JP6571007B2 - 耐衝撃性を有する塗膜を形成するための塗料組成物 - Google Patents
耐衝撃性を有する塗膜を形成するための塗料組成物 Download PDFInfo
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- JP6571007B2 JP6571007B2 JP2015559136A JP2015559136A JP6571007B2 JP 6571007 B2 JP6571007 B2 JP 6571007B2 JP 2015559136 A JP2015559136 A JP 2015559136A JP 2015559136 A JP2015559136 A JP 2015559136A JP 6571007 B2 JP6571007 B2 JP 6571007B2
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
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Description
本出願は、2014年1月24日に出願された、日本国特許出願第2014−011773号明細書(その開示全体が参照により本明細書中に援用される)に基づく優先権を主張する。
(A1−1)炭素数8以上の水酸基含有脂肪酸と多価アルコールとのエステル化物
(A1−2)炭素数8以上の水酸基含有不飽和脂肪酸の多量体
(A1−3)炭素数8以上の不飽和脂肪酸の多量体を還元したポリオール
(A1−4)炭素数8以上の不飽和脂肪酸(a1−4−1)及び/又は炭素数8以上の不飽和脂肪酸と多価アルコールとのエステル化物(a1−4−2)を水酸基変性したポリオール
からなる群より選択される少なくとも1種である項1〜4のいずれか1項に記載の塗料組成物。
ポリカプロラクトンジオール、ポリカプロラクトントリオール、ポリカプロラクトンテトラオール、ポリカーボネートジオール、及びポリアクリレートポリオールからなる群より選択される少なくとも1種のポリオール(A2)をさらに含む項1〜6のいずれか1項に記載の塗料組成物。
本発明は、(A)ポリオール、(B)ポリイソシアネート化合物及び(C)硬化触媒を含む塗料組成物であって、該成分(A)が、炭素数8以上の脂肪酸由来の構成単位を有するポリオール(A1)を含むものであり、かつ該硬化触媒(C)が、少なくとも1つのイミダゾール環を有するイミダゾール化合物であることを特徴とする塗料組成物を提供する。
本発明において(A)ポリオールは、炭素数8以上の脂肪酸由来の構成単位を有するポリオール(A1)を有するものであれば、特に限定されない。
本発明において、「炭素数8以上の脂肪酸由来の構成単位を有するポリオール(A1)」とは、脂肪酸由来の構成単位を有するポリオールであって、当該ポリオールを構成する脂肪酸由来の構成単位のうち少なくとも1個が炭素数8以上であるものを示す。
(A1−1)炭素数8以上の水酸基含有脂肪酸と多価アルコールとのエステル化物
(A1−2)炭素数8以上の水酸基含有不飽和脂肪酸の多量体
(A1−3)炭素数8以上の不飽和脂肪酸の多量体を還元したポリオール
(A1−4)炭素数8以上の不飽和脂肪酸(a1−4−1)及び/又は炭素数8以上の不飽和脂肪酸と多価アルコールとのエステル化物(a1−4−2)を水酸基変性したポリオール
等が挙げられる。
ポリカプロラクトンポリオールは、例えば、2価〜4価の多価アルコールを開始剤として、ε−カプロラクトンを開環重合することによって得ることができる。該2価以上の多価アルコールとしては、例えば、エチレングリコール、グリセリン、トリメチロールエタン、トリメチロールプロパン、ジグリセリン、ジトリメチロールプロパン、1,2,6−ヘキサントリオール、ペンタエリスリトール、トリス(2−ヒドロキシエチル)イソシアヌル酸、ジメチロールアルカン酸とモノエポキシ化合物(例えばHEXION Specialty Chemicals社製「カージュラE10」、合成高分岐飽和脂肪酸のグリシジルエステル)を反応させて得られた多価アルコール化合物等が挙げられる。これらは単独で又は2種以上組み合わせて使用することができる。
本発明において(A)ポリオールは、成分(A1)及び(A2)以外のポリオール(A3)を含んでいてもよい。成分(A3)のポリオールとしては、(A1)及び(A2)に分類されないポリオール成分であって、例えば、(A1)及び(A2)以外の多価アルコール、ポリエステルポリオール、ポリアセタールポリオール、ポリエステルアミドポリオール又はポリチオエーテルポリオールやその他の水酸基含有樹脂等が挙げられる。
ポリイソシアネート化合物(B)は、1分子中に少なくとも2個のイソシアネート基を有する化合物であって、例えば、脂肪族ポリイソシアネート、脂環族ポリイソシアネート、芳香脂肪族ポリイソシアネート、芳香族ポリイソシアネート、該ポリイソシアネートの誘導体等を挙げることができる。
本発明は、(C)硬化触媒の少なくとも一部として、少なくとも1つのイミダゾール環を有するイミダゾール化合物を用いることを特徴とする。
本発明の塗料組成物における、着色成分としては、塗料分野において公知の着色顔料や着色染料を、1種又は2種以上混合して、使用することができる。
本発明の塗料組成物は、撥水剤を含むことができる。撥水剤としては、シリコン系撥水剤、ふっ素系撥水剤、天然ワックス、合成ワックス等のワックス類等が挙げられる。
本発明の塗料組成物は、ふっ素樹脂を含むことができる。ふっ素樹脂としては、PTFE(ポリテトラフルオロエチレン)やポリフッ化ビニリデン樹脂、フルオロオレフィンとビニルエーテル等の不飽和モノマーとの共重合体、ふっ素含有アクリル樹脂、ふっ素含有ポリエステル樹脂等が挙げられる。
本発明の塗料組成物は、さらに、塗膜性能を損なわない範囲で、成分(A)以外の水酸基含有樹脂、イソシアネート基との反応性を有する化合物(例えばアミノ化合物等)、紫外線吸収剤(例えばベンゾトリアゾール系吸収剤、トリアジン系吸収剤、サリチル酸誘導体系吸収剤、ベンゾフェノン系吸収剤等)、光安定剤(例えば、ヒンダードアミン類等)、体質顔料(タルク、クレー、カオリン、バリタ、硫酸バリウム、炭酸バリウム、炭酸カルシウム、シリカ、アルミナホワイト等)、樹脂粒子、増粘剤、消泡剤、防錆剤、キレート剤(アセチルアセトン等)可塑剤、溶剤、顔料分散剤、表面調整剤、沈降防止剤等の公知の塗料用添加剤を含むことができる。
本発明の塗料組成物において、成分(D)を用いる場合、その配合割合は、成分(A)100質量部に対して、通常、1〜500質量部、好ましくは2〜300質量部、より好ましくは3〜200質量部の範囲で適宜設定できる。
本発明の塗料組成物の形態は、特に限定されるものではなく、水性塗料、有機溶剤型塗料及び無溶剤型塗料のいずれの形態であってもよい。尚、本明細書において、水性塗料とは、有機溶剤型塗料と対比される用語であって、一般に、水又は水を主成分とする媒体(水性媒体)に、塗膜形成性樹脂、顔料等を分散及び/又は溶解させた塗料を意味する。本発明の塗料組成物が水性塗料である場合、該塗料組成物中における水の含有量は、10〜90質量%、好ましくは20〜80質量%、さらに好ましくは30〜70質量%の範囲内であることが好適である。また、上記有機溶剤型塗料とは、溶媒として実質的に水を含有しない又は溶剤の全て又はほとんどが有機溶剤である塗料である。本発明の塗料組成物は、塗料の貯蔵安定性の観点から、有機溶剤型塗料又は非水分散液型塗料であることが好適である。
本発明は、被塗物に前記塗料組成物を塗装して塗膜を形成する塗膜形成方法を提供する。
金属基材としては、金属であればとくに制限なく、例えば、マグネシウム、アルミニウム、亜鉛、チタン、鉄、ニッケル、クロム、金、銀、銅、錫、白金、パラジウム、ジルコニウム、タングステン等の金属そのもの及びこれらの金属の少なくとも2種類以上の合金等の金属材料が挙げられる。2種以上の金属材料としては、Zn−Al、Zn−Ni、Zn−Fe等の合金化亜鉛、ステンレス鋼、上記金属材料でメッキした鋼等が挙げられる。
プラスチック基材としては、ポリエチレン樹脂、ポリプロピレン樹脂等のポリオレフィン樹脂;ポリカーボネート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンテレフタレート/イソフタレート等のポリエステル樹脂;スチレン−ブタジエンブロック共重合体、スチレン−アクリロニトリル、アクリロニトリル−ブタジエン−スチレン(ABS)、ポリスチレン、アクリロニトリル−スチレン−アクリレート等のスチレン系樹脂、ナイロン6、ナイロン6,6、ナイロン6,10、メタキシリレンアジパミド等のポリアミド樹脂、ポリメチルメタクリレート、メチルメタクリレート・エチルアクリレート等のアクリル樹脂;ポリ塩化ビニル樹脂、塩化ビニル−酢酸ビニル等の塩化ビニリデン樹脂や、不飽和ポリエステル樹脂、フェノール樹脂、メラミン樹脂、ユリア樹脂、ポリフェニレンエーテル樹脂、ポリオキシメチレン樹脂、ポリウレタン樹脂、エポキシ樹脂等の樹脂及び各種の繊維強化プラスチック(FRP)等のプラスチック材料を挙げることができる。上記プラスチック基材は、樹脂2種以上のハイブリッド樹脂であっても構わない。
下塗り塗膜とは、本発明の塗料組成物により形成される塗膜の下に形成される塗膜であり、下塗り塗膜を形成するための下塗り塗料は、被塗面の種類や状態等に応じて塗装される。本発明の塗料組成物により形成される塗膜との間に膜を設けることで、被塗面との付着性と、耐衝撃性を向上させることができる。さらに、下塗り塗膜は、付着性を向上させるために、2層以上の複層であってもよい。下塗り塗膜として、例えば、基材が金属基材である場合には、塗料分野で公知のプライマー塗料及び/又は中塗り塗料と呼ばれる塗料組成物を塗装し、硬化させることによって得ることができる塗膜が挙げられる。また、基材がFRP基材である場合には、ゲルコート材と呼ばれるFRP製品の表面に塗装し硬化させることにより得られる被膜等も挙げられる。
また、上記以外の被塗物としては、付着性が満足する範囲であれば、ガラス、セメント、コンクリート等の無機材料;木材;繊維材料(紙、布等)等であってもよい。
(実施例1)
ひまし油(注1) 50部、TIPAQUE CR−95(注22) 100部、酢酸ブチル 37.5部を混合し、サンドミルで分散を行い、分散ペーストを得た。得られた分散ペーストに、プラクセル410(注14) 50部、1,2−ジメチルイミダゾール0.5部、水酸基に対し1当量のスミジュール N3300(注34)を混合し固形分が80%となるように酢酸ブチルを加えて攪拌することにより、塗料組成物No.1を得た。得られた塗料組成物No.1について、後記塗装作業性(ポットライフ及びタレ抵抗性)の試験を行った。表1に評価結果を示す。
表1〜7に記載の組成とする以外は、上記実施例1と同様にして、塗料組成物No.2〜77、83〜101を得た。得られた上記塗料組成物を、表1〜7における配合量は固形分による表示である。得られた塗料組成物について、後記塗装作業性(ポットライフ及びタレ抵抗性)の試験を行った。表1〜7に評価結果を示す。
ひまし油(注1) 50部、TIPAQUE CR−95(注22) 80部、タンカル300(注43) 20部、酢酸ブチル 37.5部を混合し、サンドミルで分散を行い、分散ペーストを得た。得られた分散ペーストに、プラクセル410(注14) 50部、1,2−ジメチルイミダゾール0.5部、水酸基に対し1当量のスミジュール N3300(注34)を混合し固形分が80%となるように酢酸ブチルを加えて攪拌することにより、塗料組成物No.78を得た。
ひまし油(注1) 50部、TIPAQUE CR−95(注22) 80部、KAOLIN HA−90T(注44) 20部、酢酸ブチル 37.5部を混合し、サンドミルで分散を行い、分散ペーストを得た。得られた分散ペーストに、プラクセル410(注14) 50部、1,2−ジメチルイミダゾール0.5部、水酸基に対し1当量のスミジュール N3300(注34)を混合し固形分が80%となるように酢酸ブチルを加えて攪拌することにより、塗料組成物No.79を得た。
ひまし油(注1) 50部、TIPAQUE CR−95(注22) 80部、BARIFINE BF−20(注45) 20部、酢酸ブチル 37.5部を混合し、サンドミルで分散を行い、分散ペーストを得た。得られた分散ペーストに、プラクセル410(注14) 50部、1,2−ジメチルイミダゾール0.5部、水酸基に対し1当量のスミジュール N3300(注34)を混合し固形分が80%となるように酢酸ブチルを加えて攪拌することにより、塗料組成物No.80を得た。
ひまし油(注1) 50部、TIPAQUE CR−95(注22) 80部、サイロホービック200(注46) 20部、酢酸ブチル 37.5部を混合し、サンドミルで分散を行い、分散ペーストを得た。得られた分散ペーストに、プラクセル410(注14) 50部、1,2−ジメチルイミダゾール0.5部、水酸基に対し1当量のスミジュール N3300(注34)を混合し固形分が80%となるように酢酸ブチルを加えて攪拌することにより、塗料組成物No.81を得た。
ひまし油(注1) 50部、TIPAQUE CR−95(注22) 80部、サイロホービック200(46) 20部、BYK−161 0.5部、酢酸ブチル 37.5部を混合し、サンドミルで分散を行い、分散ペーストを得た。得られた分散ペーストに、プラクセル410(注14) 50部、1,2−ジメチルイミダゾール0.5部、水酸基に対し1当量のスミジュール N3300(注34)を混合し固形分が80%となるように酢酸ブチルを加えて攪拌することにより、塗料組成物No.82を得た。
<試験板の作製方法>
表1〜7の「被塗物」の欄に示す被塗物に、上記塗料組成物を、エアレススプレーで乾燥膜厚150μmとなるように塗装した。得られた塗膜を、表1〜7の「乾燥・硬化条件」欄に記載の条件で乾燥して試験板を得た。これらの試験板を、後記試験に供した。表1〜7に評価結果を示す。
乾燥・硬化条件1は、20℃、RH60%で7日間放置することにより乾燥、
乾燥・硬化条件2は、20℃、RH90%で7日間放置することにより乾燥、
乾燥・硬化条件3は、80℃で30分間加熱した後、20℃、RH60%で7日間放置することにより乾燥することを示す。
エピコート828(製品名、ジャパンエポキシレジン(株)製、ビスフェノールA型エポキシ樹脂、固形分100%) 82部、セイカキュア−S(製品名、和歌山精化(株)製、ジアミノジフェニルスルフォン、固形分100%) 6部、フェニルジメチルウレア(平均粒径 50μm、固形分100%) 5.0部、ジシアンジアミド(平均粒径 7μm)7部加えて、均一になるまで混合し、マトリックス樹脂用のエポキシ樹脂組成物を得た。
上記プリプレグを繊維方向が交互直交するように16枚積層して金型に設置し、プリプレグと金型の隙間を500μmに設定した。下記組成のゲルコート材を金型とプリプレグの間に注入した後に130℃に加熱しながら10kg/cm2の圧力を15分間かけてゲルコート層の積層されたガラス繊維強化プラスチック(被塗物2)を得た。
ひまし油 50部、
エピコート828(製品名、エピコートは登録商標、ビスフェノールA型エポキシ樹脂、ジャパンエポキシレジン(株)製、) 30部、
NNカオリンクレー(製品名、クレー、竹原化学社製) 50部、
を均一になるまで混合撹拌した後に、
ジフェニルメタンジイソシアネート 20部を加え、さらに均一になるまで混合撹拌した。
上記「被塗物2:FRP+ゲルコート」に示すゲルコートをした繊維強化プラスチック板上に(エポマリンGX 製品名、二液型エポキシプライマー、関西ペイント社製)を用いてエアスプレー法で厚さ50μmのプライマー層を形成したものを被塗物4とした。
アルミニウム板
後述するレインエロージョンテスト(以下、「RET」と略す)に供する場合は、後記図1のブレード形状になるように成形した上記1〜5の被塗物に、エアレススプレーを用いて乾燥膜厚150μmとなるように本発明の塗料組成物を塗装し、表1〜7の「乾燥・硬化条件」で硬化したものを試験板とした。
(注2)URIC Y−406:製品名、脂肪族系化合物変性ひまし油 水酸基価165mgKOH/g 伊藤製油社製
(注3)POLYCASTOR#10:製品名、ひまし油重合体、水酸基価160mgKOH/g 伊藤製油社製
(注4)Pripol 2033:製品名、ダイマージオール 水酸基価207mgKOH/g、CRODA社製
(注5)Sovermol 750:製品名、植物油由来のポリオール 水酸基価315mgKOH/g BASF社製
(注6)Sovermol 760:製品名、植物油由来のポリオール 水酸基価390mgKOH/g BASF社製
(注7)Sovermol 815:製品名、植物油由来のポリオール 水酸基価215mgKOH/g BASF社製
(注8)Sovermol 819:製品名、植物油由来のポリオール 水酸基価240mgKOH/g BASF社製
(注9)プラクセル 205:製品名、ポリカプロラクトンジオール、数平均分子量530、水酸基価212mgKOH/g、ダイセル社製
(注10)プラクセル 208:製品名、ポリカプロラクトンジオール、数平均分子量830、水酸基価135mgKOH/g、ダイセル社製
(注11)プラクセル 303:製品名、ポリカプロラクトントリオール、数平均分子量300、水酸基価540mgKOH/g、ダイセル社製
(注12)プラクセル 305:製品名、ポリカプロラクトントリオール、数平均分子550、水酸基価305mgKOH/g、ダイセル社製
(注13)プラクセル 309:製品名、ポリカプロラクトントリオール、数平均分子900、水酸基価187mgKOH/g、ダイセル社製
(注14)プラクセル 410:製品名、ポリカプロラクトンテトラオール、数平均分子量1,000、水酸基価224mgKOH/g、ダイセル社製
(注15)Capa 4801:製品名、ポリカプロラクトンテトラオール、数平均分子量8,000、水酸基価28mgKOH/g、Solvay Chemicals,Inc.製
(注16)デュラノール T5650J:ポリカーボネートジオール、旭化成ケミカルズ社製、数平均分子量800、水酸基価140mgKOH/g
(注17)デュラノール T5650E:ポリカーボネートジオール、旭化成ケミカルズ社製、数平均分子量500、水酸基価225mgKOH/g
(注18)ポリアクリレートポリオールNo.1: 攪拌機、温度計、還流冷却器、及び滴下装置を備えた反応容器に、酢酸ブチル40部、メトキシプロピルアセテート40部を仕込み、窒素ガスを吹き込みながら130℃で攪拌し、この中に、
スチレン 5.0部
n−ブチルアクリレート 54.0部
2−ヒドロキシエチルメタクリレート15.0部
プラクセル FM−3X(製品名、ダイセル社製、ε−カプロラクトン変性ヒドロキシエチルメタクリレート)25.0部、
アクリル酸 1.0部、
及びV−59(商品名、和光純薬株式会社製、2,2’−アゾビス(2−メチルブチロニトリル、重合開始剤)の混合物を3時間かけて均一速度で滴下し、さらに同温度で2時間熟成した。
(注19)ポリアクリレートポリオールNo.2:攪拌機、温度計、還流冷却器、及び滴下装置を備えた反応容器に、酢酸ブチル40部、メトキシプロピルアセテート40部を仕込み、窒素ガスを吹き込みながら130℃で攪拌し、
この中に、
スチレン 5.0部、
メチルメタクリレート 15.0部、
n−ブチルアクリレート 50.0部、
4−ヒドロキシブチルアクリレート 29.0部、
アクリル酸 1.0部
及びV−59(開始剤)5.0部の混合物を3時間かけて均一速度で滴下し、さらに同温度で2時間熟成した。
(注20)デスモフェン 670:製品名、ポリエステルポリオール、固形分100質量%、水酸基価142mgKOH/g、数平均分子量約2,000。住化バイエルウレタン社製
(注21)ニッポラン 800:製品名、ポリエステルポリオール、数平均分子量700、水酸基価290mgKOH/g、固形分100%、日本ポリウレタン工業社製。
(注22)TIPAQUE CR−95:製品名、チタン白、石原産業社製
(注23)ハイワックス200PF:製品名、ポリエチレンワックス、三井化学社製
(注24)BYK−333:製品名、変性ジメチルシロキサン、ビックケミー社製
(注25)モレスコホワイトP−80:製品名、流動パラフィン、MORESCO社製
(注26)2−エチルヘキサノール
(注27)メガファックF−562:製品名、パーフルオロアルキル基含有化合物、DIC社製
(注28)60%ルミフロンLF200:商品名、水酸基を有するフルオロオレフィン・ビニルエーテル共重合体、水酸基価31、固形分60%、旭硝子社製。
(注29)60%ルミフロンLF800:水酸基を有するフルオロオレフィン・ビニルエーテル共重合体、水酸基価23mgKOH/g、固形分60%、旭硝子社製、
(注30)ふっ素樹脂No.1 3−エトキシプロピオン酸エチルの600部、エタノールの170部、シクロへキシルビニルエーテル(CHVE)の60部、エチルビニルエーテル(EVE)の90部、ヒドロキシブチルビニルエーテル(HBVE)の400部、炭酸カリウムの5.0部、及びパーブチルPV(日油(株)製、有機過酸化物)の10部を、オートクレーブ内に入れて、密閉、脱気操作を行った後に、クロロトリフルオロエチレン(CTFE)の680部をオートクレーブ内に仕込み、75℃で17時間重合を行った。反応後、ろ過により炭酸カリウムを除去し、濃度調整を行うことで、ふっ素樹脂No.1の3−エトキシプロピオン酸エチル溶液(不揮発分70質量%)を得た。
(注31)50%ゼッフルGK−510:製品名、PTFE、ダイキン社製、水酸基価60mgKOH/g
(注32)ダイニオンTF9205: ポリテトラフルオロエチレンパウダー、3M社製
(注33)カイナー711:製品名、ポリフッ化ビニリデン、アルケマ社製
(注34)スミジュールN3300:製品名、ヘキサメチレンジイソシアネートのヌレート体(略:HDIヌレート) 固形分100%、NCO含有量=21.8%、住化バイエルウレタン社製
(注35)デスモジュールZ4470BA:製品名、イソホロンジイソシアネートのヌレート体(略:IPDIヌレート)、固形分70%、NCO含有量=11.9%、住化バイエルウレタン社製
(注36)デュラネート24A−90E:製品名、ヘキサメチレンジイソシアネートのビュレット体(略:HDIビュレット)固形分90%、NCO含有量=21.2%、旭化成社製
(注37)デスモジュールXP2565:製品名、ヘキサメチレンジイソシアネートのアロファネート体(略:HDIアロファネート)、固形分80%、NCO含有量=12%、Bayer社製
(注38)タケネートD−160N:製品名、トリメチロールプロパン/ヘキサメチレンジイソシアネートアダクト体(略:TMP/HDIアダクト)、固形分75% NCO含有量=12.8%三井武田ケミカル社製
(注39)タケネートD−140NF製品名、トリメチロールプロパン/イソホロンジイソシアネートアダクト体(略:TMP/IPDIアダクト)、固形分75% NCO含有量=10.6%、三井武田ケミカル社製
(注40)デスモジュールN3400:製品名、ヘキサメチレンジイソシアネートのウレトジオン体(略:HDIウレトジオン)、固形分:100%、NCO含有量:21.8%、住化バイエルウレタン社製
(注41)TLA−100:製品名、ヘキサメチレンジイソシアネートのヌレート体(略:HDIヌレート) 固形分100%、NCO含有量=23.4%、旭化成ケミカルズ社製
(注42)デスモジュールN3800:製品名、脂肪族ポリイソシアネートウレタンプレポリマー、固形分:100重量%、NCO含有量:11.0%、住化バイエルウレタン社製
(注43)タンカル300:製品名、炭酸カルシウム、竹原化学工業社製
(注44)KAOLIN HA−90T:製品名、焼成カオリン、SHANXI JINYANG CALCINED KAOLIN製
(注45)BARIFINE BF−20:製品名、硫酸バリウム、堺化学工業社製
(注46)サイロホービック200:製品名、シリカ、富士シリシア化学社製
(注47)BYK−161:製品名、顔料分散剤、BYK社製
(注48)BYK−410:製品名、増粘剤、BYK社製
(注49)Desmophen NH−1220:製品名、アミノ化合物、Bayer MaterialScience社製
(注50)HALS 292:製品名、光安定剤、BASF社製
(注51)BYK−057:製品名、シリコンフリーのポリマー系消泡剤、BYK社製
(注52)BYK−066N:製品名、シリコン系消泡剤、BYK社製
(注53)塗装作業性(硬化速度)
〔ポットライフ〕
全成分を均一に混合した前記実施例及び比較例で得た各塗料組成物を20℃で放置して、ゲル化するまでの時間を測定し、下記評価基準で評価した。
S:30分以上
A:20分以上30分未満
B:10分以上20分未満
C:10分未満
前記実施例及び比較例で得た塗料組成物を「被塗物2:FRP+ゲルコート」に、エアレススプレーで乾燥膜厚を変動させて塗装を行い、各塗装板を水平に対して60°の角度で保持したまま20℃―RH90%で乾燥・硬化させた。タレが発生する限界乾燥膜厚を目視で評価した。
S:250μm以上
A:200μm以上250μm未満
B:150μm以上200μm未満
C:150μm未満
各試験板を目視で観察し、泡跡、シワ、フクレの発生度合いを下記基準で評価した。
S:泡跡、シワ、フクレが全くない
A:微細な泡跡、シワ、フクレのいずれかが少量認められる
B:泡跡、シワ、フクレのいずれかがかなり認められる
C:泡跡、シワ、フクレのいずれかが著しく認められる。
風車ブレード(曲率半径9mm)の前縁を模擬した23cmの長さの被塗物に、前述のように各塗料組成物を塗布乾燥し、試験板を作成した。
S:5時間以上
A:4時間以上5時間未満
B:3時間以上4時間未満
C:3時間未満。
各試験板について、40℃の温水に30日間浸漬した後、水洗いした試験板の外観を下記基準で評価した。
外観〔耐水試験後〕
S:試験前の塗膜に対して、全く外観の変化のないもの
A:試験前の塗膜に対して、わずかにツヤびけ、フクレ又は変色が見られるが、製品とした時に問題ないレベル
B:試験前の塗膜に対して、若干ツヤびけ、フクレ又は変色が見られる
C:試験前の塗膜に対して、著しくツヤびけ、フクレ又は変色が見られる。
Claims (13)
- (A)ポリオール、(B)ポリイソシアネート化合物及び(C)硬化触媒を含む塗料組成物であって、該ポリオール(A)が、炭素数8以上の脂肪酸由来の構成単位を有するポリオール(A1)と、ポリカプロラクトンジオール、ポリカプロラクトントリオール、ポリカプロラクトンテトラオール、ポリカーボネートジオール、及びポリアクリレートポリオールからなる群より選択される少なくとも1種のポリオール(A2)とを含むものであり、かつ該硬化触媒(C)が、少なくとも1つのイミダゾール環を有するイミダゾール化合物を含むことを特徴とし、
該ポリオール(A1)が、
(A1−1)炭素数8以上の水酸基含有脂肪酸と多価アルコールとのエステル化物
(A1−2)炭素数8以上の水酸基含有不飽和脂肪酸の多量体
(A1−3)炭素数8以上の不飽和脂肪酸の多量体を還元したポリオール
(A1−4)炭素数8以上の不飽和脂肪酸(a1−4−1)及び/又は炭素数8以上の不飽和脂肪酸と多価アルコールとのエステル化物(a1−4−2)を水酸基変性したポリオール
からなる群より選択され、
成分(A)100質量部に対して、該ポリオール(A1)の配合量が、10〜70質量部であり、該ポリオール(A2)の配合量が、30〜90質量部の範囲内であり、
前記硬化触媒(C)が、下記一般式(I)で表されるイミダゾール化合物を含み、
R 2 及びR 3 は、各々独立して水素原子、炭素数1〜4のアルキル基、炭素数1〜4のヒドロキシアルキル基、アシル基、アルコキシカルボニル基、カルボキシル基、又はハロゲンを示すか、又はR 2 及びR 3 が 、 R 2 、R 3 が結合する炭素原子とともに芳香環を形成し、
R 4 は、水素原子、炭素数1〜12のアルキル基、炭素数2〜4のアルケニル基、アリールアルキル基、置換基を有していてもよいアリール基又は下記式(II)
前記一般式(I)で表されるイミダゾール化合物が、1−メチルイミダゾール、1,2−ジメチルイミダゾール、1−(3−ジメチルアミノプロピル)イミダゾール、1−イソブチル−2−メチルイミダゾール、1−n−ブチル−2−メチルイミダゾール及び1−ベンジル−2−メチルイミダゾールからなる群より選択される少なくとも1種である塗料組成物。 - 硬化触媒(C)として、さらにビスマス化合物を含む請求項1に記載の塗料組成物。
- 該ポリオール(A1)が、ひまし油及び水添ひまし油より選択される少なくとも1種である請求項1に記載の塗料組成物。
- 該ポリオール(A1)が(A1−2)炭素数8以上の水酸基含有不飽和脂肪酸の多量体であり、該多量体はダイマー、トリマー、及びテトラマーから選択される1種又は2種以上である請求項1に記載の塗料組成物。
- 該ポリオール(A1)が(A1−3)炭素数8以上の不飽和脂肪酸の多量体を還元したポリオールであり、該多量体はダイマー、トリマー、及びテトラマーから選択される1種又は2種以上である請求項1に記載の塗料組成物。
- 該ポリオール(A1)が、(A1−4)炭素数8以上の不飽和脂肪酸(a1−4−1)及び/又は炭素数8以上の不飽和脂肪酸と多価アルコールとのエステル化物(a1−4−2)を水酸基変性したポリオールであり、該水酸基変性したポリオールが、成分(a1−4−1)及び/又は(a1−4−2)中の不飽和基をエポキシ化させて一価又は多価アルコールとを応させたものである請求項1に記載の塗料組成物。
- 少なくとも1つのイミダゾール環を有するイミダゾール化合物の配合量が、成分(A)100質量部に対して、0.005〜8質量部である請求項1〜6のいずれか1項に記載の塗料組成物。
- さらに、着色成分(D)を含む請求項1〜7のいずれか1項に記載の塗料組成物。
- さらに、撥水剤(E)及び/又はふっ素樹脂(F)を含む請求項1〜8のいずれか1項に記載の塗料組成物。
- 被塗物に、請求項1〜9のいずれか1項に記載の塗料組成物を塗装して塗膜を形成する塗膜形成方法。
- 被塗物が、プラスチック若しくは金属の基材、該基材にエポキシ樹脂を含むゲルコート材を積層したもの、該基材にエポキシ樹脂を含むプライマー塗膜を形成したもの、又は該基材にエポキシ樹脂を含むゲルコート材を積層し、該ゲルコート材上にさらにエポキシ樹脂を含むプライマー塗膜を形成したものである、請求項10に記載の塗膜形成方法。
- 被塗物が風力発電機のブレードである、請求項10又は11に記載の塗膜形成方法。
- 被塗物に、請求項1〜9のいずれか1項に記載の塗料組成物を塗装して得られる物品。
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