JP4245637B2 - 有機無機複合塗膜、その製造方法及び水性塗料組成物 - Google Patents
有機無機複合塗膜、その製造方法及び水性塗料組成物 Download PDFInfo
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Description
本発明の有機無機複合塗膜中の無機酸化物(A)は、金属アルコキシド(C)のゾルゲル反応により得られるものである。加水分解により無機酸化物のネットワークを形成することができ、強固な塗膜が得られる点から、三価以上の金属アルコキシドを用いることが好ましい。特にテトラアルコキシシラン等の四価以上の金属アルコキシドを使用する場合には、得られる塗膜の硬度を高くすることができるため好ましい。塗膜硬度を高くする目的で、官能基数の多い金属アルコキシドを使用する場合には、全金属アルコキシド中の四価以上の金属アルコキシドの含有量が、30質量%以上であることが好ましく、50質量%以上であることがより好ましい。
本発明の有機無機複合塗膜において使用する中空ポリマー粒子は、前述の無機酸化物と複合化でき、単分散性であればよいが、その該表面が親水性であって水性媒体中で安定に分散しているものが好ましい。また、該中空ポリマー粒子の殻壁が薄いことが、得られる有機無機複合塗膜内部の多孔体構造と表面の凹凸構造を形成しやすい点から好ましい。この様な中空ポリマー粒子が容易に得られる点から、ラジカル重合性の水溶性モノマー(b1)とラジカル重合性の非水溶性モノマー(b2)とを水性媒体中で擬エマルジョン形式のラジカル重合反応を行うことにより得られるものであることが最も好ましい。
本発明の有機無機複合塗膜は、内部には球状の中空構造、表面には凹凸パターンを有するものである。本発明で言う球状の中空構造とは、金属酸化物の連続相となる塗膜断面に沿って、中空ポリマー粒子が規則的に配列した構造をいうものであって、特に三次元空間で最密充填されてなる規則性多孔体構造であることが好ましい。また、膜表面の凹凸パターンは、塗膜の表面全体にわたって、中空ポリマー粒子の配列により形成された半球状の凹凸構造をいうものであって、最密配列による半球状の凹凸パターンであることが好ましく、該パターンがハニカム状であることが最も好ましい。すなわち、無機酸化物が中空ポリマー粒子の3次元配列構造の全体に沿って連続した膜を形成しており、無機酸化物と有機ポリマーとが一体化した自己組織化的な塗膜である。
本発明の水性塗料組成物は、前述の有機無機複合塗膜を容易に与えうるものであって、中空ポリマー粒子(B)の水性分散体と、金属アルコキシド(C)と、酸触媒(D)とを含有するものである。
微粒子の形状及び中空性の観察には、キーエンス社製VE−9800走査型電子顕微鏡 (SEM)を用いた。
複合塗膜の硬さ(ユニバーサル硬度)測定には、Helmut Fischer社製のフィッシャースコープH100硬度計を用いた。
塗膜表面、断面形状の観察には、キーエンス社製VE−9800走査型電子顕微鏡 (SEM)とSII社製SPI4000原子間力顕微鏡 (AFM)を用いた。
塗膜のUV−Vis反射スペクトル測定には、日立製作所製のU−3500分光光度計を用いた。
<PNIPAM−co−PGMAからなる中空ポリマー粒子B−1の合成>
1.8gのN−イソプロピルアクリルアミド(株式会社興人製、以下NIPAMと称す。)を溶解した水溶液290mlにグリシジルメタクリレート(和光純薬工業株式会社製、以下、GMAと称す。)11.8gを加えて70℃で窒素フローしながら攪拌した(GMA/NIPAM=5.2mol/mol)。水溶性重合開始剤として、2,2’−アゾビス(2−アミジノプロパン)二塩酸塩(V−50、和光純薬工業株式会社製)0.15gを溶解した水溶液10mlを添加した。同温度で1時間攪拌することにより粒子の分散液を得た。この分散液を遠心分離操作によって洗浄した後、この微粒子の形状をSEM観察したところ、平均粒径225nmの単分散真球状の粒子であった(図1)。この微粒子を押しつぶして、形態の観察を行ったところ、粒子の中央が空洞の中空ポリマー粒子であることが確認できた(図2)。この粒子の殻壁の厚みはおよそ10nmであった。以下、この中空ポリマーをB−1と称す。
<PACMO−co−PGMAからなる中空ポリマー粒子B−2の合成>
1.8gのアクリロイルモルフォリン(株式会社興人製、以下ACMOと称す。)を溶解した水溶液290mlにGMA 13.5gを加えて70℃で窒素フローしながら攪拌した(GMA/ACMO=4.8mol/mol)水溶性重合開始剤として、V−50 0.15gを溶解した水溶液10mlを添加した。同温度で1時間攪拌することにより粒子の分散液を得た。この分散液を遠心分離操作によって洗浄した後、この微粒子の形状をSEM観察したところ、平均粒径270nmの単分散真球状の粒子であった(図3)。この微粒子を押しつぶして、形態の観察を行ったところ、粒子の中央が空洞の中空ポリマー粒子であることが確認できた(図4)。この粒子の殻壁の厚みはおよそ10nmであった。以下、この中空ポリマーをB−2と称す。
<B−1が含まれる水性塗料組成物>
合成例1で得た中空ポリマー粒子B−1の濃度が20%となる水分散体100部、10%のマレイン酸水溶液20部、シランオリゴマーMS−51(コルコート株式会社製)のイソプロパノール溶液(50%)100部を混合し、20℃の浴中2時間撹拌し、均一な分散状態である乳白色の水性塗料組成物を得た。
実施例1で調製した水性塗料組成物をガラス基材にバーコーター(5番)で塗布して得られる複合塗膜を25、80、130、180℃の各温度で30分間硬化させたところ、クラックの無い良好な膜が得られた。塗膜の物性を表1に示す。
実施例1で調製した水性塗料組成物を、ガラス板上に絵画用ブラシで塗布して絵を描いた。得られた絵柄複合塗膜表面のSEM観察から、微粒子の最密充填による規則配列の表面形態が確認された(図8)。
実施例1で調製した水性塗料組成物に木材板(杉板)を浸漬して塗布し、表面に複合塗膜を形成させた。得られた複合塗膜表面のSEM観察から、微粒子の最密充填による規則配列の表面形態が確認された(図9)。
<GN−2が含まれる水性塗料組成物>
合成例2で得た中空ポリマー粒子B−2の濃度が25%となる水分散体100部、10%のマレイン酸水溶液20部、シランオリゴマーMS−51のイソプロパノール溶液(50%)100部を混合し、20℃の浴中2時間撹拌し、均一な分散状態である乳白色の水性塗料組成物を得た。
実施例5で調製した塗料組成物をガラス基材にバーコーター(5番)で塗布して得られる複合塗膜を25、80、130、180℃の各温度で30分間硬化させたところ、クラックの無い良好な膜が得られた。塗膜の物性を表2に示す。硬化温度25℃で得られた複合塗膜表面および断面のSEM観察から、微粒子の規則的な配列パターンが確認された(図10及び図11)。また、この塗膜のAFM観察では、表面粒子配列による凹凸パターンが明確に現れ(図12)、谷間距離は370〜400nmであった(図13)。
実施例2で作製した塗膜3種類(25、80、130℃硬化後の膜)の反射スペクトルを測定したところ、いずれの膜でもピークが500〜550nmの可視光域での光応答性が示された(図14)。この現象は、表面にホールが形成したハイブリッド膜(特許文献1)、または内部にポリマー粒子を含む有機無機ハイブリッド膜(特許文献2)では全く現れなかった。即ち、本発明での塗膜表面および塗膜内部における中空粒子の規則的な配列が光反射効果をもたらしたと考えられる。
中空ポリマー粒子を用いない以外は、実施例1と同様の組成の塗液を調製し、ガラス基材にバーコーター(5番)で塗布して複合塗膜を得た。25、80℃で乾燥すると、膜には多数のクラックが発生し、膜は基板から脱落した。
Claims (11)
- 単分散性の中空ポリマー粒子(B)の水性分散体と、金属アルコキシド(C)と、酸性触媒(D)とを含有する水性塗料組成物を基材上に塗布した後、硬化することを特徴とする有機無機複合塗膜の製造方法。
- 前記中空ポリマー粒子(B)の表面が親水性である請求項1記載の有機無機複合塗膜の製造方法。
- 前記中空ポリマー粒子(B)が、ラジカル重合性の水溶性モノマー(b1)とラジカル重合性の非水溶性モノマー(b2)とを水性媒体中でラジカル重合させて得られるものである請求項1又は2記載の有機無機複合塗膜の製造方法。
- 前記中空ポリマー粒子(B)の殻壁厚みが10nm以上20nm以下で平均粒径が50nm以上150nm未満の粒子、または殻壁厚みが10nm以上80nm以下で平均粒径が150nm以上800nm以下の粒子である請求項1〜3の何れか1項記載の有機無機複合塗膜の製造方法。
- 前記金属アルコキシド(C)と前記中空ポリマー粒子(B)との使用割合が(B)/(C)で表される質量比で70/30〜5/95の範囲である請求項1〜4のいずれか1項記載の有機無機複合塗膜の製造方法。
- 請求項1〜5の何れか1項記載の製造方法で得られる有機無機複合塗膜であって、金属アルコキシド(C)のゾルゲル反応から得られる無機酸化物(A)からなるマトリクス中に、単分散性の中空ポリマー粒子(B)が3次元空間で最密充填されてなる規則性多孔体構造であることを特徴とする有機無機複合塗膜。
- 前記無機酸化物(A)が、三価以上の金属アルコキシドのゾルゲル反応により得られるものである請求項6記載の有機無機複合塗膜。
- 前記多孔体の孔径が40〜780nmの範囲にある請求項6又は7記載の有機無機複合塗膜。
- 塗膜の表面が中空ポリマー粒子(B)の最密配列による半球状の凹凸パターンを有する請求項6〜8の何れか1項記載の有機無機複合塗膜。
- 前記凹凸パターンがハニカム状である請求項9記載の有機無機複合塗膜。
- 請求項6〜10の何れか1項記載の有機無機複合塗膜を形成させる水性塗料組成物であって、
単分散性の中空ポリマー粒子(B)の水性分散体と、金属アルコキシド(C)と、酸触媒(D)とを含有することを特徴とする水性塗料組成物。
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CN200880008139.3A CN101631626B (zh) | 2007-03-14 | 2008-03-06 | 有机无机复合涂膜、使用其的结构色膜及它们的制造方法 |
PCT/JP2008/054044 WO2008120529A1 (ja) | 2007-03-14 | 2008-03-06 | 有機無機複合塗膜、これを用いる構造色膜及びそれらの製造方法 |
KR1020097015456A KR101082877B1 (ko) | 2007-03-14 | 2008-03-06 | 유기 무기 복합 도막, 이것을 사용하는 구조 색막 및 그들의 제조 방법 |
EP08721464A EP2135684A4 (en) | 2007-03-14 | 2008-03-06 | ORGANIC / INORGANIC COMPOSITE COATING FILM, STRUCTURAL COLOR FILM OBTAINED THEREFROM AND METHOD OF MANUFACTURING THEREOF |
US12/530,903 US8486494B2 (en) | 2007-03-14 | 2008-03-06 | Organic/inorganic composite coating film, structural color film using the same, and preparation methods thereof |
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