JP7438146B2 - 金属基材の耐食性を改善する方法 - Google Patents
金属基材の耐食性を改善する方法 Download PDFInfo
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- JP7438146B2 JP7438146B2 JP2020571392A JP2020571392A JP7438146B2 JP 7438146 B2 JP7438146 B2 JP 7438146B2 JP 2020571392 A JP2020571392 A JP 2020571392A JP 2020571392 A JP2020571392 A JP 2020571392A JP 7438146 B2 JP7438146 B2 JP 7438146B2
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Classifications
-
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Description
(a)基材上に硬化性電着可能コーティング組成物を電気泳動的に付着させて、基材の少なくとも一部を覆って電着コーティングを形成することと、
(b)基材上の電着コーティングを硬化させるのに十分な温度までおよび時間にわたって基材を加熱することとを含む。硬化性電着可能コーティング組成物は、水性媒体中に分散された樹脂相を含み、樹脂相は
(1)カソード上に電着可能な、非ゲル化活性水素含有、カチオン性塩の基含有樹脂と、
(2)少なくとも部分的にブロックされたポリイソシアネート硬化剤と、
(3)顔料成分とを含む。顔料成分は、少なくとも0.2ミクロンの平均球相当径を有する無機板状顔料を含み、無機板状顔料は、電着可能コーティング組成物が少なくとも0.5の顔料対結合剤比を示すような量で樹脂相中に存在する。電着可能コーティング組成物は、電着可能コーティング組成物中の固形物の総重量に基づいて、8重量%未満の粉砕ビヒクルを含む。改善とは、硬化性電着可能コーティング組成物でコーティングした後および上記のように硬化させた後、金属基材が、水性媒体中に分散された樹脂相を含む硬化性電着可能コーティング組成物であって、樹脂相が、上記のような(1)カソード上に電着可能な、非ゲル化活性水素含有、カチオン性塩の基含有樹脂と、(2)少なくとも部分的にブロックされたポリイソシアネート硬化剤とを含有するが、顔料成分(3)を含有しない、硬化性電着可能コーティング組成物でコーティングされた同じ材料の金属基材と比較して、改善された塩水噴霧耐食性を示すことを意味する。
1.金属基材の耐食性を改善する方法であって、
(a)基材上に硬化性電着可能コーティング組成物を電気泳動的に付着させて、基材の少なくとも一部を覆って電着コーティングを形成することであって、電着可能コーティング組成物が、水性媒体中に分散された樹脂相を含み、当該樹脂相が
(1)カソード上に電着可能な、非ゲル化活性水素含有、カチオン性塩の基含有樹脂と、
(2)少なくとも部分的にブロックされたポリイソシアネート硬化剤と、
(3)顔料成分であって、顔料成分が、少なくとも0.2ミクロンの平均球相当径を有する無機板状顔料を含み、無機板状顔料が、電着可能コーティング組成物が少なくとも0.5の顔料対結合剤比を示すような量で樹脂相中に存在する、顔料成分とを含み、電着可能コーティング組成物が、電着可能コーティング組成物中の固形物の総重量に基づいて8重量%未満の粉砕ビヒクルを含有する、形成することと、
(b)基材上の電着コーティングを硬化させるのに十分な温度までおよび時間にわたって基材を加熱することとを含む、方法。
2.カチオン性塩の基含有樹脂(1)が、ポリエポキシドポリマー、アクリルポリマー、ポリウレタンポリマー、および/またはポリエステルポリマーから調製される、態様1に記載の方法。
3.カチオン性塩の基含有樹脂(1)が、カチオン性アミン塩の基を含有する態様1または2に記載の方法。
4.無機板状顔料がクレイおよび/またはタルクを含む、態様1から4のいずれかに記載の方法。
5.無機板状顔料が、0.2~5.0ミクロンの平均球相当径を有するカオリンクレイを含む、態様1から4のいずれかに記載の方法。
6.電着可能コーティング組成物が、少なくとも1の顔料対結合剤比を示す、態様1から5のいずれかに記載の方法。
7.カオリンクレイが0.2~3.5ミクロンの平均球相当径を有する、態様5に記載の方法。
8.無機板状顔料が、0.6~1.9ミクロンの平均球相当径を有するタルクを含む、態様4に記載の方法。
9.硬化性電着可能コーティング組成物が、粉砕ビヒクルを本質的に含まない、態様1~8のいずれかに記載の方法。
10.樹脂相を水性媒体中に分散させる前に、顔料成分をカチオン性塩の基含有樹脂(1)中に分散させる、態様1~9のいずれかに記載の方法。
実施例R1:電着可能コーティング組成物のためのブロックされたポリイソシアネート架橋剤(架橋剤I)の調製
電着可能コーティング樹脂での使用に適したブロックされたポリイソシアネート架橋剤(架橋剤I)は以下の方法で調製された。以下の表1に列挙される成分2~5を、全還流するように設定されたフラスコ中で、窒素下で撹拌しながら混合した。混合物を35℃の温度に加熱し、成分1を、反応発熱により温度が上昇するように滴下し、100℃未満に維持した。成分1の添加が完了した後、反応混合物中に110℃の温度を確立し、IR分光法によって残留イソシアネートが検出されなくなるまで、反応混合物をその温度に保持した。次いで、成分6を添加し、反応混合物を30分間撹拌し、周囲温度に冷却した。
電着可能コーティング組成物の配合に使用するのに適したカチオン性、アミン官能化、ポリエポキシド系のポリマー樹脂を以下の方法で調製した。以下の表2に列挙される成分1~5を、窒素下で撹拌しながら全還流するように設定したフラスコ中で合わせた。混合物を130℃の温度に加熱し、発熱させた(最大175℃)。反応混合物中に145℃の温度を確立し、次いで反応混合物を2時間保持した。次いで、成分6~8を反応混合物中に導入し、110℃の温度を反応混合物中で確立した。次いで、成分9および10を反応混合物に迅速に添加し、反応混合物を発熱させた。反応混合物中に121℃の温度を確立し、反応混合物を1時間保持した。保持後、熱源を反応混合物から除去し、成分11をゆっくりと導入した。フラスコの内容物を室温に冷却しながら撹拌した。得られた樹脂合成生成物1(RSP1)は65重量%の固形物含有量であった。
2上記実施例R1参照。
31当量のジエチレントリアミンと2当量のMIBKとのジケチミン反応生成物72.7重量%(MIBK中)。
配合:顔料(ASP-900、1.5ミクロンの平均球相当径を有するBASFから入手可能なカオリン)を樹脂(RSP1)に添加し、高剪断下で10分間混合し、続いて触媒ペースト(二酸化ジブチルスズ、DBTO)、分散剤(DYNASYLAN4148、エボニックインダストリーズ(Evonik Industries)から入手可能)およびジエチレングリコールモノブチルエーテル-ホルムアルデヒド付加物を添加した。高剪断混合をさらに50分間続けた。得られたペーストを100gの水性スルファミン酸中に分散させ、20分間混合し、次いで残りの水で希釈した。
**パネルは、850時間の塩水噴霧曝露後に試験した実施例1(対照)を除いて、1000時間の塩水噴霧曝露後に試験した。
本発明の好ましい実施形態によれば、例えば、以下が提供される。
(項1)
金属基材の耐食性を改善する方法であって、
(a)前記基材上に硬化性電着可能コーティング組成物を電気泳動的に付着させて、前記基材の少なくとも一部を覆って電着コーティングを形成することであって、前記電着可能コーティング組成物が、水性媒体中に分散された樹脂相を含み、前記樹脂相が
(1)カソード上に電着可能な、非ゲル化活性水素含有、カチオン性塩の基含有樹脂と、
(2)少なくとも部分的にブロックされたポリイソシアネート硬化剤と、
(3)顔料成分であって、前記顔料成分が、少なくとも0.2ミクロンの平均球相当径を有する無機板状顔料を含み、前記無機板状顔料が、前記電着可能コーティング組成物が少なくとも0.5の顔料対結合剤比を示すような量で前記樹脂相中に存在する、顔料成分と、を含み、前記電着可能コーティング組成物が、前記電着可能コーティング組成物中の固形物の総重量に基づいて8重量%未満の粉砕ビヒクルを含有する、
形成することと、
(b)前記基材上の前記電着コーティングを硬化させるのに十分な温度までおよび時間にわたって前記基材を加熱することと、を含む方法。
(項2)
前記カチオン性塩の基含有樹脂(1)が、ポリエポキシドポリマー、アクリルポリマー、ポリウレタンポリマー、および/またはポリエステルポリマーから調製される、上記項1に記載の方法。
(項3)
前記カチオン性塩の基含有樹脂(1)が、カチオン性アミン塩の基を含有する、上記項1に記載の方法。
(項4)
前記無機板状顔料がクレイおよび/またはタルクを含む、上記項1に記載の方法。
(項5)
前記無機板状顔料が、0.2~5.0ミクロンの平均球相当径を有するカオリンクレイを含む、上記項4に記載の方法。
(項6)
前記電着可能コーティング組成物が、少なくとも1の顔料対結合剤比を示す、上記項5に記載の方法。
(項7)
前記カオリンクレイが0.2~3.5ミクロンの平均球相当径を有する、上記項5に記載の方法。
(項8)
前記電着可能コーティング組成物が、少なくとも1の顔料対結合剤比を示す、上記項7に記載の方法。
(項9)
前記無機板状顔料が、0.6~1.9ミクロンの平均球相当径を有するタルクを含む、上記項4に記載の方法。
(項10)
前記硬化性電着可能コーティング組成物が、粉砕ビヒクルを本質的に含まない、上記項1に記載の方法。
(項11)
前記樹脂相を前記水性媒体中に分散させる前に、前記顔料成分を前記カチオン性塩の基含有樹脂(1)中に分散させる、上記項10に記載の方法。
Claims (10)
- 金属基材の耐食性を改善する方法であって、
(a)前記基材上に硬化性電着可能コーティング組成物を電気泳動的に付着させて、前記基材の少なくとも一部を覆って電着コーティングを形成することであって、前記電着可能コーティング組成物が、水性媒体中に分散された樹脂相を含み、前記樹脂相が
(1)カソード上に電着可能な、非ゲル化活性水素含有、カチオン性塩の基含有樹脂と、
(2)少なくとも部分的にブロックされたポリイソシアネート硬化剤と、
(3)前記カチオン性塩の基含有樹脂(1)または前記ポリイソシアネート硬化剤(2)のいずれかまたは両方に分散させられた顔料成分であって、前記顔料成分が、少なくとも0.2ミクロンの平均球相当径を有するクレイおよび/またはタルクを含む無機板状顔料を含み、前記無機板状顔料が、前記電着可能コーティング組成物が少なくとも0.5のクレイおよび/またはタルク顔料対結合剤比を示すような量で前記樹脂相中に存在する、顔料成分と、を含み、前記電着可能コーティング組成物が、前記電着可能コーティング組成物中の固形物の総重量に基づいて8重量%未満の粉砕ビヒクルを含有する、
形成することと、
(b)前記基材上の前記電着コーティングを硬化させるのに十分な温度までおよび時間にわたって前記基材を加熱することと、を含む方法。 - 前記カチオン性塩の基含有樹脂(1)が、ポリエポキシドポリマー、アクリルポリマー、ポリウレタンポリマー、および/またはポリエステルポリマーから調製される、請求項1に記載の方法。
- 前記カチオン性塩の基含有樹脂(1)が、カチオン性アミン塩の基を含有する、請求項1に記載の方法。
- 前記無機板状顔料が、0.2~5.0ミクロンの平均球相当径を有するカオリンクレイを含む、請求項1に記載の方法。
- 前記電着可能コーティング組成物が、少なくとも1のクレイ顔料対結合剤比を示す、請求項4に記載の方法。
- 前記カオリンクレイが0.2~3.5ミクロンの平均球相当径を有する、請求項4に記載の方法。
- 前記電着可能コーティング組成物が、少なくとも1のクレイ顔料対結合剤比を示す、請求項6に記載の方法。
- 前記無機板状顔料が、0.6~1.9ミクロンの平均球相当径を有するタルクを含む、請求項1に記載の方法。
- 前記硬化性電着可能コーティング組成物が、粉砕ビヒクルを本質的に含まない、請求項1に記載の方法。
- 前記樹脂相を前記水性媒体中に分散させる前に、前記顔料成分を前記カチオン性塩の基含有樹脂(1)中に分散させる、請求項9に記載の方法。
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