition, these surfactants exert a plasticizing effect and deteriorate the strength of the coating film. SUMMARY OF THE INVENTION An object of the present invention is to provide a powder slurry coating which is improved in water resistance, acid rain resistance and coating strength, in which the above-mentioned problems are improved.
[0005]
[Means for Solving the Problems]
The present inventors have intensively studied to solve the above problems, and as a result, have reached the present invention. That is, the present invention comprises, in an aqueous medium, fine particles (A) comprising a resin (a) having active hydrogen, a curing agent (C), and a reactive surfactant (B) having active hydrogen. It is a water-dispersed powder slurry paint.
The present invention is also a coating film obtained by applying and baking the above water-dispersed powder slurry coating.
Hereinafter, the present invention will be described in detail.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
The reactive surfactant (B) having active hydrogen in the present invention comprises a hydrophilic part containing active hydrogen and a hydrophobic part.
[0007]
The reactive surfactant (B) preferably has 1 to 20 active hydrogen groups per molecule of the above (B) molecule, from the viewpoint of the water resistance of the film obtained from the aqueous dispersion obtained using the same. The content is more preferably 1 to 15, more preferably 1 to 10, particularly preferably 1 to 5.
[0008]
Examples of the active hydrogen group contained in the reactive surfactant (B) include an alcoholic hydroxyl group, a phenolic hydroxyl group, an amino group, a phosphoric acid group, and a thiol group.
Of these, alcoholic hydroxyl groups and phenolic hydroxyl groups are preferred.
[0009]
Examples of the hydrophilic portion of the reactive surfactant (B) include, for example, a nonionic group containing an active hydrogen [polyoxyethylene group, hydroxyl group, etc.], an anionic group containing an active hydrogen [group of a carboxylate, Sulfonate group, sulfate group, phosphate group, etc.], cationic group containing active hydrogen [primary amine group, secondary amine group, tertiary amine] A salt group, a quaternary ammonium salt group, etc.] and an active hydrogen-containing zwitterionic group [amino acid salt group, betaine group, etc.], or two or more hydrophilic groups.
Among these, it is preferable to contain a nonionic group containing active hydrogen [polyoxyethylene group, hydroxyl group, etc.].
[0010]
The content of the hydrophilic group is preferably at least 0.1% by weight, more preferably at least 0.5% by weight, particularly preferably at least 1.0% by weight, based on the weight of the reactive surfactant (B). , Preferably 97% by weight or less, more preferably 95% by weight or less, particularly preferably 90% by weight or less.
When the hydrophilic group is an oxyethylene unit, the content of the hydrophilic group is preferably 20% by weight or more, more preferably 30% by weight, based on the weight of the reactive surfactant (B). %, Particularly preferably at least 50% by weight, preferably at most 90% by weight, more preferably at most 85% by weight, particularly preferably at most 80% by weight. When the oxyethylene unit is at least 20% by weight and at most 90% by weight, a stable slurry coating can be obtained with strong emulsifying power.
[0011]
The hydrophobic portion of the reactive surfactant (B) is not particularly limited, and examples thereof include a hydrocarbon group having 3 to 100 or more carbon atoms [alkyl group (butyl group, hexyl group, dodecyl group, cetyl group, etc.), Alkylene group (butylene group, hexylene group, etc.), alkenyl group (oleyl group, etc.), hydrocarbon group having 6 to 100 carbon atoms including aromatic ring ｛styrenated phenyl group, bisphenols (bisphenol A, bisphenol S, bisphenol F, etc.) )), A residue obtained by removing a hydroxyl group, an alkylphenyl group, a compound obtained by adding a vinyl monomer to these compounds, etc.), a (poly) oxyalkylene (C3-10) group (degree of polymerization: 100 or less) (poly Oxypropylene groups, polyoxybutylene groups, polystyrene oxide groups, etc.) and polyorganosiloxanes (degree of polymerization 2 100) group (polydimethylsiloxane groups, polydiethylsiloxane group, etc.) and the like. Among them, those having an aromatic ring-containing hydrocarbon group having 6 to 100 carbon atoms, particularly, a residue excluding a hydroxyl group of a styrenated phenyl group and bisphenols (bisphenol A, bisphenol S, bisphenol F, etc.) , An alkylphenyl group, and those obtained by adding a vinyl monomer to these compounds.
[0012]
Examples of the reactive surfactant (B) in the present invention include an active hydrogen-containing nonionic surfactant, an active hydrogen-containing cationic surfactant, an active hydrogen-containing anionic surfactant, and an active hydrogen-containing amphoteric surfactant. And the like.
Examples of the active hydrogen-containing nonionic surfactant include a nonylphenol ethylene oxide adduct, a stearate ethylene oxide adduct, and the like.
Examples of the active hydrogen-containing cationic surfactant include 2-heptadecenyl-hydroxyethylimidazoline, triethanolamine monostearate formate, and the like.
Examples of the active hydrogen-containing anionic surfactant include sodium polystyrene sulfonate and hydroxyethyl methacrylate copolymer, and examples of the active hydrogen-containing amphoteric surfactant include lauryl dihydroxyethyl betaine.
Among these, active hydrogen-containing nonionic surfactants are preferable, and among them, an addition reaction product (b3) comprising a monohydric phenol or a monohydric aromatic alcohol (b1) and a vinyl monomer (b2), or an alkylene oxide thereof. The adduct (b4) is preferred.
[0013]
The above-mentioned monohydric phenol or monovalent aromatic alcohol (b1) is not particularly restricted but includes, for example, phenol, alkyl (1 to 18 carbon atoms) phenol (for example, nonylphenol, dodecylphenol, octylphenol and the like), arylalkylated phenol ( For example, cumyl phenol, etc.), alkyl (C1-18) ethers of bisphenols (for example, monomethyl ether of bisphenol A, monobutyl ether of bisphenol A, monobutyl ether of bisphenol S, etc.), and a mixture of two or more of the above And the like.
Of these, phenol and cumylphenol are preferred.
Examples of the monovalent aromatic alcohol include benzyl alcohol, 2-biphenylethanol, and 4-biphenylethanol. Of these, benzyl alcohol is preferred.
[0014]
It does not specifically limit as a vinyl monomer (b2), For example, an aliphatic vinyl hydrocarbon, an alicyclic vinyl hydrocarbon, an aromatic vinyl hydrocarbon, etc. can be used.
Examples of the aliphatic vinyl hydrocarbon include, for example, ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 7-octadiene, α-olefins other than the above, and the like. Examples of the alicyclic vinyl hydrocarbon include cyclohexene, (di) cyclopentadiene, pinene, limonene, indene, vinylcyclohexene, and ethylidene bicycloheptene. Examples of the aromatic vinyl hydrocarbon include styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, and benzyl. Styrene, crotylbenzene, vinylnaphthalene, divinylbenzene, divinyltoluene, divinylxylene, divinylketone, trivinylbenzene and the like.
Of these, styrene is preferred.
[0015]
The method of adding the monohydric phenol or the monohydric aromatic alcohol (b1) and the vinyl monomer (b2) to the addition reaction product (b3) is not particularly limited, but a Friedel-Crafts reaction is preferred.
As a method of the Friedel-Crafts reaction, a known method can be used. For example, a vinyl monomer (b2) is added to a monohydric phenol or a monovalent aromatic alcohol (b1) and a known Lewis acid catalyst (for example, iron chloride). , Aluminum chloride, etc.).
[0016]
In the present invention, an alkylene oxide is further added to the addition reaction product (b3) obtained by adding the above-mentioned monohydric phenol or monovalent aromatic alcohol (b1) and the above-mentioned vinyl monomer (b2) (b4). It may be.
The alkylene oxide (hereinafter abbreviated as AO, having 1 to 30 carbon atoms) to be used is not particularly limited. Examples thereof include ethylene oxide (hereinafter, abbreviated as EO), propylene oxide (hereinafter, abbreviated as PO), and 1,2. -, 1,3- or 2,3-butylene oxide, tetrahydrofuran, α-olefin (C4-30) oxide, epichlorohydrin, styrene oxide, and a mixture of two or more of the above. Of these, EO is preferred. The mode of addition is preferably random and / or block.
The addition mole number of the alkylene oxide is preferably 1 to 30 mol, more preferably 1 to 10 mol, and still more preferably 1 to 5 mol.
[0017]
In the addition reaction product (b3), the weight ratio of the monohydric phenol or the monohydric aromatic alcohol (b1) as the structural unit, the vinyl monomer (b2), and the added AO is preferably (1 to 5). ) / (1-20) / (0-50), and more preferably (1-3) / (1-10) / (1-25).
[0018]
The weight average molecular weight of the reactive surfactant (B) is preferably from 1,000 to 150,000, more preferably from 5,000 to 100,000, particularly preferably from 10,000 to 25,000. The weight average molecular weight is preferably 1,000 or more from the viewpoint of obtaining sufficient surface activity, and is preferably 150,000 or less from the viewpoint of obtaining a low-viscosity and stable aqueous resin dispersion. The weight average molecular weight can be measured by a gel permeation chromatography (GPC) method. That is, a polymer solution is passed through a column filled with polystyrene gel or the like, and the polymer concentration and molecular weight of the eluate are detected as a function of the amount of elution.
[0019]
The HLB of the reactive surfactant (B) in the present invention is preferably 5 to 40 from the viewpoint of emulsifying the ethylenically unsaturated monomer and dispersing the resin fine particles into a stable aqueous dispersion or aqueous emulsion. Preferably, 5-20 are more preferable. The HLB of the reactive surfactant (B) is adjusted, for example, by adjusting the type and content of the hydrophobic group and adjusting the type and content of the hydrophilic group in the reactive surfactant (B). be able to. The HLB can be determined, for example, by the method of Oda described in Takehiko Fujimoto, “Introduction to a New Edition of Surfactants,” Sanyo Chemical Industries, Ltd., p.197, 1992. That is, the numerical values of the inorganic (hydrophilic) or organic (hydrophobic) of each functional group are evaluated based on the number of carbon atoms, and the numerical values of the organic and inorganic properties (for example, the numerical values of the third and the fourth literatures in the above document) Using the type of hydrophobic group and its content and the type and content of hydrophilic group in the reactive surfactant (B), the organic value and The inorganic value is determined, and the HLB is calculated by the following equation.
HLB = 10 × (inorganic / organic)
[0020]
In the water-dispersed powder slurry coating of the present invention, the fine particles (A) are composed of a resin (a) containing active hydrogen.
In the present invention, the resin (a) containing active hydrogen [alcoholic hydroxyl group, phenolic hydroxyl group, amino group, carboxylic acid group, phosphoric acid group, thiol group, etc.] is, for example, an acrylic resin (a (1)), Examples thereof include polyester resins (a-2), polyurethane resins (a-3), and epoxy resins (a-4), which contain active hydrogen groups.
The active hydrogen equivalent of the resin (a) is preferably 10 to 10,000, more preferably 10 to 1,000, and still more preferably 10 to 400.
[0021]
Examples of the monomer constituting the acrylic resin (a-1) include (i) [(meth) acrylic acid ester having no hydroxyl group, acrylamide, acrylonitrile] (a-1) 1; (ii) [having a hydroxyl group (Meth) acrylic acid ester, (meth) acrylic acid] (a-1); (iii) Other monomers (a-1) 3 if necessary.
[0022]
The weight percent ratio of the monomer (a-1), the monomer (a1-2) and the monomer (a-1) in the acrylic resin (a-1) is preferably (0-80). ) / (1-100) / (0-50), and more preferably (1-50) / (1-50) / (0-20).
[0023]
The acrylic resin (a 1) is produced by a known polymerization method such as solution polymerization, bulk polymerization, suspension polymerization and the like. The weight average molecular weight is preferably from 1,000 to 200,000, more preferably from 2,000 to 100,000, and still more preferably from 3,000 to 50,000.
[0024]
Examples of the monomer (a (1) 1) include acrylamide, acrylonitrile, (meth) acrylate, (meth) acrylate (cyclo) alkyl ester [the (meth) acrylate and alcohols having 1 to 25 carbon atoms (methyl alcohol) With ethyl alcohol, butyl alcohol, stearyl alcohol, ethylene glycol, 1,4-butanediol, cyclohexanol, etc.], and isobornyl (meth) acrylate.
Of these, preferred are methyl (meth) acrylate and n-butyl (meth) acrylate.
Examples of the monomer (a (1) 2) include acrylic acid, methacrylic acid, hydroxyalkyl (2-4 carbon atoms) (meth) acrylate, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) A) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
Of these, preferred is 2-hydroxyethyl (meth) acrylate.
Examples of the monomer (a (1) 3) include styrene, and among them, styrene is preferred.
[0025]
Examples of the active hydrogen group of the acrylic resin (a (1)) include an alcoholic hydroxyl group derived from an acrylate or methacrylate monomer having a hydroxyl group, and a carboxylic acid group derived from an acrylic acid or methacrylic acid monomer.
[0026]
Examples of the polyester resin (a {circle around (2)}) include low-molecular-weight polyols and / or condensed polyester polyols obtained by reacting polyalkylene ether diols having a weight average molecular weight of 5,000 or less with polycarboxylic acids, and ring-opening of lactones Polylactone diols obtained by polymerization, polycarbonate diols obtained by reacting low molecular diols with carbonic acid diesters of lower alcohols (such as methanol) and the like are included.
[0027]
Examples of the low-molecular polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-, 1,3-butanediol, neopentyl glycol, and 1,6-hexanediol; Diols [for example, those described in JP-B-45-1474: bis (hydroxymethyl) cyclohexane, bis (hydroxyethyl) benzene, ethylene oxide adduct of bisphenol A, and the like], and a mixture of two or more thereof are exemplified. .
Examples of the polyalkylene ether diol having a weight average molecular weight of 5,000 or less include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, and a mixture of two or more of these.
[0028]
Examples of the polycarboxylic acids include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, etc.), and dicarboxylic acids of these dicarboxylic acids. Ester-forming derivatives such as acid anhydrides and lower alkyl (1-4 carbon atoms) esters and mixtures of two or more of these; lactones include, for example, ε-caprolactone, γ-butyrolactone, γ-valerolactone And mixtures of two or more of these.
[0029]
Polyesterification is carried out by a conventional method, for example, by converting a low-molecular-weight polyol and / or a polyether polyol having a weight-average molecular weight of 5,000 or less to a polycarboxylic acid or an ester-forming derivative thereof (eg, an anhydride (eg, maleic anhydride, phthalic anhydride, etc. ), Lower esters (dimethyl adipate, dimethyl terephthalate, etc.), halides, etc.) or their anhydrides and alkylene oxides (eg, ethylene oxide and / or propylene oxide). Production by a method in which an active hydrogen group is left at a terminal by using a certain polyol in excess, or a method in which a lactone is added to an initiator (a low molecular weight diol and / or a polyether diol having a weight average molecular weight of 5,000 or less). Can be.
[0030]
Specific examples of the polyester resin (a (2)) include, for example, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, and polybutylene hexade. Methylene adipate diol, polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diol, polycaprolactone diol or triol, polyhexamethylene Carbonate diol and the like.
[0031]
As for the ratio of the constituent components of the hydroxyl group-containing polyester, the ratio of the polyol to the polycarboxylic acid is preferably 2/1 to 1/1 as the molar ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. , More preferably 1.5 / 1 to 1/1, and still more preferably 1.3 / 1 to 1.02 / 1. In the case of other components, the ratio is the same except that the components are changed. The weight average molecular weight is preferably from 1,000 to 50,000, more preferably from 2,000 to 20,000, even more preferably from 3,000 to 15,000.
[0032]
Examples of the active hydrogen group of the polyester resin (a (2)) include an alcoholic hydroxyl group and a carboxylic acid group at the polycondensation terminal of an alcohol and a carboxylic acid.
[0033]
Examples of the polyurethane resin (a <3>) include a polyadduct of a polyol and a diisocyanate.
[0034]
Specific examples of the diisocyanate include those exemplified below.
{Circle around (1)} Aliphatic diisocyanates having 2 to 18 carbon atoms (excluding carbon in the NCO group, the same applies hereinafter) [for example, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4 -Trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6- Diisocyanatohexanoate, etc.];
(2) alicyclic diisocyanate having 4 to 15 carbon atoms [for example, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI) , Bis (2-isocyanatoethyl) -4-cyclohexene and the like];
(3) Aromatic diisocyanate having 6 to 14 carbon atoms [for example, 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4 ′ -Or 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4 '-Diisocyanatodiphenylmethane, crude MDI, 1,5-naphthylene diisocyanate, etc.];
(4) C8-C15 araliphatic diisocyanate [eg, m- or p-xylylenediisocyanate (XDI), α, α, α ′, α′-tetramethylxylylenediisocyanate (TMXDI), etc.];
(5) Modified products of these diisocyanates [eg, modified diisocyanates having a carbodiimide group, a uretdione group, a uretoimine group, a urea group, etc.];
(6) and mixtures of two or more of (1) to (5).
Preferred of these are HDI and MDI.
[0035]
Specific examples of the polyol include, for example, compounds having a structure in which an alkylene oxide (hereinafter abbreviated as AO) is added to an active hydrogen atom-containing polyfunctional compound, and a mixture of two or more thereof.
[0036]
Examples of active hydrogen atom-containing polyfunctional compounds include polyhydric alcohols (a-3), polyhydric phenols (a-3) 2, amines (a-3) 3, and polycarboxylic acids. (A ▲ 3４4), phosphoric acids (a ▲ 3 ▼ 5), polythiol (a ▲ 3 ▼ 6) and the like.
[0037]
Examples of the polyhydric alcohol (a (3) 1) include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, and bis ( Dihydric alcohols such as (hydroxymethyl) cyclohexane and bis (hydroxyethyl) benzene; glycerin, trimethylolpropane, pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylitol, mannitol, dipentaerythritol, glucose, fructose, sho Examples thereof include polyhydric alcohols having 3 to 8 valences such as sugars.
[0038]
Examples of the polyhydric phenols (a (3) 2) include bisphenols such as bisphenol A, bisphenol F, and bisphenol S, in addition to polyhydric phenols such as pyrogallol, catechol, and hydroquinone.
[0039]
Examples of the amines (a ▲ 3 ▼ 3) include ammonia, monoamines such as alkylamines having 1 to 20 carbon atoms (such as butylamine) and aniline; and fats such as ethylenediamine, trimethylenediamine, hexamethylenediamine, and diethylenetriamine. Group polyamines; piperazine, N-aminoethylpiperazine and other heterocyclic polyamines described in JP-B-55-21044; alicyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; phenylenediamine, tolylenediamine, diethyltolylenediamine Aromatic polyamines such as amines, xylylenediamine, diphenylmethanediamine, diphenyletherdiamine, polyphenylmethanepolyamine; and monoethanolamine, diethanolamine, Noruamin, like alkanol amines such as triisopropanolamine.
[0040]
Examples of the polycarboxylic acid (a (3) 4) include aliphatic polycarboxylic acids such as succinic acid and adipic acid, and aromatic polycarboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid.
[0041]
Examples of the phosphoric acids (a ▲ 3 ▼ 5) include phosphoric acid, phosphorous acid, phosphonic acid and the like. Examples of the polythiol (a (3) 6) include a polyvalent polythiol compound obtained by reacting a glycidyl group-containing compound with hydrogen sulfide.
[0042]
The active hydrogen atom-containing compounds described above may be used in combination of two or more.
[0043]
Examples of AO to be added to the above active hydrogen atom-containing compound include ethylene oxide (EO), propylene oxide (PO), 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran (THF), Styrene oxide, α-olefin oxide, epichlorohydrin and the like can be mentioned.
[0044]
AO may be used alone or in combination of two or more types. In the latter case, a block addition (chip type, balance type, active secondary type, etc.) or a random addition or a mixed system of both (a chip added after random addition: in the molecule) Having 0 to 50% by weight (preferably 5 to 40% by weight) of ethylene oxide chains arbitrarily distributed, and having EO chains of 0 to 30% by weight (preferably 5 to 25% by weight) chipped at molecular terminals ]. Among these AOs, preferred are EO alone, PO alone, THF alone, a combination of PO and EO, and a combination of PO and / or EO with THF (in the case of a combination, random, block and a mixed system of both).
[0045]
The addition of AO to an active hydrogen atom-containing compound can be carried out in a usual manner, without a catalyst or in the presence of a catalyst (alkali catalyst, amine catalyst, acidic catalyst) (particularly in the latter stage of AO addition). The reaction is carried out in one or more stages under normal pressure or pressure.
[0046]
The degree of unsaturation of the polyol is preferably as small as possible, preferably 0.1 meq / g or less, more preferably 0.05 meq / g or less, and still more preferably 0.02 meq / g or less.
[0047]
The ratio of the polyol to the diisocyanate is preferably 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, as the molar ratio [OH] / [NCO] of the hydroxyl group [OH] and the isocyanate group [NCO]. 1, more preferably 1.3 / 1 to 1.02 / 1. In the case of other components, the ratio is the same except that the components are changed. The weight average molecular weight is preferably from 1,000 to 50,000, more preferably from 2,000 to 20,000, even more preferably from 3,000 to 15,000.
[0048]
Examples of the active hydrogen group of the polyurethane resin (a (3)) include an active hydrogen group that is not urethanized and is derived from a compound containing an active hydrogen atom, and hydrogen in a urethane bond.
[0049]
Examples of the epoxy resin (a-4) include an addition condensate of a polyepoxide (a-4) 1 and a polycarboxylic acid (a-4) 2. During this addition polymerization, a hydroxyl group containing an active hydrogen group is generated.
Examples of the active hydrogen group of the epoxy resin (a <4>) include an alcoholic active hydrogen group generated by epoxidation.
[0050]
Examples of the polycarboxylic acid (a <4> 2) include those described above. Further, the polyepoxide (a <4> 1) may be any of aromatic, heterocyclic, alicyclic or aliphatic.
[0051]
Examples of the aromatic polyepoxide (a <4> 1) include glycidyl ethers of polyhydric phenols, such as bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, and bisphenol AD. Diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene Diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybifu Phenyl diglycidyl ether, glycidyl ether of phenol or cresol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A with 3 mol of epichlorohydrin, obtained by condensation reaction of phenol and glyoxal, glutaraldehyde, or formaldehyde And polyglycidyl ethers of polyphenols obtained by the condensation reaction of resorcinol and acetone.
Further, in the present invention, as the aromatic polyepoxide, for example, a diglycidyl urethane compound obtained by an addition reaction of tolylene diisocyanate or diphenylmethane diisocyanate with glycidol, a glycidyl group-containing polyurethane obtained by reacting a polyol with the two reactants It also includes a (pre) polymer and a diglycidyl ether of an alkylene oxide (ethylene oxide or propylene oxide) adduct of bisphenol A.
[0052]
Examples of the heterocyclic polyepoxide (a <4> 1) include trisglycidylmelamine.
[0053]
Examples of the alicyclic polyepoxide (a <4> 1) include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, and ethylene glycol bisepoxydicyclopentyl. Ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3 , 4-epoxy-6-methylcyclohexylmethyl) butylamine. The alicyclic polyepoxide also includes a nuclear hydrogenated product of the aromatic polyepoxide compound.
[0054]
Examples of the aliphatic polyepoxide (a <4> 1) include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids, and glycidyl aliphatic amines.
Examples of polyglycidyl ethers of polyhydric aliphatic alcohols include, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and trimethylolpropane triane. Glycidyl ether, pentaerythritol tetraglycidyl ether, and sorbitol polyglycidyl ether.
Examples of the polyglycidyl ester of polyvalent fatty acid include diglycidyl adipate.
Examples of the glycidyl aliphatic amine include N, N, N ', N'-tetraglycidylhexamethylenediamine.
In the present invention, the aliphatic polyepoxide also includes a (co) polymer of glycidyl (meth) acrylate.
[0055]
Of these, preferred is a condensate of bisphenol A diglycidyl ether and adipic acid. The weight average molecular weight is preferably from 1,000 to 200,000, more preferably from 2,000 to 100,000, and still more preferably from 3,000 to 50,000.
[0056]
The fine particles (A) are made of a resin (a) containing active hydrogen, and if necessary, may be made of the resin (a) and a curing agent (C). The resin (a) and the curing agent (C) are mixed, for example, by dissolving in an organic solvent or by melt-kneading.
[0057]
Examples of the organic solvent include aromatic hydrocarbon solvents, aliphatic or alicyclic hydrocarbon solvents, halogen solvents, ester or ester ether solvents, ether solvents, ketone solvents, and alcohol solvents. Amide solvents, sulfoxide solvents, heterocyclic compound solvents, and mixed solvents of two or more of these. Of these, ether solvents, ester ether solvents and aromatic hydrocarbon solvents are preferred.
[0058]
Examples of the aromatic hydrocarbon solvent include toluene, xylene, ethylbenzene, tetralin and the like.
Examples of the aliphatic or alicyclic hydrocarbon solvent include n-hexane, n-heptane, mineral spirit, cyclohexane and the like.
Examples of the halogen-based solvent include methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene, and the like.
Examples of the ester solvent include ethyl acetate, butyl acetate and the like.
Examples of the ester ether solvent include methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and the like.
Examples of the ether-based solvent include diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether.
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone.
Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, and benzyl alcohol.
Examples of the amide solvent include dimethylformamide, dimethylacetamide and the like.
Examples of the sulfoxide-based solvent include dimethyl sulfoxide.
Examples of the heterocyclic compound-based solvent include N-methylpyrrolidone.
[0059]
The curing agent (C) is not particularly limited as long as it is a compound containing two or more functional groups capable of reacting with active hydrogen in one molecule, and for example, an isocyanate group-containing compound which may be blocked ( C1), an epoxy group-containing compound (C2), a silyl ether group-containing compound (C3), a melamine resin (C4), and a (hemi) acetal group-containing compound (C5).
Of these, preferred are the isocyanate group-containing compound (C1) and / or the epoxy group-containing compound (C2) which may be blocked.
[0060]
The isocyanate group-containing compound (C1) which may be blocked is not particularly limited as long as it is a compound having two or more isocyanate groups in one molecule. For example, the diisocyanates exemplified above, Modified products (such as modified products containing urethane group, carbodiimide group, allophanate group, urea group, buret group, isocyanurate group or oxazolidone group), HDI isocyanurate, HDI buret, IPDI isocyanurate, IPDI buret, crude MDI Crude diaminodiphenylmethane {a condensation product of formaldehyde and an aromatic amine (aniline or the like) or a mixture thereof: a phosgenated product of a mixture of diaminodiphenylmethane and a small amount (for example, 5 to 20% by weight) of a trifunctional or higher polyamine}; Polyisocyanate (PAPI), and these blocked isocyanate compounds.
Of these, HDI isocyanurate and IPDI isocyanurate are preferred.
[0061]
Examples of the isocyanate group blocking agent include lactams (such as ε-caprolactam, δ-valerolactam, and γ-butyrolactam), phenols (such as phenol, cresol, ethylphenol, butylphenol, nonylphenol, and dinonylphenol), and oximes. (Methyl ethyl ketone oxime (hereinafter abbreviated as MEK oxime), acetophenone oxime, benzophenone oxime, etc.), alcohols (methanol, ethanol, butanol cyclohexanol, etc.), diketones (dimethyl malonate, diethyl malonate, methyl acetoacetate, methyl acetoacetate, ethyl acetoacetate) , Acetylacetone, etc.), mercaptans (butyl mercaptan, dodecyl mercaptan, etc.), uretdiones (isophorone diisocyanate dimer, hexamethylene dimer) Socia sulfonate dimer), amides (acetanilide, acetamide, etc.), imides (succinimide, maleimide, etc.) and sulfites (sodium bisulfite, etc.), and mixtures of two or more of the above.
Of these, alcohols, lactams, oximes, and phenols are preferred, and methanol, ethanol, and methyl ethyl ketone oxime are particularly preferred.
[0062]
Examples of the epoxy group-containing compound (C2) include aliphatic, alicyclic, heterocyclic and aromatic polyepoxide compounds. Examples of such a polyepoxide compound include the polyepoxides exemplified above, and glycidyl aromatic polyamines.
Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline and N, N, N ′, N′-tetraglycidyldiphenylmethanediamine.
Of these, polyglycidyl ethers of polyhydric aliphatic alcohols and glycidyl ethers of polyhydric phenols are preferred.
[0063]
Examples of the silyl ether group-containing compound (C3) include compounds having the following silyl ether groups (1) to (4).
[0064]
Embedded image

[0065]
As the melamine resin (C4), generally, a mixture of melamine and aldehyde and a partially polycondensed product thereof can be used.
Examples of melamine include melamine, methylol melamine, methylated methylol melamine, and butylated methylol melamine.
Examples of the aldehyde include formaldehyde, acetaldehyde, butyraldehyde, acrolein, and furfural.
[0066]
Examples of the (hemi) acetal group-containing compound (C5) include benzaldehyde diethyl acetal, benzaldehyde butyl acetal, benzaldehyde amyl acetal, benzaldehyde benzyl acetal, propionaldehyde butyl acetal, propionaldehyde amyl acetal, propionaldehyde benzyl acetal, and the like.
[0067]
The ratio of the active hydrogen-containing resin (a) to the curing agent (C) is preferably 1 as a molar ratio of the active hydrogen group of the resin (a) to the functional group capable of reacting with the active hydrogen of the curing agent (C). / 1 or more and 2/1 or less, more preferably 1.2 / 1 or more and 1.8 / 1 or less, still more preferably 1.3 / 1 or more and 1.6 / 1 or less. By reacting at a molar ratio of 1/1 or more, it is possible to prevent the surface shape of the coating film from being deteriorated due to an excessive side reaction of the curing agent functional group. In addition, by reacting at a molar ratio of 2/1 or less, active hydrogen of the active hydrogen-containing resin can sufficiently react, and a coating film having excellent coating performance such as strength and smoothness can be obtained. .
[0068]
In the water-dispersed powder slurry coating of the present invention, the content of the reactive surfactant (B) is preferably 0.1 to 10 with respect to the total weight of the fine particles (A) and the reactive surfactant (B). %, More preferably 0.5 to 8% by weight, most preferably 1 to 5% by weight.
[0069]
The resin content in the aqueous dispersion powder slurry coating obtained by the method of the present invention is preferably 20 to 75% by weight, more preferably 20 to 60% by weight. The resin content is a value measured according to JIS K5400-1979 (paint general test method).
The viscosity at 25 ° C. of the water-dispersed powder slurry coating of the present invention is preferably from 10 to 100,000 mPa · s, and more preferably from 50 to 5,000 mPa · s. The average particle size of the fine particles (A) in the slurry coating is 0.1 to 50 μm, preferably 0.5 to 20 μm, and more preferably 1.0 to 10 μm. The particle size may be measured by an electron microscope, a sedimentation method, an electrozone method, a dynamic light scattering method, or the like, but the measurement by the dynamic light scattering method is preferred from the viewpoint of suitability of the measured particle size range.
In the slurry coating of the present invention, the particle shape of the fine particles (A) may be irregular or spherical, but the spherical shape is preferable in terms of the smoothness and uniformity of the coating film. Here, the term “spherical” refers to particles having a ratio of the major axis / minor axis of the particles in the range of 1.0 to 1.5. The fine particles (A) are spherical with an average ratio of major axis / minor axis of 1.0 to 1.5, preferably 1.0 to 1.2.
The major axis / minor axis ratio is determined by observing the particles using an optical microscope, and defining the shortest distance between two parallel lines that are in contact with the contour in the plane view of the particles according to the definition of Heywood as the minor axis, and the maximum distance between the parallel lines perpendicular to the outline. The length is defined as the major axis, and the ratio of the major axis to the minor axis measured is calculated and obtained.
When the resin content is 20 to 75% by weight, the dispersibility of the fine particles (A) in water becomes good, and when the dispersion viscosity is 10 to 100,000 mPa · s, the handling as a coating material becomes easy. When the average particle diameter of the fine particles (A) is from 0.1 to 50 μm, there is no sedimentation of the particles in water, and the evaporation of water and the adjustment of viscosity during baking become easy. When the ratio of major axis / minor axis is in the range of 1.0 to 1.5, a coating film having excellent smoothness and uniformity can be obtained.
[0070]
As long as the effects of the present invention are not impaired, other known emulsifiers or surfactants (nonionic emulsifiers and surfactants, anionic emulsifiers and surfactants, cationic emulsifiers) may be used together with the reactive surfactant (B) if necessary. And various reactive emulsifiers and surfactants other than those in the present invention, into which a surfactant, a blocked isocyanate group, a carboxylic acid group, an epoxy group, a vinyl group, an acid anhydride, etc. are introduced. . When used in combination, the amount of the other emulsifier and surfactant is preferably 44% by weight or less, more preferably 37% by weight or less, based on the total amount of the emulsifier or surfactant.
[0071]
The water-dispersed powder slurry coating obtained by the method of the present invention may contain, if necessary, known additives (D) (for example, a viscoelasticity modifier, a dynamic surface tension modifier, a reaction accelerator, Fillers, thickeners, heat or weather resistant stabilizers, leveling agents, defoamers, preservatives, colorants, etc.) can be optionally included.
[0072]
Examples of the viscoelasticity adjusting agent include a polymer type viscoelasticity adjusting agent such as a polycarboxylic acid type, a polysulfonic acid type, a polyether-modified carboxylic acid type and a polyether type, and an association type viscoelasticity adjusting agent such as a urethane-modified polyether type. Is mentioned. The amount is preferably 10.0% or less, more preferably 0.1 or more and 5% or less, based on the water-dispersed powder slurry coating.
[0073]
Examples of the dynamic surface tension adjuster include an acetylene glycol-based dynamic surface tension adjuster, a fluorine-based dynamic surface tension adjuster, and a silicone-based dynamic surface tension adjuster. The compounding amount is preferably 0.05% or more and 20.0% or less, more preferably 0.1 or more and 10% or less based on the slurry paint.
[0074]
Examples of the reaction accelerator include amine compounds such as diazabicyclooctane and 1,8-diazabicyclo (5,4,0) -undecene-7, and metal-containing compounds such as dibutyltin dilaurate and zirconium octylate. The compounding amount is preferably 5.00% or less, more preferably 0.1% or more and 3% or less, based on the water-dispersed powder slurry coating.
[0075]
Examples of the weather stabilizer include salicylic acid-based ultraviolet absorbers such as phenyl salicylate and p-tert-butylphenyl salicylate; benzophenone-based ultraviolet absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone; Benzotriazole ultraviolet absorbers such as (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2-ethylhexyl-2-cyano- Examples include cyanoacrylate ultraviolet absorbers such as 3,3'-diphenylacrylate, and hindered amine light stabilizers such as octylated diphenylamine and isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate. Be The amount is preferably 10% or less, more preferably 0.5% or more and 3% or less, based on the water-dispersed powder slurry coating.
[0076]
The leveling agent is not particularly limited. For example, olefin resins such as low molecular polyethylene and low molecular polypropylene, olefin copolymers such as ethylene-acryl copolymer and ethylene-methacryl copolymer, and (meth) acryl copolymer And polyvinylpyrrolidone. The compounding amount is preferably 6% or less, more preferably 0.5% or more and 3% or less based on the water-dispersed powder slurry coating.
[0077]
The colorant used as necessary is not particularly limited, and examples thereof include inorganic pigments, organic pigments, and dyes. Examples of the inorganic pigment include titanium oxide, carbon black, chromium oxide, and ferrite. As organic pigments, azo pigments such as azo lake type, monoazo type, disazo type, chelated azo type, benzimidazolone type, phthalocyanine type, quinacridone type, dioxazine type, isoindolinone type, thioindigo type, perylene type, quinophthalone type, anthraquinone And other polycyclic pigments. Dyes include nigrosine and aniline dyes. The mixing amount varies depending on the type of the coloring agent, but is preferably 30% or less, more preferably 1.0% or more and 10% or less, based on the water-dispersed powder slurry coating.
[0078]
Examples of the method for producing the water-dispersed powder slurry coating of the present invention include, but are not limited to, the following methods.
{Circle around (1)} Solvent removal method [in an aqueous medium containing a reactive surfactant (B) (water or a mixed solvent of water and a water-miscible solvent of an alcohol such as methanol or isopropanol or a ketone solvent such as acetone; if necessary) The above-mentioned resin (a), curing agent (C), and various additives (D) are dissolved in the above-mentioned organic solvent, and dispersed in a reaction vessel with a homomixer or the like. The pressure is reduced to 0.1 to 15 Torr while heating to a maximum of 100 ° C. if necessary, and the above water-miscible solvent and the organic solvent alone are mainly desolvated so that water remains, and the average particle diameter is 0.1 μm. Method of dispersing resin particles having a size of about 50 μm in water];
{Circle around (2)} Pulverized particle dispersion method [The resin (a), the curing agent (C) and the various additives (D) are melt-kneaded, cooled and pulverized to obtain resin particles having an average particle diameter of 0.1 to 50 μm. , An aqueous medium containing a reactive surfactant (B) and, if necessary, various additives (D), and a disperser or the like for dispersing in a reaction vessel].
The concentration of the resin (a) and the curing agent (C) in the organic solvent in the production according to (1) is preferably 20 to 75% by weight, more preferably 40 to 60% by weight.
The temperature in the system of the aqueous resin dispersion is preferably -5 to 100C, more preferably 30 to 80C, and the solvent removal is preferably 0.1 to 50 hours, more preferably 2 to 10 hours.
[0079]
Examples of the disperser used in the method for producing the resin aqueous dispersion include a homomixer, a high-pressure homomixer, a disperser, a high-pressure homogenizer, a static mixer, a film emulsifier, a fill mix, an ultrasonic disperser, and the like. . Of these, a homomixer is preferred.
[0080]
In the present invention, the reactive surfactant (B) exhibits good surfactant activity and dispersion stability. At the same time, by applying the water-dispersed powder slurry paint of the present invention and then baking, the surfactant (B) causes a chemical bond with the curing agent (C) and is taken into the film, resulting in excellent water resistance. Shows properties and strength.
[0081]
The water-dispersed powder slurry coating of the present invention can be applied using a conventional coating equipment for water-based coating or a spray coating machine which is a coating equipment for solvent coating, and does not require a new equipment.
In the method of forming a coating film, the water-dispersed powder slurry coating is applied by spraying to an object to be coated so that the wet film thickness is preferably 10 μm or more and 200 μm or less, more preferably 10 μm or more and 100 μm or less. While the paint floats from the spray nozzle to the object to be coated, the moisture in the paint evaporates and the resin content increases. The paint resin content (% by weight) at the time of application to the object to be coated can be expressed by the difference between the value obtained by dividing the difference between the amount of applied paint and the weight of the coated film after heating by the amount of applied paint and 100. It is preferably 50% by weight or more and 95% by weight or less, more preferably 60% by weight or more and 90% by weight or less. When the resin content in the applied paint is 50% by weight or more, no sagging of the paint occurs. A smooth coating film can be formed.
The coated object is preferably at a temperature of 100 ° C. or more and 200 ° C. or less, more preferably 120 ° C. or more and 180 ° C. or less, preferably 5 minutes or more and 60 minutes or less, more preferably 5 minutes or more and 30 minutes or less, particularly Preferably, the coating film can be formed by heating for 5 to 20 minutes.
The film thickness of the coated object obtained by applying and baking the coating material of the present invention is preferably 10 μm or more and 150 μm or less, more preferably 15 μm or more and 50 μm or less.
[0082]
The slurry paint obtained by the method of the present invention can be used particularly as a top coat for automobiles or for painting various products such as buildings and home electric appliances.
[0083]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Production Examples and Examples, but the present invention is not limited thereto. In the following, "parts" indicates parts by weight and "%" indicates% by weight.
[0084]
Production Example 1
A reaction vessel equipped with a stirrer, a dropping funnel, a nitrogen gas inlet tube, a thermometer, and a reflux condenser was charged with 23 parts of 4-α-cumylphenol and 0.35 part of a Lewis acid catalyst (Galleon Earth, manufactured by Mizusawa Chemical Industry Co., Ltd.). Under stirring, the inside of the system was replaced with nitrogen gas, and the temperature was raised to 110 ° C. At the same temperature, 77 parts of styrene were added dropwise over 3 hours, and the mixture was further reacted at the same temperature for 5 hours. After cooling to 30 ° C., the catalyst was separated by filtration to obtain 95 parts of (B0-1) obtained by adding 7 mol of styrene to 1 mol of 4-α-cumylphenol (number average molecular weight: 900). . 45 parts of EO was added to 55 parts of (B0-1) to obtain 100 parts of a reactive surfactant [B-1] having an oxyethylene unit content of 55% by weight and a weight average molecular weight of 2,400.
[0085]
Production Example 2
Hydroxyl group-containing hydrocarbon obtained by the same Friedel-Crafts reaction as in Production Example 1 [2 moles of styrene and 5 moles of α-methylstyrene added to 1 mole of 4-α-cumylphenol; number average molecular weight 1 , 100] and 55 parts of EO were added to obtain 100 parts of a reactive surfactant [B-2] having an oxyethylene unit content of 55% by weight and a weight average molecular weight of 2,600.
[0086]
Production Example 3
Hydroxyl group-containing hydrocarbon obtained by the same Friedel-Crafts reaction as in Production Example 1 [2 mol of styrene and 1 mol of α-methylstyrene added to 1 mol of phenol; number average molecular weight 400] 35 parts of EO and 65 parts of EO Was added to obtain 100 parts of a reactive surfactant [B-3] having an oxyethylene unit content of 65% by weight and a weight average molecular weight of 2,000.
[0087]
Production Example 4
23.7 parts of the reactive surfactant [B-1] obtained in Production Example 1, 73.2 parts of polyethylene glycol (number average molecular weight 6,000) and 3.0 parts of hexamethylene diisocyanate (hereinafter abbreviated as HDI) Was reacted at 80 ° C. for 3 hours to obtain 100 parts of a reactive surfactant [B-4] having an oxyethylene unit content of 83% by weight and a weight average molecular weight of 10,000.
[0088]
Production Example 5
88.3 parts of dodecylbenzyl alcoholamine was neutralized with 11.7 parts of hydrochloric acid to obtain 100 parts of a reactive surfactant [B-5] having a number average molecular weight of 312.5.
[0089]
Production Example 6
48.8 parts of lauric acid and 51.2 parts of diethanolamine were heated and dehydrated and condensed while stirring under a nitrogen stream to obtain 100 parts of a reactive surfactant [B-6] having a number average molecular weight of 392.
[0090]
Production Example 7
15.4 parts of stearylamine and 84.6 parts of ethylene oxide are heated while stirring under a nitrogen stream to carry out an ethylene oxide addition reaction, and a reactive surfactant having a weight average molecular weight of 1,300 and oxyethylene unit of 84.6% by weight [ B-7] 100 parts were obtained.
[0091]
Preparation of acrylic hydroxy functional resin
250 parts of xylene were placed in the reactor and heated to 100 ° C., then the mixture in the following proportions was added dropwise for about 3 hours. The reaction during that time was performed under a nitrogen atmosphere. After completion of the dropwise addition, the reaction was continued at 100 ° C. for 2 hours while maintaining the temperature.
(1) Styrene 23 parts
(2) Methyl methacrylate 23 parts
(3) 20 parts of butyl acrylate
(4) 33 parts of hydroxyethyl acrylate
(5) Peroxy D (manufactured by NOF Corporation, peroxide) 1 part
After the completion of the reaction, the organic solvent and the residual monomer were removed by distillation under reduced pressure, and then vacuum drying was performed to obtain an acrylic hydroxy functional resin [acrylic resin 1] having a hydroxyl equivalent of 420 and a weight average molecular weight of 32,000.
59 parts of [acrylic resin 1] obtained above and 41 parts of MEK oxime-blocked HDI trimer (Duranate, manufactured by Asahi Kasei) are kneaded at 100 ° C. by using a heating kneader and then pulverized to about 5 μm to give an average particle diameter of 7 μm. [Acrylic resin 2] having a major axis / minor axis ratio of 1.2 was obtained.
[0092]
Preparation of polyester resin
200 parts of neopentyl glycol, 93 parts of ethylene glycol and 355 parts of terephthalic acid were charged into the reactor, and the reaction was allowed to proceed for 2 hours while heating at 230 ° C. to distill off generated water. Thereafter, 0.2 parts of dibutyltin oxide is added, and the reaction is continued until the acid value becomes 0.5 or less, whereby a weight average molecular weight of 12,000 having a hydroxyl group at both terminals used for the coating film of the present invention. Thus, a polyester resin [Polyester Resin 1] having a hydroxyl value of 16.5 mgKOH / g was obtained.
93 parts of [Polyester Resin 1] obtained above and 7 parts of HDI trimer (manufactured by Asahi Kasei Co., Ltd., duranate) blocked with MEK oxime were kneaded at 100 ° C. by using a heating kneader, pulverized to about 5 μm, and average particle diameter of 7 μm. [Polyester resin 2] having a major axis / minor axis ratio of 1.2 was obtained.
[0093]
Adjustment of epoxy resin
400 parts of xylene was charged into the reactor, and the temperature was raised to 80 ° C. under a nitrogen atmosphere. Thereto, a mixture of 67 parts of bisphenol A diglycidyl ether and 33 parts of adipic acid was dropped over 6 hours. After the completion of the dropwise addition, the reaction was carried out at the same temperature for 5 hours. After the completion of the reaction, the organic solvent was distilled under reduced pressure to obtain an epoxy resin [Epoxy resin 1] having a weight average molecular weight of 8,000 and a hydroxyl value of 120 mgKOH / g. Was.
57 parts of [Epoxy resin 1] obtained above and 43 parts of HDI trimer (manufactured by Asahi Kasei Co., Ltd., duranate) blocked with MEK oxime were kneaded using a heating kneader at 100 ° C., and then pulverized to about 5 μm to obtain an average particle diameter of 7 μm. Thus, an epoxy resin [epoxy resin 2] having a major axis / minor axis ratio of 1.2 was obtained.
[0094]
Preparation example of dispersion
Reactive surfactants [B-1] to [B-7] obtained in Production Examples 1 to 7, sodium laurate [B'-8] as a non-reactive surfactant, laurylamine hydrochloride [B '-9] was dispersed in 100 parts of water to obtain a dispersion. These are referred to as [dispersion 1] to [dispersion 9].
[0095]
Examples 1 to 7, Comparative Examples 1 and 2
In a beaker, 59 parts of [acrylic resin 1], 41 parts of MEK oxime-blocked HDI trimer (manufactured by Asahi Kasei Corporation, duranate), and 100 parts of tetrahydrofuran are mixed, and these are dispersed in [dispersion liquid 1] to [dispersion liquid 9]. ], And mixed for 1 minute at 9,000 rpm using an Ultra Disperser (manufactured by Yamato Scientific Co., Ltd.) to obtain an average particle size of 5 µm. After mixing, this mixed solution was put into a four-necked flask equipped with a stirring bar and a thermometer, and the solvent was removed at 25 ° C. under reduced pressure for 10 hours. Next, 0.1 part of a urethane-forming catalyst [“TEDA”, manufactured by Tosoh Corporation], 0.1 part of a light-resistant stabilizer [“DIC-TBS”, manufactured by Dainippon Ink and Chemicals, Inc.], and a viscoelasticity imparting agent [“SN Thickener-651”] , Manufactured by San Nopco Co., Ltd.] to obtain a resin aqueous dispersion paint having an average particle diameter, a ratio of major axis / minor axis, and viscosity as shown in Table 1.
[0096]
Examples 8 to 14, Comparative Examples 3 and 4
To 100 parts of [dispersion 1] to [dispersion 9] obtained by the dispersion preparation example, 100 parts of the acrylic hydroxy-functional resin fine powder [acrylic resin 2] obtained above was added, and an ultra disperser was added. (Manufactured by Yamato Scientific Co., Ltd.) and mixed at a rotation speed of 9,000 rpm for 1 minute. Then, 0.1 part of a urethane-forming catalyst [“TEDA”, manufactured by Tosoh Corporation] and 0.1 part of a light-resistant stabilizer [“DIC-TBS”, manufactured by Dainippon Ink & Chemicals, Inc.] were added, respectively, and the average particle diameter, major axis / minor axis were added. A resin aqueous dispersion paint having a ratio and a viscosity as shown in Table 2 was obtained.
[0097]
Examples 15 to 21, Comparative Examples 5 to 6
In a beaker, 93 parts of [Polyester Resin 1], 7 parts of MEK oxime-blocked HDI trimer (manufactured by Asahi Kasei Corporation, duranate) and 100 parts of tetrahydrofuran are mixed, and these are dispersed in [Dispersion 1] to [Dispersion 9]. ], And mixed for 1 minute at 9,000 rpm using an Ultra Disperser (manufactured by Yamato Scientific Co., Ltd.) to obtain an average particle size of 5 µm. After mixing, this mixed solution was put into a four-necked flask equipped with a stirring bar and a thermometer, and the solvent was removed at 25 ° C. under reduced pressure for 10 hours. Next, 0.1 part of a urethanization catalyst [“TEDA”, manufactured by Tosoh Corporation], 0.1 part of a light-resistant stabilizer [“DIC-TBS”, manufactured by Dainippon Ink and Chemicals, Inc.], and a viscoelasticity imparting agent [“SN Thickener-651”] , Manufactured by San Nopco Co., Ltd.] to obtain a resin aqueous dispersion paint having an average particle diameter, a ratio of major axis / minor axis, and viscosity as shown in Table 3.
[0098]
Examples 22 to 28, Comparative Examples 7 to 8
To 100 parts of [dispersion liquid 1] to [dispersion liquid 9] obtained by the dispersion preparation example, 100 parts of the fine powder of the polyester-based hydroxy functional resin [polyester resin 2] obtained above was added, and an ultra disperser was added. (Manufactured by Yamato Scientific Co., Ltd.) and mixed at a rotation speed of 9,000 rpm for 1 minute. Then, 0.1 part of a urethane-forming catalyst [“TEDA”, manufactured by Tosoh Corporation] and 0.1 part of a light-resistant stabilizer [“DIC-TBS”, manufactured by Dainippon Ink & Chemicals, Inc.] were added, respectively, and the average particle diameter, major axis / minor axis were added. A resin aqueous dispersion paint having a ratio and a viscosity as shown in Table 4 was obtained.
[0099]
Examples 29 to 35, Comparative Examples 9 to 10
In a beaker, 57 parts of epoxy resin [Epoxy resin 1], 43 parts of MEK oxime-blocked HDI trimer (Duranate, manufactured by Asahi Kasei), 2 parts of benzoin (degassing agent), and 1 part of KP322 (Shin-Etsu Chemical leveling agent) And 100 parts of methyl ethyl ketone, and the mixture was added to 100 parts of [dispersion liquid 1] to [dispersion liquid 9]. Then, using an ultra disperser (manufactured by Yamato Scientific Co., Ltd.), the mixture was heated to 1 at a rotation speed of 9,000 rpm. After mixing for 5 minutes, the average particle size was 5 μm. After mixing, this mixed solution was put into a four-necked flask equipped with a stirring bar and a thermometer, and the solvent was removed at 25 ° C. under reduced pressure for 10 hours. Next, 0.1 part of a urethanization catalyst [“TEDA”, manufactured by Tosoh Corporation], 0.1 part of a light-resistant stabilizer [“DIC-TBS”, manufactured by Dainippon Ink and Chemicals, Inc.], and a viscoelasticity imparting agent [“SN Thickener-651” , Manufactured by San Nopco Co., Ltd.] to obtain a resin aqueous dispersion paint having an average particle diameter, a ratio of major axis / minor axis and viscosity as shown in Table 5.
[0100]
Examples 36 to 42, Comparative examples 11 to 12
To 100 parts of [dispersion liquid 1] to [dispersion liquid 9] obtained according to the dispersion example, 100 parts of the epoxy resin fine powder [epoxy resin 2] obtained above was added, and an ultra disperser (Yamato Scientific Co., Ltd.) was added. Was mixed at 9,000 rpm for 1 minute. Then, 0.1 part of a light stabilizer [“DIC-TBS”, manufactured by Dainippon Ink and Chemicals, Ltd.] was added to each, and a resin aqueous dispersion paint having an average particle diameter, a major axis / minor axis ratio and a viscosity shown in Table 6 was prepared. Obtained.
[0101]
Each resin aqueous dispersion obtained by the above method was evaluated by the following test methods. The results are shown in Tables 1 to 6.
[0102]
(Preparation of test pieces)
The obtained aqueous resin dispersion paint was spray-coated on a zinc phosphate-treated steel sheet, pre-baked at 80 ° C. for 10 minutes, and baked and dried at 150 ° C. for 20 minutes to obtain a coating film having a thickness of 0.03 mm.
(Test method)
Measurement of water absorption: The coating film obtained above was immersed in water at 25 ° C. for 1 hour, and the weight gain was measured to determine the water absorption.
Extract content ratio: 10.0 g of the heat-cured coating film obtained above was extracted with ethanol using a Soxhlet extractor at 78 ° C. for 2 hours. Value reduced by the extractables content of the coating.
Evaluation of acid rain resistance: 0.4 g of a 30% sulfuric acid aqueous solution was dropped on the coating film obtained above, heated at 80 ° C. for 30 minutes with a circulating drier, washed with water, and the coated surface was visually evaluated. .
：: No change was observed on the painted surface.
Δ: Some traces of dripping are observed.
×: Marks, whitening or blisters are remarkably observed on the drop marks.
Measurement of coating film strength: The surface hardness of the coating film obtained above was measured with a Fischer hardness meter (Fisher scope H100V manufactured by Fischer Instruments). (Load: 0.4-100mN, indentation depth: 5μm) This test method can numerically calculate the coating hardness of the paint with high accuracy, and in a single test, the coating hardness, Young's modulus, etc. Elements can be evaluated. The strength of the coating film can be evaluated by measuring the surface hardness. It is determined that the greater the hardness value, the greater the coating film strength.
[0103]
[Table 1]

[0104]
[Table 2]

[0105]
[Table 3]

[0106]
[Table 4]

[0107]
[Table 5]

[0108]
[Table 6]

[0109]
【The invention's effect】
The water-dispersed powder slurry coating of the present invention is incorporated into the cured coating film because the reactive surfactant used as the dispersant has active hydrogen in the molecule. Therefore, the cured coating film has excellent water resistance, acid rain resistance, and hardness.
Because of the above-mentioned effects, the water-dispersed powder slurry coating of the present invention is extremely useful, for example, for coatings for automobiles, buildings, industrial machines and the like, particularly for automotive topcoats.

Claims (12)

Water comprising a fine particle (A) comprising a resin (a) having active hydrogen, a curing agent (C), and a reactive surfactant (B) having active hydrogen in an aqueous medium. Dispersed powder slurry paint. The water-dispersed powder slurry coating according to claim 1, wherein the fine particles (A) comprise the resin (a) and the curing agent (C). The aqueous dispersion powder slurry coating according to claim 1 or 2, wherein the reactive surfactant (B) is a nonionic surfactant having active hydrogen. The water-dispersed powder slurry coating according to any one of claims 1 to 3, wherein the reactive surfactant (B) contains a hydrophobic part having an aromatic ring and a hydrocarbon group having 6 to 100 carbon atoms. The reactive surfactant (B) is an addition reaction product (b3) comprising a monohydric phenol or a monohydric aromatic alcohol (b1) and a vinyl monomer (b2) or an alkylene oxide adduct thereof (b4). A water-dispersed powder slurry coating according to any one of claims 1 to 4. The aqueous dispersion according to any one of claims 1 to 5, wherein the reactive surfactant (B) contains an oxyethylene unit as a hydrophilic part in an amount of 20% by weight or more and 90% by weight or less based on the weight of the (B). Powder slurry paint. The water-dispersed powder slurry coating according to any one of claims 1 to 6, wherein the resin (a) is at least one selected from the group consisting of an acrylic resin, a polyester resin, a polyurethane resin, and an epoxy resin. The aqueous dispersion powder slurry coating according to any one of claims 1 to 7, wherein the curing agent (C) is a compound having an isocyanate group which may be blocked and / or a compound having an epoxy group. The water-dispersed powder slurry coating according to any one of claims 1 to 8, wherein the fine particles (A) have an average particle size of 0.1 µm or more and 50 µm or less. The water-dispersed powder slurry coating according to any one of claims 1 to 9, wherein the fine particles (A) are spherical having a major axis / minor axis ratio of 1.0 to 1.5. 11. The method according to claim 1, wherein the fine particles (A) are obtained by dispersing a solvent solution of the resin (a1) and, if necessary, the curing agent (C) in water and removing the solvent. A water-dispersed powder slurry paint as described in the above. A coating film obtained by applying and baking the water-dispersed powder slurry coating material according to claim 1.