JP6706937B2 - 流雪性塗料、流雪性塗膜及び屋根部材 - Google Patents
流雪性塗料、流雪性塗膜及び屋根部材 Download PDFInfo
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- JP6706937B2 JP6706937B2 JP2016048710A JP2016048710A JP6706937B2 JP 6706937 B2 JP6706937 B2 JP 6706937B2 JP 2016048710 A JP2016048710 A JP 2016048710A JP 2016048710 A JP2016048710 A JP 2016048710A JP 6706937 B2 JP6706937 B2 JP 6706937B2
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- coating
- fatty acid
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- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- SOLUNJPVPZJLOM-UHFFFAOYSA-N trizinc;distiborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-][Sb]([O-])([O-])=O.[O-][Sb]([O-])([O-])=O SOLUNJPVPZJLOM-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008170 walnut oil Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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- Paints Or Removers (AREA)
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Description
酸化硬化性を有する樹脂成分(A)、フッ素系界面活性剤(B)及び有機溶剤を含み、樹脂成分(A)固形分質量100質量部を基準とするフッ素系界面活性剤(B)の配合量が、0.1〜5.0質量部の範囲内であって、塗装後初期の乾燥塗膜の動的水接触角が転落角で60°以下にある、流雪塗料、流雪性塗膜、屋根表面に流雪性を付与する方法、流雪性を有する屋根部材、に関する。
本発明において樹脂成分(A)は、酸化硬化性を有する樹脂であれば製法、材料等特に制限はないが、好適な樹脂としては、例えば、乾性油脂肪酸及び/又は半乾性油脂肪酸を製造原料として含む樹脂を挙げることができる。
SiXnY4−n 式(1)
(式中、Xは、水酸基又はアルコキシ基を表し、Yは、置換基を有していてもよい1価の炭化水素基を表し、そしてnは、1〜4の整数を表す。)
で表される、同一又は異なる2以上のオルガノシランが化学結合することにより生成した樹脂、例えば、オリゴマーであることができ、式(1)で表されるオルガノシランが、直鎖状、又は分岐鎖状に結合されることができる。また、上記シリコーン樹脂は、ケイ素原子と直接結合する炭化水素基を有することが好ましい。
等が挙げられる。
本発明の流雪塗料はフッ素系界面活性剤(B)を含むことを特徴とする。フッ素系界面活性剤(B)としては、フッ素置換された炭化水素鎖以外に親水性基を有する化合物が挙げられる。親水性基としては、例えば、スルホン酸、カルボン酸、リン酸等のアミンまたは金属塩、3級アミンのハロゲン化塩、水酸基、またはポリオキシアルキレン基等が挙げられる。
また、本発明の塗料は、顔料;有機金属化合物;シランカップリング剤:樹脂成分(A)以外のアクリル樹脂、フッ素樹脂、ウレタン樹脂、シリコーン樹脂等の改質用樹脂;有機溶剤;反応性希釈剤;付着付与剤、沈降防止剤、消泡剤、分散剤、湿潤剤、脱水剤、紫外線吸収剤、光安定化剤等の塗料用添加剤等を含むことができる。
本発明の塗料は着色塗料、艶消し塗料又はクリヤー塗料のいずれであってもよく、それによって顔料の配合量及び組成を適宜調整することができる。
また、本発明では顔料分の一部として、導電性無機顔料を含むことが適している。
かかる導電性無機顔料としては、例えばアンチモン酸亜鉛、ガリウムドープ酸化亜鉛、アンチモンドープ酸化すず、インジウムドープ酸化すず、リンドープ酸化すず、アルミニウムドープ酸化亜鉛、ニオブドープ酸化すず、フッ素ドープ酸化すず、ガリウムドープ酸化すず等が挙げられ、これらの中から単独で又は2種以上を組み合わせて使用することができる。
かかる導電性無機顔料の好ましい含有量としては、樹脂成分(A)固形分100質量部を基準として、0.05〜20質量部、好ましくは0.1〜10質量部の範囲内であることができる。
本発明の塗料が適用される被塗物としては、電線、橋桁、車両、航空機、電気通信施設、道路交通標識、ガードレール、遮音壁、建築物の屋根、側壁、信号機等の着氷防止が求められる物品を挙げることができる。
これらのうち、屋根面としては、新設でも既存の屋根のいずれでもよく、また、素材の種類、旧塗膜の種類や有無など特に制限されるものではない。
製造例1
反応容器に、下記アルキド樹脂溶液(*)36.5部(固形分23.7部)及び「スワゾール1000」(商品名、丸善石油化学社製、芳香族炭化水素系溶剤)23部を配合し、攪拌しながら120℃まで昇温した。
(モノマー組成物)
スチレン 23部
メチルメタクリレート 17.7部
2−エチルヘキシルアクリレート 10部
i−ブチルメタクリレート 22.5部
ヒドロキシエチルメタクリレート 2.3部
アクリル酸 0.8部
(開始剤溶液)
ターシャリーブチルパーオキサイド 5部
「スワゾール1000」 10部
(*)アルキド樹脂溶液:大豆油脂肪酸/無水フタル酸/ペンタエリスリトール/グリセリン=477部/147部/133部/4部の縮合体、希釈溶剤「スワゾール1000」、固形分65%。
フラスコ中にミネラルスピリット72部を仕込み、窒素ガスを通気しながら、115℃まで撹拌を行いながら昇温した。次いで、温度を115℃に保ちながら下記のモノマーなどの混合物を4時間かけて滴下した。
スチレン 25部
メタクリル酸n−ブチル 15部
メタクリル酸i−ブチル 20部
アクリル酸2−エチルヘキシル 20部
メタクリル酸グリシジル 20部
2,2′−アゾビスイソブチロニトリル 1部
次いで115℃で2時間熟成した後、140℃に昇温してからアマニ油脂肪酸30部及び反応触媒としてN,N−ジメチルアミノエタノール0.4部を加え、160℃で5時間保持して脂肪酸の付加反応を行った。反応終了後、ミネラルスピリット31部を加えて希釈して不揮発分50%の褐色透明で粘調な脂肪酸変性共重合体溶液を得た。
次に100℃まで冷却し、フラスコに水分離器を装備し、シリコーン樹脂「SH−6018」(東レ・ダウコーニング・シリコーン(株)製)20部、ミネラルスピリット20部及びテトラ−n−ブチルチタネート0.20部を加え、165℃まで昇温し、還流系中で水分離器で水を分離しながら5時間反応させて不揮発分約55%の褐色透明で粘調な乾性油脂肪酸変性アクリル樹脂溶液(A−2)を得た。樹脂の重量平均分子量は6万であった。
反応容器に、「スワゾール1000」(商品名、丸善石油化学社製、芳香族炭化水素系溶剤)23部を配合し、攪拌しながら120℃まで昇温した。
次いで、反応容器内液を同温度で保持、攪拌しながら、下記モノマー組成物及び開始剤溶液をそれぞれ3時間かけて滴下し、反応させた。
その後冷却させ、「スワゾール1000」(商品名、丸善石油化学社製、芳香族炭化水素系溶剤)で固形分が55%になるまで希釈し、酸化硬化性のないアクリル樹脂溶液(A−3)を得た。重量平均分子量は50000であった。
(モノマー組成物)
スチレン 23部
メチルメタクリレート 17.7部
2−エチルヘキシルアクリレート 10部
i−ブチルメタクリレート 22.5部
ヒドロキシエチルメタクリレート 2.3部
アクリル酸 0.8部
(開始剤溶液)
ターシャリーブチルパーオキサイド 4部
「スワゾール1000」 10部。
実施例1〜12及び比較例1〜5
下記配合組成にて塗料(X−1)〜(X−17)を製造し、下記評価試験に供した。結果を表1に併せて示す。
尚、塗料(X−7)は艶消しタイプであり、塗料(X−8)はクリヤータイプであり、(X−9)〜(X−12)は、導電性顔料含有タイプである。
(注2)シリコン系添加剤:テトラエトキシシラン縮合物。
軟鋼板に、各塗料を乾燥膜厚が50μmとなるようにアプリケーターで塗装し、20℃、7日間乾燥させたものを試験塗板とした。
(*1)光沢
各試験塗板を、BYK社製のグロスメータ「micro-TRI-gloss」(商品名、光沢計)を使用し、測定角度60度にて測定した。
(*2)L*値
各試験塗板のL*値を「MA−68II」(商品名、多角度分光光度計、X−Rite社製)を使用し、測定した。
(*3)摩擦係数
各試験塗板の摩擦係数を滑り抵抗性試験機「HEIDON」(商品名、ポータブル摩擦計)を用いて測定した。
(*4)静的接触角(°)
各試験塗板に、純水10μlを滴下し、測定温度20℃にて滴下後1分の接触角を型式CA−X(協和界面科学株式会社)のモニターを見て測定した。表中の値は3回測定したときの平均値である。
(*5)転落角(°)
各試験塗板の上に純水20μlを滴下し、測定温度20℃にて塗板を傾けた際に水滴が動き出した時の塗板の角度を転落角とした。測定は動的水接触角測定装置「DSA−100 micro」(商品名、KRUSS社製)を用いた。
(*6)凍結融解試験後の転落角
各試験塗板を、−20℃、16時間で曝した後、45℃、8時間で曝すサイクルを1サイクルとして10サイクル試験をした後に、転落角を測定した。
(*7)流雪性
冬季直前に、北海道札幌市の倉庫のトタン屋根(傾斜角度20度程度)に各塗料を乾燥膜厚が50μmとなるように、2m幅で分割塗装し、常温で乾燥させ、流雪性評価用屋根塗装を行った後、積雪時における屋根からの流雪状態を観察し、下記基準にて目視評価した。
5:雪が全く残っていない。
4:屋根表面のうち雪で覆われている部分が半分より少ない。
3:屋根表面のうち雪で覆われている部分が半分程度。
2:屋根表面のうち、雪で覆われている部分が半分を超えるが、雪で覆われていない部分も認められる。
1:屋根表面が全面雪で覆われている。
Claims (10)
- 酸化硬化性を有する樹脂成分(A)、フッ素系界面活性剤(B)及び有機溶剤を含み、樹脂成分(A)固形分質量100質量部を基準とするフッ素系界面活性剤(B)の配合量が、0.1〜5.0質量部の範囲内であって、塗装後初期の乾燥塗膜の動的水接触角が転落角で60°以下である、流雪塗料。
- 酸化硬化性を有する樹脂成分(A)が、乾性油脂肪酸及び/又は半乾性油脂肪酸を製造原料として含む樹脂である、請求項1に記載の流雪塗料。
- 樹脂成分(A)が、(メタ)アクリロイル基含有化合物を製造原料としてさらに含む樹脂である、請求項2に記載の塗料。
- 樹脂成分(A)が、乾性油脂肪酸及び半乾性油脂肪酸以外の酸成分、並びに多価アルコール成分を、製造原料としてさらに含む樹脂である、請求項2又は3に記載の塗料。
- 樹脂成分(A)が、シリコーン樹脂を製造原料としてさらに含む樹脂である、請求項2ないし4のいずれか1項に記載の塗料。
- 顔料をさらに含む、請求項1ないし5のいずれか1項に記載の塗料。
- 有機金属化合物をさらに含む、請求項1ないし6のいずれか1項に記載の塗料。
- 請求項1ないし7のいずれか1項に記載の塗料を用いて形成された、流雪性塗膜。
- 屋根表面に、請求項1ないし7のいずれか1項に記載の塗料を塗装することを含む、屋根表面に流雪性を付与する方法。
- 請求項8に記載の流雪性塗膜を備えた、流雪性を有する屋根部材。
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