JPWO2020262549A1 - Cationic electrodeposition coating composition - Google Patents
Cationic electrodeposition coating composition Download PDFInfo
- Publication number
- JPWO2020262549A1 JPWO2020262549A1 JP2020562220A JP2020562220A JPWO2020262549A1 JP WO2020262549 A1 JPWO2020262549 A1 JP WO2020262549A1 JP 2020562220 A JP2020562220 A JP 2020562220A JP 2020562220 A JP2020562220 A JP 2020562220A JP WO2020262549 A1 JPWO2020262549 A1 JP WO2020262549A1
- Authority
- JP
- Japan
- Prior art keywords
- electrodeposition coating
- coating composition
- cationic electrodeposition
- formula
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 61
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 48
- 239000008199 coating composition Substances 0.000 title claims abstract description 47
- 150000001875 compounds Chemical class 0.000 claims abstract description 77
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 50
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 49
- 239000003822 epoxy resin Substances 0.000 claims abstract description 49
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 42
- 238000000576 coating method Methods 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 24
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 24
- 125000003277 amino group Chemical group 0.000 claims abstract description 23
- 125000000962 organic group Chemical group 0.000 claims abstract description 21
- 239000000470 constituent Substances 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 7
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- 238000013007 heat curing Methods 0.000 claims description 2
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- 238000001816 cooling Methods 0.000 description 3
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- 238000009472 formulation Methods 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
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- 238000005259 measurement Methods 0.000 description 3
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- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/24—Homopolymers or copolymers of amides or imides
- C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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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
- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/04—Electrophoretic coating characterised by the process with organic material
- C25D13/06—Electrophoretic coating characterised by the process with organic material with polymers
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- Chemical & Material Sciences (AREA)
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- Molecular Biology (AREA)
- Paints Or Removers (AREA)
Abstract
エッジ部の防食性、平面部の耐水性及び仕上がり性に優れたカチオン電着塗料組成物、並びにこれらの諸塗膜性能に優れた塗装物品を提供することを課題とする。解決手段として、アミノ基含有エポキシ樹脂（Ａ）と、ブロック化ポリイソシアネート化合物（Ｂ）と、下記式（Ｉ）及び／又は式（ＩＩ）で表されるモノマーを構成成分として有するポリビニル化合物（Ｃ）とを含有するカチオン電着塗料組成物を提供する。ＣＨ２＝ＣＨ−ＮＨ−Ｃ（＝Ｏ）−Ｒ・・・（Ｉ）（式中、Ｒは炭素数１以上の有機基である。）ＣＨ２＝Ｃ（−Ｒ１）−Ｃ（＝Ｏ）−Ｎ（−Ｒ２）（−Ｒ３）・・・（ＩＩ）（式中、Ｒ１は水素原子又はメチル基である。Ｒ２及びＲ３は同じでも異なっていてもよく、水素原子又は炭素数１以上の有機基であって、Ｒ２及びＲ３は互いに繋がって環状構造になっていてもよい。また、Ｒ２とＲ３のどちらか一方又は両方が炭素数１以上の有機基である。）It is an object of the present invention to provide a cationic electrodeposition coating composition having excellent corrosion resistance of an edge portion, water resistance of a flat portion and finishing property, and a coated article having excellent coating film performance thereof. As a solution, a polyvinyl compound (C) containing an amino group-containing epoxy resin (A), a blocked polyisocyanate compound (B), and a monomer represented by the following formulas (I) and / or formula (II) as constituent components. ) And a cationic electrodeposition coating composition. CH2 = CH-NH-C (= O) -R ... (I) (In the formula, R is an organic group having 1 or more carbon atoms.) CH2 = C (-R1) -C (= O)- N (-R2) (-R3) ... (II) (In the formula, R1 is a hydrogen atom or a methyl group. R2 and R3 may be the same or different, and are an organic hydrogen atom or an organic having 1 or more carbon atoms. R2 and R3 may be connected to each other to form a cyclic structure, and either or both of R2 and R3 are organic groups having one or more carbon atoms.)
Description
本発明は、アミノ基含有エポキシ樹脂、ブロック化ポリイソシアネート化合物、及び特定のポリビニル化合物を有するカチオン電着塗料組成物に関する。 The present invention relates to a cationic electrodeposition coating composition having an amino group-containing epoxy resin, a blocked polyisocyanate compound, and a specific polyvinyl compound.
カチオン電着塗料組成物は、塗装作業性に優れ、且つ形成される塗膜の防食性が良好なことから、これらの性能が要求される自動車ボディ、自動車部品、電気機器部品及びその他の機器等などの導電性金属製品向け下塗り塗料として広く使用されている。 Since the cationic electrodeposition coating composition has excellent coating workability and good corrosion resistance of the formed coating film, automobile bodies, automobile parts, electrical equipment parts, and other equipment that require these performances, etc. It is widely used as an undercoat paint for conductive metal products such as.
被塗物が鋭いエッジ部を有する場合、塗料の加熱硬化時にエッジ部の塗膜が薄くなってしまうことがあり、防食性が劣ることとなる。そのため、エッジ部を有する被塗物の塗装においては、エッジ部の防食性を向上させる手段が求められている。 When the object to be coated has a sharp edge portion, the coating film on the edge portion may become thin when the paint is heat-cured, resulting in inferior corrosion resistance. Therefore, in painting an object to be coated having an edge portion, a means for improving the corrosion resistance of the edge portion is required.
エッジ部の防錆性を向上させる方法として、特許文献１には電着塗料中にポリアクリルアミド樹脂を含有することが開示されている。また、特許文献２には、電着塗料中にポリビニルホルムアミド樹脂を含有することが開示されている。上記樹脂を含有することにより、エッジ部における防食性を向上することができるが、高極性樹脂を含有することになるため、厳しい腐食条件下ではエッジ部の防食性が十分に得られない場合があった。
As a method for improving the rust prevention property of the edge portion, Patent Document 1 discloses that the electrodeposition coating material contains a polyacrylamide resin. Further,
発明が解決しようとする課題は、エッジ部の防食性、平面部の耐水性及び仕上がり性に優れたカチオン電着塗料組成物、並びにこれらの諸塗膜性能に優れた塗装物品を提供することである。 The problem to be solved by the present invention is to provide a cationic electrodeposition coating composition having excellent corrosion resistance at the edge portion, water resistance at the flat portion and finishing property, and a coated article having excellent coating film performance thereof. be.
発明者等は、上記課題を解決するために鋭意検討した結果、アミノ基含有エポキシ樹脂（Ａ）、ブロック化ポリイソシアネート化合物（Ｂ）、及び特定のポリビニル化合物（Ｃ）を有するカチオン電着塗料組成物によって、上記課題の解決が達成できることを見出し、本発明を完成するに至った。 As a result of diligent studies to solve the above problems, the inventors have made a cationic electrodeposition coating composition having an amino group-containing epoxy resin (A), a blocked polyisocyanate compound (B), and a specific polyvinyl compound (C). We have found that a solution to the above-mentioned problems can be achieved by using a compound, and have completed the present invention.
即ち、本発明は、以下のカチオン電着塗料組成物、カチオン電着塗料の塗装方法、及び電着塗装された塗装物品を提供するものである。
項１．アミノ基含有エポキシ樹脂（Ａ）と、ブロック化ポリイソシアネート化合物（Ｂ）と、下記式（Ｉ）及び／又は式（ＩＩ）で表されるモノマーを構成成分として有するポリビニル化合物（Ｃ）とを含有するカチオン電着塗料組成物。
ＣＨ２＝ＣＨ−ＮＨ−Ｃ（＝Ｏ）−Ｒ・・・（Ｉ）
（式中、Ｒは炭素数１以上の有機基である。）
ＣＨ２＝Ｃ（−Ｒ１）−Ｃ（＝Ｏ）−Ｎ（−Ｒ２）（−Ｒ３）・・・（ＩＩ）
（式中、Ｒ１は水素原子又はメチル基である。Ｒ２及びＲ３は同じでも異なっていてもよく、水素原子又は炭素数１以上の有機基であって、Ｒ２及びＲ３は互いに繋がって環状構造になっていてもよい。また、Ｒ２とＲ３のどちらか一方又は両方が炭素数１以上の有機基である。）
項２．ポリビニル化合物（Ｃ）が、前記式（Ｉ）及び／又は式（ＩＩ）で表されるモノマーを構成成分として２０モル％以上含有することを特徴とする項１に記載のカチオン電着塗料組成物。
項３．ポリビニル化合物（Ｃ）が、前記式（Ｉ）で表されるモノマーのみを構成成分とすることを特徴とする項１に記載のカチオン電着塗料組成物。
項４．前記式（Ｉ）で表されるモノマーが、ビニルアセトアミド、Ｎ−ビニルプロピオン酸アミド、Ｎ−ビニル酪酸アミドからなる群より選ばれる少なくとも一種であることを特徴とする項１〜３のいずれか１項に記載のカチオン電着塗料組成物。
項５．ポリビニル化合物（Ｃ）が、前記式（ＩＩ）で表されるモノマーのみを構成成分とすることを特徴とする項１に記載のカチオン電着塗料組成物。
項６．ポリビニル化合物（Ｃ）が、ハンセンの溶解度パラメータにおけるδｈが１４ＭＰａ１／２以下であることを特徴とする項１〜５のいずれか１項に記載のカチオン電着塗料組成物。
項７．ポリビニル化合物（Ｃ）が、ハンセンの溶解度パラメータにおけるδｈが１０ＭＰａ１／２以下であることを特徴とする項１〜５のいずれか１項に記載のカチオン電着塗料組成物。
項８．ポリビニル化合物（Ｃ）が、アミノ基含有エポキシ樹脂（Ａ）及びブロック化ポリイソシアネート化合物（Ｂ）の固形分合計質量１００質量部を基準として、塗料組成物中に、０．０１〜３０質量部含有することを特徴とする項１〜７のいずれか１項に記載のカチオン電着塗料組成物。
項９．項１〜８のいずれか１項に記載のカチオン電着塗料組成物からなる電着塗料浴に金属被塗物を浸漬し、電着塗装する塗装方法。
項１０．項９に記載の塗装方法によって塗膜を形成し、次いで加熱硬化する工程を含む塗装物品の製造方法。That is, the present invention provides the following cationic electrodeposition coating composition, a coating method for cationic electrodeposition coating, and an electrodeposited coated article.
Item 1. Contains an amino group-containing epoxy resin (A), a blocked polyisocyanate compound (B), and a polyvinyl compound (C) containing a monomer represented by the following formula (I) and / or formula (II) as a constituent component. Cationic electrodeposition coating composition.
CH 2 = CH-NH-C (= O) -R ... (I)
(In the formula, R is an organic group having 1 or more carbon atoms.)
CH 2 = C (-R 1 ) -C (= O) -N (-R 2 ) ( -R 3 ) ... (II)
(In the formula, R 1 is a hydrogen atom or a methyl group. R 2 and R 3 may be the same or different, and are a hydrogen atom or an organic group having 1 or more carbon atoms, and R 2 and R 3 are mutual. It may be connected to form a cyclic structure. Further, either one or both of R 2 and R 3 are organic groups having 1 or more carbon atoms.)
Item 5.
Item 6. The cationic electrodeposition coating composition according to any one of Items 1 to 5, wherein the polyvinyl compound (C) has a δh of 14 MPa 1/2 or less in the Hansen solubility parameter.
Item 7. The cationic electrodeposition coating composition according to any one of Items 1 to 5, wherein the polyvinyl compound (C) has a δh of 10 MPa 1/2 or less in the Hansen solubility parameter.
Item 8. The polyvinyl compound (C) is contained in the coating composition in an amount of 0.01 to 30 parts by mass based on 100 parts by mass of the total solid content of the amino group-containing epoxy resin (A) and the blocked polyisocyanate compound (B). The cationic electrodeposition coating composition according to any one of Items 1 to 7, wherein the composition is characterized by the above.
Item 9. A coating method for immersing a metal object to be coated in an electrodeposition coating bath comprising the cationic electrodeposition coating composition according to any one of Items 1 to 8 and subjecting the metal to the electrodeposition coating.
Item 10. Item 9. A method for producing a coated article, which comprises a step of forming a coating film by the coating method according to Item 9 and then heat-curing.
本発明のカチオン電着塗料組成物は、エッジ部の防食性、平面部の耐水性及び仕上がり性に優れ、特に厳しい腐食条件下でもエッジ部の防食性が良好である。具体的には、本発明品が塗装された自動車ボディは、融雪塩が散布された環境下を長期間走行しても、腐食劣化が少ない。 The cationic electrodeposition coating composition of the present invention is excellent in corrosion resistance of the edge portion, water resistance and finish property of the flat surface portion, and is excellent in corrosion resistance of the edge portion even under particularly severe corrosion conditions. Specifically, the automobile body coated with the product of the present invention has little corrosion deterioration even when it is driven for a long period of time in an environment where snowmelt salt is sprayed.
１．直径８ｍｍの穴を示す。
２．４枚ボックス法の付きまわり性試験用治具における外板（Ａ面）を示す。
３．４枚ボックス法の付きまわり性試験用治具における内板（Ｇ面）を示す。
４．電着塗料浴を示す。1. 1. A hole with a diameter of 8 mm is shown.
The outer plate (A side) in the jig for the wraparound test of the 2.4-sheet box method is shown.
The inner plate (G surface) of the jig for the wraparound test of the 3.4-sheet box method is shown.
4. Indicates an electrodeposition paint bath.
本発明は、アミノ基含有エポキシ樹脂（Ａ）、ブロック化ポリイソシアネート化合物（Ｂ）、及び特定のポリビニル化合物（Ｃ）を有するカチオン電着塗料組成物に関する。以下、詳細に述べる。 The present invention relates to a cationic electrodeposition coating composition having an amino group-containing epoxy resin (A), a blocked polyisocyanate compound (B), and a specific polyvinyl compound (C). The details will be described below.
アミノ基含有エポキシ樹脂（Ａ）
本発明で用いることができるアミノ基含有エポキシ樹脂（Ａ）としては、例えば、（１）エポキシ樹脂と第１級モノ−及びポリアミン、第２級モノ−及びポリアミン又は第１、２級混合ポリアミンとの付加物（例えば、米国特許第３，９８４，２９９号明細書参照）；（２）エポキシ樹脂とケチミン化された第１級アミノ基を有する第２級モノ−及びポリアミンとの付加物（例えば、米国特許第４，０１７，４３８号 明細書参照）；（３）エポキシ樹脂とケチミン化された第１級アミノ基を有するヒドロキシ化合物とのエーテル化により得られる反応物（例えば、特開昭５９−４３０１３号公報参照）等を挙げることができる。Amino group-containing epoxy resin (A)
Examples of the amino group-containing epoxy resin (A) that can be used in the present invention include (1) an epoxy resin and a primary mono- and polyamine, a secondary mono-and a polyamine, or a primary and secondary mixed polyamine. (See, for example, US Pat. No. 3,984,299); (2) Additives of epoxy resin and secondary mono- and polyamines having a ketiminated primary amino group (eg,). , US Pat. No. 4,017,438); (3) Reactant obtained by etherification of an epoxy resin and a ketiminated hydroxy compound having a primary amino group (for example, JP-A-59). -Refer to Japanese Patent Application Laid-Open No. 43013) and the like.
上記のアミノ基含有エポキシ樹脂（Ａ）の製造に使用されるエポキシ樹脂（Ａ−１）は、１分子中にエポキシ基を少なくとも１個、好ましくは２個以上有する化合物であり、その分子量は、少なくとも３００、好ましくは４００〜４，０００、さらに好ましくは８００〜２，５００の範囲内の数平均分子量及び少なくとも１６０、好ましくは１８０〜２，５００、さらに好ましくは４００〜１，５００の範囲内のエポキシ当量を有するものが適している。かかるエポキシ樹脂としては、例えば、ポリフェノール化合物とエピハロヒドリン（例えば、エピクロルヒドリン等）との反応によって得られるものを使用することができる。 The epoxy resin (A-1) used for producing the above amino group-containing epoxy resin (A) is a compound having at least one epoxy group, preferably two or more epoxy groups in one molecule, and its molecular weight is: A number average molecular weight in the range of at least 300, preferably 400 to 4,000, more preferably 800 to 2,500 and at least 160, preferably 180 to 2,500, even more preferably 400 to 1,500. Those having an epoxy equivalent are suitable. As such an epoxy resin, for example, one obtained by reacting a polyphenol compound with epichlorohydrin (for example, epichlorohydrin or the like) can be used.
上記エポキシ樹脂の形成のために用いられるポリフェノール化合物としては、例えば、ビス（４−ヒドロキシフェニル）−２，２−プロパン［ビスフェノールＡ］、ビス（４−ヒドロキシフェニル）メタン［ビスフェノールＦ］、ビス（４−ヒドロキシシクロヘキシル）メタン［水添ビスフェノールＦ］、２，２−ビス（４−ヒドロキシシクロヘキシル）プロパン［水添ビスフェノールＡ］、４，４’−ジヒドロキシベンゾフェノン、ビス（４−ヒドロキシフェニル）−１，１−エタン、ビス（４−ヒドロキシフェニル）−１，１−イソブタン、ビス（４−ヒドロキシ−３−ｔｅｒｔ−ブチル−フェニル）−２，２−プロパン、ビス（２−ヒドロキシナフチル）メタン、テトラ（４−ヒドロキシフェニル）−１，１，２，２−エタン、４，４’−ジヒドロキシジフェニルスルホン、フェノールノボラック、クレゾールノボラックなどを挙げることができる。 Examples of the polyphenol compound used for forming the epoxy resin include bis (4-hydroxyphenyl) -2,2-propane [bisphenol A], bis (4-hydroxyphenyl) methane [bisphenol F], and bis ( 4-Hydroxycyclohexyl) methane [hydrogenated bisphenol F], 2,2-bis (4-hydroxycyclohexyl) propane [hydrogenated bisphenol A], 4,4'-dihydroxybenzophenone, bis (4-hydroxyphenyl) -1, 1-ethane, bis (4-hydroxyphenyl) -1,1-isobutane, bis (4-hydroxy-3-tert-butyl-phenyl) -2,2-propane, bis (2-hydroxynaphthyl) methane, tetra ( 4-Hydroxyphenyl) -1,1,2,2-ethane, 4,4'-dihydroxydiphenylsulfone, phenol novolac, cresol novolac and the like can be mentioned.
また、ポリフェノール化合物とエピハロヒドリンとの反応によって得られるエポキシ樹脂としては、中でも、ビスフェノールＡから誘導される下記式（１）のエポキシ樹脂が好適である。
さらに下記式（１）のエポキシ樹脂とポリフェノール化合物とを反応させて高分子量化及び／又は多官能化したエポキシ樹脂を用いることもでき、なかでも該ポリフェノール化合物としてはビスフェノールＡが好適である。Further, as the epoxy resin obtained by the reaction of the polyphenol compound and epihalohydrin, the epoxy resin of the following formula (1) derived from bisphenol A is particularly preferable.
Further, it is also possible to use an epoxy resin having a high molecular weight and / or polyfunctionalization by reacting the epoxy resin of the following formula (1) with a polyphenol compound, and bisphenol A is particularly preferable as the polyphenol compound.
ここで、ｎ＝０〜８で示されるものが好適である。 Here, those represented by n = 0 to 8 are preferable.
かかるエポキシ樹脂の市販品としては、例えば、三菱化学（株）からｊＥＲ８２８ＥＬ、ｊＥＲ１００２、ｊＥＲ１００４、ｊＥＲ１００７なる商品名で販売されているものが挙げられる。 Examples of commercially available products of such epoxy resins include those sold by Mitsubishi Chemical Corporation under the trade names jER828EL, jER1002, jER1004, and jER1007.
また、上記エポキシ樹脂（Ａ−１）としては、樹脂骨格中にポリアルキレンオキシド鎖を含有しているエポキシ樹脂を使用することができる。通常、このようなエポキシ樹脂は、（α）エポキシ基を少なくとも１個、好ましくは２個以上有するエポキシ樹脂と、アルキレンオキシド又はポリアルキレンオキシドを反応せしめてポリアルキレンオキシド鎖を導入する方法、（β）上記ポリフェノール化合物と、エポキシ基を少なくとも１個、好ましくは２個以上有するポリアルキレンオキシドとを反応せしめてポリアルキレンオキシド鎖を導入する方法などにより得ることができる。また、既にポリアルキレンオキシド鎖を含有しているエポキシ樹脂を用いても良い。（例えば、特開平８−３３７７５０号 明細書参照）
ポリアルキレンオキシド鎖中のアルキレン基としては、炭素数が２〜８のアルキレン基が好ましく、エチレン基、プロピレン基またはブチレン基がより好ましく、プロピレン基が特に好ましい。
上記のポリアルキレンオキシド鎖の含有量は、塗料安定性、仕上り性及び防食性向上の観点から、アミノ基含有エポキシ樹脂の固形分質量を基準にして、ポリアルキレンオキシドの構成成分としての含有量で、通常１．０〜１５質量％、好ましくは２．０〜９．５質量％、より好ましくは３．０〜８．０質量％の範囲内が適当である。Further, as the epoxy resin (A-1), an epoxy resin containing a polyalkylene oxide chain in the resin skeleton can be used. Usually, such an epoxy resin is a method of introducing a polyalkylene oxide chain by reacting an epoxy resin having at least one (α) epoxy group, preferably two or more, with an alkylene oxide or a polyalkylene oxide (β). ) It can be obtained by a method of introducing a polyalkylene oxide chain by reacting the above polyphenol compound with a polyalkylene oxide having at least one epoxy group, preferably two or more epoxy groups. Further, an epoxy resin already containing a polyalkylene oxide chain may be used. (For example, refer to Japanese Patent Application Laid-Open No. 8-337750)
As the alkylene group in the polyalkylene oxide chain, an alkylene group having 2 to 8 carbon atoms is preferable, an ethylene group, a propylene group or a butylene group is more preferable, and a propylene group is particularly preferable.
The content of the above polyalkylene oxide chain is the content as a constituent component of the polyalkylene oxide based on the solid content mass of the amino group-containing epoxy resin from the viewpoint of improving paint stability, finish and corrosion resistance. , Usually 1.0 to 15% by mass, preferably 2.0 to 9.5% by mass, more preferably 3.0 to 8.0% by mass.
上記（１）のアミノ基含有エポキシ樹脂（Ａ）の製造に使用される第１級モノ−及びポリアミン、第２級モノ−及びポリアミン又は第１、２級混合ポリアミンとしては、例えば、モノメチルアミン、ジメチルアミン、モノエチルアミン、ジエチルアミン、モノイソプロピルアミン、ジイソプロピルアミン、モノブチルアミン、ジブチルアミンなどのモノ−もしくはジ−アルキルアミン；モノエタノールアミン、ジエタノールアミン、モノ（２−ヒドロキシプロピル）アミン、モノメチルアミノエタノールなどのアルカノールアミン；エチレンジアミン、プロピレンジアミン、ブチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミンなどのアルキレンポリアミンなどを挙げることができる。 Examples of the primary mono- and polyamine, secondary mono- and polyamine, and primary and secondary mixed polyamines used in the production of the amino group-containing epoxy resin (A) of the above (1) include monomethylamine. Mono- or di-alkylamines such as dimethylamine, monoethylamine, diethylamine, monoisopropylamine, diisopropylamine, monobutylamine, dibutylamine; monoethanolamine, diethanolamine, mono (2-hydroxypropyl) amine, monomethylaminoethanol, etc. Alkanolamines; alkylene polyamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine and triethylenetetramine can be mentioned.
上記（２）のアミノ基含有エポキシ樹脂（Ａ）の製造に使用されるケチミン化された第１級アミノ基を有する第２級モノ−及びポリアミンとしては、例えば、上記（１）のアミン付加エポキシ樹脂の製造に使用される第１、２級混合ポリアミンのうち、例えば、ジエチレントリアミン、ジプロピレントリアミンなどにケトン化合物を反応させて生成させたケチミン化物を挙げることができる。 Examples of the secondary mono- and polyamine having a ketiminated primary amino group used in the production of the amino group-containing epoxy resin (A) of the above (2) include the amine-added epoxy of the above (1). Among the primary and secondary mixed polyamines used in the production of resins, for example, ketiminated products produced by reacting a ketone compound with diethylenetriamine, dipropylenetriamine and the like can be mentioned.
上記（３）のアミノ基含有エポキシ樹脂（Ａ）の製造に使用されるケチミン化された第１級アミノ基を有するヒドロキシ化合物としては、例えば、上記（１）のアミノ基含有エポキシ樹脂（Ａ）の製造に使用される第１級モノ−及びポリアミン、第２級モノ−及びポリアミン又は第１、２級混合ポリアミンのうち、第１級アミノ基とヒドロキシル基を有する化合物、例えば、モノエタノールアミン、モノ（２−ヒドロキシプロピル）アミンなどにケトン化合物を反応させてなるヒドロキシル基含有ケチミン化物を挙げることができる。 Examples of the hydroxy compound having a ketiminated primary amino group used in the production of the amino group-containing epoxy resin (A) of the above (3) include the amino group-containing epoxy resin (A) of the above (1). Of the primary mono-and polyamines, secondary mono- and polyamines or primary and secondary mixed polyamines used in the production of, compounds having a primary amino group and a hydroxyl group, such as monoethanolamine, Examples thereof include hydroxyl group-containing ketimines obtained by reacting a ketone compound with mono (2-hydroxypropyl) amine or the like.
このようなアミノ基含有エポキシ樹脂（Ａ）のアミン価としては、３０〜８０ｍｇＫＯＨ／ｇ樹脂固形分の範囲、さらには４０〜７０ｍｇＫＯＨ／ｇ樹脂固形分の範囲とすることが、水分散性と防食性向上の点から好ましい。 The amine value of such an amino group-containing epoxy resin (A) should be in the range of 30 to 80 mgKOH / g resin solid content and further in the range of 40 to 70 mgKOH / g resin solid content in terms of water dispersibility and anticorrosion. It is preferable from the viewpoint of improving the property.
またアミノ基含有エポキシ樹脂（Ａ）は、必要に応じて、変性剤により変性を図ることができる。このような変性剤は、エポキシ樹脂との反応性を有する樹脂又は化合物であれば特に限定されず、例えばポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリアミドアミン、ポリカルボン酸、脂肪酸、ポリイソシアネート化合物、ポリイソシアネート化合物を反応させた化合物、ε−カプロラクトンなどのラクトン化合物、アクリルモノマー、アクリルモノマーを重合反応させた化合物、キシレンホルムアルデヒド化合物、エポキシ化合物も変性剤として用いることができる。これらの変性剤は、１種を単独で又は２種以上を併用して用いることができる。
これらのうち、変性剤としては、特に付きまわり性及び／又は防食性の観点から、少なくとも１種の飽和及び／又は不飽和脂肪酸を用いることが好ましい。使用しうる脂肪酸としては、炭素数８〜２２の長鎖脂肪酸が好ましく、例えば、カプリル酸、カプリン酸、オクタン酸、ノナン酸、デカン酸、ラウリン酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、マルガリン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸等が挙げられる。中でも、炭素数１０〜２０の長鎖脂肪酸がより好ましく、炭素数１３〜１８の長鎖脂肪酸がさらに好ましい。Further, the amino group-containing epoxy resin (A) can be modified with a modifying agent, if necessary. Such a modifier is not particularly limited as long as it is a resin or compound having reactivity with an epoxy resin, and is, for example, a polyol, a polyether polyol, a polyester polyol, a polyamide amine, a polycarboxylic acid, a fatty acid, a polyisocyanate compound, or a poly. Compounds obtained by reacting isocyanate compounds, lactone compounds such as ε-caprolactone, acrylic monomers, compounds obtained by polymerizing acrylic monomers, xyleneformaldehyde compounds, and epoxy compounds can also be used as modifiers. These denaturants can be used alone or in combination of two or more.
Of these, as the denaturing agent, it is preferable to use at least one saturated and / or unsaturated fatty acid, particularly from the viewpoint of circumvention and / or anticorrosion. As the fatty acid that can be used, a long-chain fatty acid having 8 to 22 carbon atoms is preferable. , Stearic acid, oleic acid, linoleic acid, linolenic acid and the like. Among them, long-chain fatty acids having 10 to 20 carbon atoms are more preferable, and long-chain fatty acids having 13 to 18 carbon atoms are even more preferable.
上記のアミン化合物と変性剤のエポキシ樹脂（Ａ−１）への付加反応は、通常、適当な溶媒中で、約８０〜約１７０℃、好ましくは約９０〜約１５０℃の温度で１〜６時間程度、好ましくは１〜５時間程度で行なうことができる。 The addition reaction of the above amine compound and the modifier to the epoxy resin (A-1) is usually carried out in a suitable solvent at a temperature of about 80 to about 170 ° C., preferably about 90 to about 150 ° C., 1 to 6 It can be carried out in about an hour, preferably about 1 to 5 hours.
上記の溶媒としては、例えば、トルエン、キシレン、シクロヘキサン、ｎ−ヘキサンなどの炭化水素系；酢酸メチル、酢酸エチル、酢酸ブチルなどのエステル系；アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルアミルケトンなどのケトン系；ジメチルホルムアミド、ジメチルアセトアミドなどのアミド系；メタノール、エタノール、ｎ−プロパノール、ｉｓｏ−プロパノールなどのアルコール系、エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル等のエーテルアルコール系化合物；あるいはこれらの混合物などが挙げられる。 Examples of the above solvent include hydrocarbon systems such as toluene, xylene, cyclohexane and n-hexane; ester systems such as methyl acetate, ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl amyl ketone. Systems; amide systems such as dimethylformamide and dimethylacetamide; alcohol-based compounds such as methanol, ethanol, n-propanol and iso-propanol, ether alcohol-based compounds such as ethylene glycol monobutyl ether and diethylene glycol monoethyl ether; or mixtures thereof. Can be mentioned.
上記の変性剤の使用割合は、厳密に制限されるものではなく、塗料組成物の用途等に応じて適宜変えることができるが、仕上り性及び防食性向上の観点から、アミノ基含有エポキシ樹脂の固形分質量を基準にして、通常０〜５０質量％、好ましくは３〜３０質量％、より好ましくは６〜２０質量％の範囲内が適当である。 The proportion of the above-mentioned modifier used is not strictly limited and can be appropriately changed depending on the intended use of the coating composition, etc., but from the viewpoint of improving the finish and corrosion resistance, the amino group-containing epoxy resin Based on the solid content mass, it is usually in the range of 0 to 50% by mass, preferably 3 to 30% by mass, and more preferably 6 to 20% by mass.
ブロック化ポリイソシアネート化合物（Ｂ）
ブロック化ポリイソシアネート化合物（Ｂ）は、ポリイソシアネート化合物とイソシアネートブロック剤とのほぼ化学理論量での付加反応生成物である。ブロック化ポリイソシアネート化合物（Ｂ）で使用されるポリイソシアネート化合物としては、公知のものを使用することができ、例えば、トリレンジイソシアネート、キシリレンジイソシアネート、フェニレンジイソシアネート、ジフェニルメタン−２，２’−ジイソシアネート、ジフェニルメタン−２，４’−ジイソシアネート、ジフェニルメタン−４，４’−ジイソシアネート、クルードＭＤＩ［ポリメチレンポリフェニルイソシアネート］、ビス（イソシアネートメチル）シクロヘキサン、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、メチレンジイソシアネート、イソホロンジイソシアネートなどの芳香族、脂肪族又は脂環族ポリイソシアネート化合物；これらのポリイソシアネート化合物の環化重合体又はビゥレット体；又はこれらの組合せを挙げることができる。Blocked polyisocyanate compound (B)
The blocked polyisocyanate compound (B) is an addition reaction product of the polyisocyanate compound and the isocyanate blocking agent in a substantially chemical theoretical amount. As the polyisocyanate compound used in the blocked polyisocyanate compound (B), known ones can be used, for example, tolylene diisocyanate, xylylene diisocyanate, phenylenedi isocyanate, diphenylmethane-2,2'-diisocyanate, etc. Diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, crude MDI [polymethylenepolyphenylisocyanate], bis (isocyanatemethyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate, etc. Aromatic, aliphatic or alicyclic polyisocyanate compounds; cyclized polymers or billets of these polyisocyanate compounds; or combinations thereof can be mentioned.
特に、トリレンジイソシアネート、キシリレンジイソシアネート、フェニレンジイソシアネート、ジフェニルメタン−２，４’−ジイソシアネート、ジフェニルメタン−４，４’−ジイソシアネート、クルードＭＤＩ等（好ましくはクルードＭＤＩ等）の芳香族ポリイソシアネート化合物が防食性の為により好ましい。 In particular, aromatic polyisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, phenylenediisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, and crude MDI (preferably crude MDI and the like) are anticorrosive. It is more preferable because of this.
一方、前記イソシアネートブロック剤は、ポリイソシアネート化合物のイソシアネート基に付加してブロックするものであり、そして付加によって生成するブロック化ポリイソシアネート化合物は常温において安定であるが、塗膜の焼付け温度（通常約１００〜約２００℃）に加熱した際、ブロック剤が解離して遊離のイソシアネート基を再生することが望ましい。 On the other hand, the isocyanate blocking agent is added to the isocyanate group of the polyisocyanate compound to block it, and the blocked polyisocyanate compound produced by the addition is stable at room temperature, but the baking temperature of the coating film (usually about about). It is desirable that the blocking agent dissociates and regenerates the free isocyanate group when heated to 100 to about 200 ° C.).
ブロック化ポリイソシアネート化合物（Ｂ）で使用されるブロック剤としては、例えば、メチルエチルケトオキシム、シクロヘキサノンオキシムなどのオキシム系化合物；フェノール、パラ−ｔ−ブチルフェノール、クレゾールなどのフェノール系化合物；ｎ−ブタノール、２−エチルヘキサノール、フェニルカルビノール、メチルフェニルカルビノール、エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、エチレングリコール、プロピレングリコールなどのアルコール系化合物；ε−カプロラクタム、γ−ブチロラクタムなどのラクタム系化合物；マロン酸ジメチル、マロン酸ジエチル、アセト酢酸エチル、アセト酢酸メチル、アセチルアセトンなどの活性メチレン系化合物等（好ましくは、アルコール系化合物等）が挙げられる。 Examples of the blocking agent used in the blocked polyisocyanate compound (B) include oxime compounds such as methyl ethyl ketooxime and cyclohexanone oxime; phenol compounds such as phenol, parat-butylphenol and cresol; n-butanol, 2 -Alcohol compounds such as ethylhexanol, phenylcarbinol, methylphenylcarbinol, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, ethylene glycol, propylene glycol; lactam compounds such as ε-caprolactam and γ-butyrolactam; dimethyl malonate , Active oxime compounds such as diethyl malonate, ethyl acetoacetate, methyl acetoacetate, acetylacetone and the like (preferably alcohol compounds and the like).
ポリビニル化合物（Ｃ）
本発明のカチオン電着塗料組成物で用いることができるポリビニル化合物（Ｃ）は、下記式（Ｉ）及び／又は式（ＩＩ）で表されるアミド基含有モノマーを構成成分として有するポリビニル化合物であり、なかでも、少なくとも１種の下記式（Ｉ）を有することが好ましい。
ＣＨ２＝ＣＨ−ＮＨ−Ｃ（＝Ｏ）−Ｒ・・・（Ｉ）
（式中、Ｒは炭素数１以上の有機基である。）
ＣＨ２＝Ｃ（−Ｒ１）−Ｃ（＝Ｏ）−Ｎ（−Ｒ２）（−Ｒ３）・・・（ＩＩ）
（式中、Ｒ１は水素原子又はメチル基である。Ｒ２及びＲ３は同じでも異なっていてもよく、水素原子又は炭素数１以上の有機基であって、Ｒ２及びＲ３は互いに繋がって環状構造になっていてもよい。また、Ｒ２とＲ３のどちらか一方又は両方が炭素数１以上の有機基である。）Polyvinyl compound (C)
The polyvinyl compound (C) that can be used in the cationic electrodeposition coating composition of the present invention is a polyvinyl compound having an amide group-containing monomer represented by the following formulas (I) and / or formula (II) as a constituent component. Among them, it is preferable to have at least one of the following formulas (I).
CH 2 = CH-NH-C (= O) -R ... (I)
(In the formula, R is an organic group having 1 or more carbon atoms.)
CH 2 = C (-R 1 ) -C (= O) -N (-R 2 ) ( -R 3 ) ... (II)
(In the formula, R 1 is a hydrogen atom or a methyl group. R 2 and R 3 may be the same or different, and are a hydrogen atom or an organic group having 1 or more carbon atoms, and R 2 and R 3 are mutual. It may be connected to form a cyclic structure. Further, either one or both of R 2 and R 3 are organic groups having 1 or more carbon atoms.)
上記式（Ｉ）のＲは、炭素数１以上の有機基である。炭素数１以上の有機基としては、例えば、炭素数１以上の炭化水素基（例えば、アルキル基、シクロアルキル基、アリール基、アルケニル基等）、炭素数１以上のヒドロキシアルキル基、炭素数１以上のアルコキシ基、及び炭素数２以上のアルコキシアルキル基からなる群より選ばれる少なくとも１種があげられる。これらのうち、炭素数１以上のアルキル基が好ましく、炭素数１〜１０のアルキル基がより好ましく、炭素数１〜５のアルキル基がより好ましい。 R in the above formula (I) is an organic group having 1 or more carbon atoms. Examples of the organic group having 1 or more carbon atoms include a hydrocarbon group having 1 or more carbon atoms (for example, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, etc.), a hydroxyalkyl group having 1 or more carbon atoms, and 1 carbon number of carbon atoms. At least one selected from the group consisting of the above alkoxy group and the alkoxyalkyl group having 2 or more carbon atoms can be mentioned. Of these, an alkyl group having 1 or more carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
上記式（ＩＩ）のＲ２及びＲ３は、同じでも異なっていてもよく、水素原子又は炭素数１以上の有機基であって、Ｒ２及びＲ３は互いに繋がって環状構造になっていてもよい。また、Ｒ２とＲ３のどちらか一方又は両方が炭素数１以上の有機基である。
炭素数１以上の有機基としては、例えば、炭素数１以上の炭化水素基（例えば、アルキル基、シクロアルキル基、アリール基、アルケニル基等）、炭素数１以上のヒドロキシアルキル基、炭素数１以上のアルコキシ基、及び炭素数２以上のアルコキシアルキル基からなる群より選ばれる少なくとも１種があげられる。また、Ｒ２及びＲ３は互いに繋がって環状構造になる場合には、Ｒ２及びＲ３が結合する窒素原子を異項原子として少なくとも含み、さらに酸素、窒素、硫黄を異項原子として含んでいてもよい炭素数４以上の複素環を有する。
炭素数１以上の有機基の炭素数としては、１〜１０が好ましく、１〜４がより好ましく、１〜２がさらに好ましい。
これらのうち、炭素数１以上のアルキル基又は炭素数１以上のヒドロキシアルキル基が好ましく、炭素数１〜１０のアルキル基又は炭素数１〜１０のヒドロキシアルキル基がより好ましく、炭素数１〜５のアルキル基又は炭素数１〜５のヒドロキシアルキル基がより好ましい。また、Ｒ２とＲ３は、一方が水素原子でもう一方が炭素数１以上のアルキル基又は炭素数１以上のヒドロキシアルキル基である場合、両方とも炭素数１以上のアルキル基又は炭素数１以上のヒドロキシアルキル基である場合が好ましい。 R 2 and R 3 of the above formula (II) may be the same or different, and are hydrogen atoms or organic groups having 1 or more carbon atoms, and R 2 and R 3 are connected to each other to form a cyclic structure. May be good. Further, either one or both of R 2 and R 3 are organic groups having 1 or more carbon atoms.
Examples of the organic group having 1 or more carbon atoms include a hydrocarbon group having 1 or more carbon atoms (for example, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, etc.), a hydroxyalkyl group having 1 or more carbon atoms, and 1 carbon number of carbon atoms. At least one selected from the group consisting of the above alkoxy group and the alkoxyalkyl group having 2 or more carbon atoms can be mentioned. Further, when R 2 and R 3 are connected to each other to form a cyclic structure, at least the nitrogen atom to which R 2 and R 3 are bonded is contained as a heteroatom, and oxygen, nitrogen and sulfur are further contained as a heteroatom. It has a heterocycle having 4 or more carbon atoms.
The number of carbon atoms of the organic group having 1 or more carbon atoms is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 to 2.
Of these, an alkyl group having 1 or more carbon atoms or a hydroxyalkyl group having 1 or more carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms is more preferable, and 1 to 5 carbon atoms are more preferable. Alkyl groups or hydroxyalkyl groups having 1 to 5 carbon atoms are more preferable. Further, when one of R 2 and R 3 is a hydrogen atom and the other is an alkyl group having 1 or more carbon atoms or a hydroxyalkyl group having 1 or more carbon atoms, both are an alkyl group having 1 or more carbon atoms or 1 carbon atom. The above hydroxyalkyl group is preferable.
上記式（Ｉ）のモノマーとしては、例えば、ビニルアセトアミド、Ｎ−ビニルプロピオン酸アミド、Ｎ−ビニル酪酸アミド、ジアセトンアクリルアミドからなる群より選ばれる少なくとも一種が挙げられる。これらは、エッジ部の防食性、耐水性、及び仕上がり性の観点から好適である。なかでも、ビニルアセトアミド、Ｎ−ビニルプロピオン酸アミド、Ｎ−ビニル酪酸アミドからなる群より選ばれる少なくとも１種を含む事が好ましく、ビニルアセトアミドを含むことがより好ましい。
また、上記ポリビニル化合物（Ｃ）が、上記式（Ｉ）を含有する場合は、上記式（Ｉ）で表されるモノマーのみを構成成分とすることが好ましい。Examples of the monomer of the above formula (I) include at least one selected from the group consisting of vinylacetamide, N-vinylpropionic acid amide, N-vinylbutyric acid amide, and diacetoneacrylamide. These are suitable from the viewpoint of corrosion resistance, water resistance, and finish of the edge portion. Among them, it is preferable to contain at least one selected from the group consisting of vinylacetamide, N-vinylpropionic acid amide, and N-vinylbutyric acid amide, and it is more preferable to contain vinylacetamide.
When the polyvinyl compound (C) contains the formula (I), it is preferable that only the monomer represented by the formula (I) is a constituent component.
上記式（ＩＩ）のモノマーとしては、例えば、Ｎ−アルキル（メタ）アクリルアミド、Ｎ−ヒドロキシアルキル（メタ）アクリルアミド、Ｎ−ヒドロキシアルキル−Ｎ−アルキル（メタ）アクリルアミド、Ｎ−アルキル（メタ）アクリルアミドアルキルエーテル、Ｎ−ヒドロキシアルキル（メタ）アクリルアミドアルキルエーテル、Ｎ，Ｎ−ジヒドロキシアルキル（メタ）アクリルアミド、Ｎ，Ｎ−ジアルキル（メタ）アクリルアミド、Ｎ−ヒドロキシ，Ｎ−アルキル（メタ）アクリルアミド、Ｎ−ヒドロキシアルキル（メタ）アクリルアミドアルキルエーテル、Ｎ−アルキル（メタ）アクリルアミドアルキルエーテル、（メタ）アクリロイルモルホリン、ジアルキルアミノエチル（メタ）アクリルアミド及びその塩あるいは４級化物、ジアルキルアミノプロピル（メタ）アクリルアミド及びその塩あるいは４級化物などからなる群より選ばれる少なくとも１種が挙げられる。なかでも、Ｎ，Ｎ−ジアルキルアクリルアミド、Ｎ−アルキルアクリルアミド、Ｎ−ヒドロキシアルキルアクリルアミドからなる群より選ばれる少なくとも１種を含む事が好ましく、Ｎ，Ｎ−ジメチルアクリルアミド及び／又はＮ−ヒドロキシエチルアクリルアミドを含むことがより好ましく、Ｎ−ヒドロキシエチルアクリルアミドを含むことがさらに好ましい。
上記Ｒ２及びＲ３の炭素数としては、１〜１０が好ましく、１〜４がより好ましく、１〜２がさらに好ましい。
また、上記ポリビニル化合物（Ｃ）が、上記式（ＩＩ）を含有する場合は、（メタ）アクリルアミドを含まないことが好ましく、上記式（ＩＩ）で表されるモノマーのみを構成成分とすることが好ましい。Examples of the monomer of the above formula (II) include N-alkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide, N-hydroxyalkyl-N-alkyl (meth) acrylamide, and N-alkyl (meth) acrylamide alkyl. Ether, N-hydroxyalkyl (meth) acrylamide alkylether, N, N-dihydroxyalkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N-hydroxy, N-alkyl (meth) acrylamide, N-hydroxyalkyl (Meta) acrylamide alkyl ether, N-alkyl (meth) acrylamide alkyl ether, (meth) acryloylmorpholin, dialkylaminoethyl (meth) acrylamide and its salts or quaternized products, dialkylaminopropyl (meth) acrylamide and its salts or 4 At least one selected from the group consisting of graded products and the like can be mentioned. Among them, it is preferable to contain at least one selected from the group consisting of N, N-dialkylacrylamide, N-alkylacrylamide, and N-hydroxyalkylacrylamide, and N, N-dimethylacrylamide and / or N-hydroxyethylacrylamide. It is more preferable to contain N-hydroxyethyl acrylamide, and it is further preferable to contain N-hydroxyethyl acrylamide.
The number of carbon atoms of R 2 and R 3 is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 to 2.
When the polyvinyl compound (C) contains the above formula (II), it is preferable that it does not contain (meth) acrylamide, and only the monomer represented by the above formula (II) may be a constituent component. preferable.
上記ポリビニル化合物（Ｃ）は、上記式（Ｉ）及び／又は式（ＩＩ）のアミド基含有モノマーと共に、必要に応じて、エチレン性不飽和結合を有する任意の単量体と共重合させることが可能である。共重合させ得る単量体としては、例えば（メタ）アクリル酸およびその塩、（メタ）アクリル酸エステル、（メタ）アクリロニトリル、ジアルキルアミノアルキル（メタ）アクリレート及びその塩あるいはその４級化物、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタム、酢酸ビニル、スチレン等が例示され、１種でも２種以上でも使用できる。 The polyvinyl compound (C) can be copolymerized with any monomer having an ethylenically unsaturated bond, if necessary, together with the amide group-containing monomer of the formula (I) and / or the formula (II). It is possible. Examples of the monomers that can be copolymerized include (meth) acrylic acid and a salt thereof, (meth) acrylic acid ester, (meth) acrylonitrile, dialkylaminoalkyl (meth) acrylate and a salt thereof, or a quaternized product thereof, N-. Examples thereof include vinylpyrrolidone, N-vinylcaprolactam, vinyl acetate, styrene, etc., and one type or two or more types can be used.
上記式（Ｉ）及び／又は式（ＩＩ）のモノマーの含有割合は、ポリビニル化合物（Ｃ）を構成する全モノマーを基準として、通常２０モル％以上、好ましくは４０モル％以上、より好ましくは６０モル％以上、さらに好ましくは９０モル％以上、特に好ましくは１００モル％であることがエッジ防食性の観点から好適である。 The content ratio of the monomers of the formula (I) and / or the formula (II) is usually 20 mol% or more, preferably 40 mol% or more, more preferably 60, based on all the monomers constituting the polyvinyl compound (C). From the viewpoint of edge corrosion resistance, it is preferable that the content is mol% or more, more preferably 90 mol% or more, and particularly preferably 100 mol%.
上記ポリビニル化合物（Ｃ）の合成方法としては、それ自体既知の方法を特に制限なく用いることができ、例えば、ビニルカルボン酸アミドを水溶液状で重合する方法（特公昭６３−９５２３号）、単量体水溶液をＨＬＢが９〜２０である非イオン系乳化剤（乳化剤）の存在下、炭化水素分散媒中に油中水型で懸濁重合する方法（特開平５−９７９３１号）などを好適に用いることができる。 As the method for synthesizing the polyvinyl compound (C), a method known per se can be used without particular limitation. For example, a method of polymerizing a vinylcarboxylic acid amide in an aqueous form (Japanese Patent Publication No. 63-9523), a single amount. A method of suspend-polymerizing a body aqueous solution in a water-in-oil type in a hydrocarbon dispersion medium in the presence of a nonionic emulsifier (emulsifier) having an HLB of 9 to 20 (Japanese Patent Laid-Open No. 5-97931) is preferably used. be able to.
ポリビニル化合物（Ｃ）の重量平均分子量としては、通常１０００〜１０００万であり、好ましくは５０００〜５００万であり、より好ましくは１万〜１００万であり、さらに好ましくは１０万〜１００万が好適である。 The weight average molecular weight of the polyvinyl compound (C) is usually 10 to 10 million, preferably 5000 to 5 million, more preferably 10,000 to 1 million, still more preferably 100,000 to 1 million. Is.
尚、本明細書において、数平均分子量及び重量平均分子量は、ゲルパーミエーションクロマトグラフ（ＧＰＣ）を用いて測定した保持時間（保持容量）を、同一条件で測定した分子量既知の標準ポリスチレンの保持時間（保持容量）によりポリスチレンの分子量に換算して求めた値である。具体的には、ゲルパーミエーションクロマトグラフとして、「ＨＬＣ８１２０ＧＰＣ」（商品名、東ソー社製）を使用し、カラムとして、「ＴＳＫｇｅｌ Ｇ−４０００ＨＸＬ」、「ＴＳＫｇｅｌ Ｇ−３０００ＨＸＬ」、「ＴＳＫｇｅｌ Ｇ−２５００ＨＸＬ」及び「ＴＳＫｇｅｌ Ｇ−２０００ＨＸＬ」（商品名、いずれも東ソー社製）の４本を使用し、移動相テトラヒドロフラン、測定温度４０℃、流速１ｍＬ／ｍｉｎ及び検出器ＲＩの条件下で測定することができる。 In the present specification, the number average molecular weight and the weight average molecular weight are the holding times (holding capacity) measured by using a gel permeation chromatograph (GPC), and the holding time of standard polystyrene having a known molecular weight measured under the same conditions. It is a value obtained by converting to the molecular weight of polystyrene by (retention capacity). Specifically, "HLC8120GPC" (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph, and "TSKgel G-4000HXL", "TSKgel G-3000HXL", "TSKgel G-2500HXL" are used as columns. And "TSKgel G-2000HXL" (trade name, all manufactured by Tosoh Corporation) can be used for measurement under the conditions of mobile phase tetrahydrofuran, measurement temperature 40 ° C., flow velocity 1 mL / min and detector RI. ..
カチオン電着塗料組成物に上記ポリビニル化合物（Ｃ）を含有することでエッジ防食性が向上する理由としては、極性基（アミド基）により被塗物へのヌレ性が向上することで端部に十分な膜厚が確保でき、かつモノマーの側鎖部分においてアミド基のほかに疎水基（炭素数１以上の有機基）を有することで防食性（耐水性）が向上すると考えられる。 The reason why the edge corrosion resistance is improved by containing the above-mentioned polyvinyl compound (C) in the cationic electrodeposition coating composition is that the polar group (amide group) improves the wettability to the object to be coated, so that the edge portion is improved. It is considered that the corrosion resistance (water resistance) is improved by ensuring a sufficient film thickness and having a hydrophobic group (organic group having 1 or more carbon atoms) in addition to the amide group in the side chain portion of the monomer.
上記ポリビニル化合物（Ｃ）は、エッジ部の防食性及び付きまわり性の観点から、ハンセンの溶解度パラメータにおけるδｈ（水素結合項）が、１４ＭＰａ１／２以下であることが好ましく、１０ＭＰａ１／２以下であることがより好ましい。また、１ＭＰａ１／２以上であることが好ましく、３ＭＰａ１／２以上であることが好ましい。
ハンセンの溶解度パラメータ（ＨＳＰ）は、ある物質が他のある物質にどのくらい溶けるのかという溶解性を表す指標である。ＨＳＰは溶解性を３次元のベクトルで表す。この３次元ベクトルは、代表的には、分散項（δｄ）、極性項（δｐ）、水素結合項（δｈ）で表すことができる。分散項（δｄ）は分散力による効果、分極項（δｐ）は双極子間力による効果、水素結合項（δｈ）は水素結合力による効果を示す。水素結合項（δｈ）が高いと他成分との相互作用により塗料の粘性が発現するが、逆に極性が強くなりすぎると被塗物への付きまわり性が劣ることになる。
本明細書で用いているハンセン溶解度パラメーター（ＨＳＰ値）は、ＨＳＰｉＰ（Ｈａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒｓ ｉｎ Ｐｒａｃｔｉｃｅ）というソフトを用いて算出することができる。 The polyvinyl compound (C) preferably has a δh (hydrogen bond term) of 14 MPa 1/2 or less in the Hansen solubility parameter from the viewpoint of corrosion resistance and wrapping property of the edge portion, and is preferably 10 MPa 1/2 or less. Is more preferable. Further, it is preferably 1 MPa 1/2 or more, and preferably 3 MPa 1/2 or more.
The Hansen solubility parameter (HSP) is an index of the solubility of a substance in another substance. HSP represents solubility as a three-dimensional vector. This three-dimensional vector can be typically represented by a dispersion term (δd), a polarity term (δp), and a hydrogen bond term (δh). The dispersion term (δd) indicates the effect due to the dispersion force, the polarization term (δp) indicates the effect due to the dipole interpole force, and the hydrogen bond term (δh) indicates the effect due to the hydrogen bond force. If the hydrogen bond term (δh) is high, the viscosity of the paint develops due to the interaction with other components, but conversely, if the polarity becomes too strong, the adhesion to the object to be coated becomes inferior.
The Hansen solubility parameter (HSP value) used in the present specification can be calculated using software called HSPiP (Hansen Solubility Parameters in Practice).
カチオン電着塗料組成物について
本発明のカチオン電着塗料組成物におけるアミノ基含有エポキシ樹脂（Ａ）、及びブロック化ポリイソシアネート化合物（Ｂ）の配合割合としては、上記成分（Ａ）及び（Ｂ）の固形分合計質量を基準にして、成分（Ａ）を５〜９５質量％、好ましくは５０〜８０質量％、成分（Ｂ）を５〜９５質量％、好ましくは２０〜５０質量％の範囲内であることが、塗料安定性が良好で、仕上がり性、防食性に優れた塗装物品を得る為にも好ましい。上記範囲を外れると、上記の塗料特性及び塗膜性能のいずれかを損なうことがあり好ましくない。
また、成分（Ｃ）の配合割合としては、上記樹脂（Ａ）及び化合物（Ｂ）の固形分合計１００質量部を基準として、通常０．０１〜３０質量部含有し、好ましくは０．０５〜２０質量部含有し、より好ましくは０．１〜１０質量部含有し、さらに好ましくは０．２〜２質量部含有することが、エッジ部の防食性や仕上がり性など優れた塗装物品を得る為にも好ましい。About the cationic electrodeposition coating composition The blending ratios of the amino group-containing epoxy resin (A) and the blocked polyisocyanate compound (B) in the cationic electrodeposition coating composition of the present invention include the above components (A) and (B). The component (A) is in the range of 5 to 95% by mass, preferably 50 to 80% by mass, and the component (B) is in the range of 5 to 95% by mass, preferably 20 to 50% by mass, based on the total mass of the solid content of the above. It is also preferable to obtain a coated article having good paint stability and excellent finish and corrosion resistance. If it is out of the above range, either the above coating properties or the coating film performance may be impaired, which is not preferable.
The blending ratio of the component (C) is usually 0.01 to 30 parts by mass, preferably 0.05 to 30 parts by mass, based on 100 parts by mass of the total solid content of the resin (A) and the compound (B). The content of 20 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0.2 to 2 parts by mass is for obtaining a coated article having excellent corrosion resistance and finish of the edge portion. Also preferable.
本発明のカチオン電着塗料組成物の製造方法は、特に限定されるものではないが、例えば、上記樹脂（Ａ）、及び化合物（Ｂ）に加え、必要に応じて、界面活性剤や表面調整剤等の各種添加剤を十分に混合して調合樹脂とした後、水分散化し、これにポリビニル化合物（Ｃ）、顔料分散ペースト、水や有機溶剤、中和剤などを十分に混合して得ることができる。上記中和剤としては、公知の有機酸を特に制限なく用いることができ、なかでもギ酸、乳酸又はこれらの混合物が好適である。
上記の顔料分散ペーストは、着色顔料、防錆顔料及び体質顔料などの顔料をあらかじめ微細粒子に分散したものであって、例えば、顔料分散用樹脂、中和剤及び顔料を配合し、ボールミル、サンドミル、ペブルミル等の分散混合機中で分散処理して、顔料分散ペーストを調製できる。The method for producing the cationic electrodeposition coating composition of the present invention is not particularly limited, but for example, in addition to the above resin (A) and compound (B), a surfactant and surface adjustment are required, if necessary. Various additives such as agents are sufficiently mixed to prepare a compounded resin, which is then water-dispersed, and a polyvinyl compound (C), a pigment-dispersed paste, water, an organic solvent, a neutralizing agent, etc. are sufficiently mixed thereto. be able to. As the neutralizing agent, known organic acids can be used without particular limitation, and formic acid, lactic acid or a mixture thereof is particularly preferable.
The above pigment dispersion paste is obtained by pre-dispersing pigments such as coloring pigments, rust preventive pigments and extender pigments into fine particles. For example, a pigment dispersion resin, a neutralizing agent and a pigment are blended, and a ball mill or a sand mill is used. , Pigment dispersion paste can be prepared by dispersion treatment in a dispersion mixer such as Pebble Mill.
上記顔料分散用樹脂としては、公知のものを特に制限なく使用でき、例えば水酸基及びカチオン性基を有するエポキシ樹脂やアクリル樹脂、界面活性剤等、３級アミン型エポキシ樹脂、４級アンモニウム塩型エポキシ樹脂、３級スルホニウム塩型エポキシ樹脂、３級アミン型アクリル樹脂、４級アンモニウム塩型アクリル樹脂、３級スルホニウム塩型アクリル樹脂などを使用できる。 As the pigment dispersion resin, known ones can be used without particular limitation. For example, epoxy resins having hydroxyl groups and cationic groups, acrylic resins, surfactants and the like, tertiary amine type epoxy resins and quaternary ammonium salt type epoxys can be used. A resin, a tertiary sulfonium salt type epoxy resin, a tertiary amine type acrylic resin, a quaternary ammonium salt type acrylic resin, a tertiary sulfonium salt type acrylic resin, or the like can be used.
上記顔料としては、公知のものを特に制限なく使用でき、例えば、酸化チタン、カーボンブラック、ベンガラ等の着色顔料；クレー、マイカ、バリタ、炭酸カルシウム、シリカなどの体質顔料；リンモリブデン酸アルミニウム、トリポリリン酸アルミニウム、酸化亜鉛（亜鉛華）等の防錆顔料；を添加することができる。 As the above pigment, known pigments can be used without particular limitation. For example, coloring pigments such as titanium oxide, carbon black and red iron oxide; extender pigments such as clay, mica, varita, calcium carbonate and silica; aluminum phosphate molybdate and tripolyline. Anti-corrosion pigments such as aluminum acid and zinc oxide (silica) can be added.
さらに、腐食抑制又は防錆を目的として、ビスマス化合物を含有させることができる。上記ビスマス化合物としては、例えば、酸化ビスマス、水酸化ビスマス、塩基性炭酸ビスマス、硝酸ビスマス、ケイ酸ビスマス及び有機酸ビスマス等を用いることができる。 Further, a bismuth compound can be contained for the purpose of suppressing corrosion or preventing rust. As the bismuth compound, for example, bismuth oxide, bismuth hydroxide, basic bismuth carbonate, bismuth nitrate, bismuth silicate, bismuth organic acid and the like can be used.
また、塗膜硬化性の向上を目的として、ジブチル錫ジベンゾエート、ジオクチル錫オキサイド、ジブチル錫オキサイト゛等の有機錫化合物を用いることができる。前記酸化亜鉛（亜鉛華）等の防錆顔料及び／又はビスマス化合物を適用（増量）及び／又は微細化して用いることによって、これらの有機錫化合物を含有せずに、塗膜硬化性の向上を図ることもできる。これらの顔料の配合量は、樹脂（Ａ）、化合物（Ｂ）の合計樹脂固形分１００質量部あたり１〜１００質量部、特に１０〜５０質量部の範囲内が好ましい。 Further, for the purpose of improving the curability of the coating film, an organic tin compound such as dibutyltin dibenzoate, dioctyltin oxide, or dibutyltin oxide can be used. By applying (increasing the amount) and / or refining the rust preventive pigment and / or bismuth compound such as zinc oxide (zinc oxide), the curability of the coating film can be improved without containing these organic tin compounds. You can also plan. The blending amount of these pigments is preferably in the range of 1 to 100 parts by mass, particularly 10 to 50 parts by mass, per 100 parts by mass of the total resin solid content of the resin (A) and the compound (B).
塗装方法
本発明は、前述のカチオン電着塗料組成物からなる電着浴に被塗物を浸漬する工程、及び被塗物を陰極として通電する工程を含む、カチオン電着の塗装方法を提供する。Coating Method The present invention provides a cationic electrodeposition coating method including a step of immersing an object to be coated in an electrodeposition bath made of the above-mentioned cationic electrodeposition coating composition and a step of energizing the object to be coated as a cathode. ..
本発明のカチオン電着塗料組成物の被塗物としては、自動車ボディ、２輪車部品、家庭用機器、その他の機器等が挙げられ、金属であれば特に制限はない。 Examples of the object to be coated with the cationic electrodeposition coating composition of the present invention include automobile bodies, two-wheeled vehicle parts, household equipment, other equipment, and the like, and are not particularly limited as long as they are metals.
被塗物としての金属板としては、冷延鋼板、合金化溶融亜鉛めっき鋼板、電気亜鉛めっき鋼板、電気亜鉛−鉄二層めっき鋼板、有機複合めっき鋼板、Ａｌ素材、Ｍｇ素材など、並びにこれらの金属板を必要に応じてアルカリ脱脂等の表面を洗浄化した後、リン酸塩化成処理、クロメート処理等の表面処理を行ったものが挙げられる。 Metal plates as objects to be coated include cold-rolled steel sheets, alloyed hot-dip galvanized steel sheets, electrogalvanized steel sheets, electrozinc-iron double-layer plated steel sheets, organic composite plated steel sheets, Al materials, Mg materials, and these metals. Examples thereof include those in which the surface of the plate is cleaned by alkali degreasing or the like as necessary, and then surface treatment such as phosphate chemical conversion treatment or chromate treatment is performed.
カチオン電着塗料組成物は、カチオン電着塗装によって所望の被塗物基材表面に塗装することができる。カチオン電着の塗装方法は、一般的には、脱イオン水等で希釈して固形分濃度が約５〜４０質量％とし、好ましくは１０〜２５質量％とし、さらにｐＨを４．０〜９．０、好ましくは５．５〜７．０の範囲内に調整したカチオン電着塗料組成物を浴として、通常、浴温１５〜３５℃に調整し、負荷電圧１００〜４００Ｖ好ましくは１５０〜３５０Ｖの条件で被塗物を陰極として通電することによって行う。電着塗装後、通常、被塗物に余分に付着したカチオン電着塗料を落とすために、限外濾過液（ＵＦ濾液）、逆浸透透過水（ＲＯ水）、工業用水、純水等で十分に水洗する。 The cationic electrodeposition coating composition can be applied to a desired surface of a substrate to be coated by cationic electrodeposition coating. The cathodic electrodeposition coating method is generally diluted with deionized water or the like to have a solid content concentration of about 5 to 40% by mass, preferably 10 to 25% by mass, and a pH of 4.0 to 9 by mass. Using the cationic electrodeposition coating composition adjusted in the range of 0.0, preferably 5.5 to 7.0, as a bath, the bath temperature is usually adjusted to 15 to 35 ° C., and the load voltage is 100 to 400 V, preferably 150 to 350 V. This is performed by energizing the object to be coated as a cathode under the conditions of. After electrodeposition coating, ultra-filtered solution (UF filtrate), reverse osmosis permeated water (RO water), industrial water, pure water, etc. are usually sufficient to remove excess cationic electrodeposition paint adhering to the object to be coated. Wash with water.
電着塗膜の膜厚は、特に制限されるものではないが、一般的には、乾燥塗膜に基づいて５〜４０μｍ、好ましくは１０〜３０μｍの範囲内とすることができる。また、塗膜の焼き付け乾燥は、電着塗膜を電気熱風乾燥機、ガス熱風乾燥機などの乾燥設備を用いて、塗装物表面の温度で１１０〜２００℃、好ましくは１４０〜１８０℃にて、時間としては１０〜１８０分間、好ましくは２０〜５０分間、電着塗膜を加熱して行う。上記焼付け乾燥により硬化塗膜を得ることができる。 The film thickness of the electrodeposition coating film is not particularly limited, but is generally in the range of 5 to 40 μm, preferably 10 to 30 μm based on the dry coating film. Further, the coating film is baked and dried by using a drying facility such as an electric hot air dryer or a gas hot air dryer to dry the electrodeposited coating film at a temperature of 110 to 200 ° C., preferably 140 to 180 ° C. The electrodeposition coating film is heated for 10 to 180 minutes, preferably 20 to 50 minutes. A cured coating film can be obtained by the above baking and drying.
以下、製造例、実施例及び比較例により、本発明をさら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。各例中の「部」は質量部、「％」は質量％を示す。 Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited thereto. In each example, "part" indicates a mass part and "%" indicates a mass%.
アミノ基含有エポキシ樹脂の製造
製造例１
撹拌機、温度計、窒素導入管および還流冷却器を取りつけたフラスコに、ｊＥＲ８２８ＥＬ（商品名、ジャパンエポキシレジン社製エポキシ樹脂、エポキシ当量１９０、数平均分子量３５０）１２００部に、ビスフェノールＡ ５００部及びジメチルベンジルアミン０．２部を加え、１３０℃でエポキシ当量８５０になるまで反応させた。
次に、ジエタノールアミン１６０部及びジエチレントリアミンとメチルイソブチルケトンとのケチミン化物６５部を加え、１２０℃で４時間反応させた後、エチレングリコールモノブチルエーテル４８０ｇを加え、固形分８０％のアミノ基含有エポキシ樹脂（Ａ−１）溶液を得た。アミノ基含有エポキシ樹脂（Ａ−１）は、アミン価５９ｍｇＫＯＨ／ｇ、数平均分子量２１００であった。Production of Amino Group-Containing Epoxy Resin Production Example 1
In a flask equipped with a stirrer, thermometer, nitrogen introduction tube and reflux condenser, 1200 parts of jER828EL (trade name, epoxy resin manufactured by Japan Epoxy Resin, epoxy equivalent 190, number average molecular weight 350), 500 parts of bisphenol A and 0.2 part of dimethylbenzylamine was added and reacted at 130 ° C. until the epoxy equivalent was 850.
Next, 160 parts of diethanolamine and 65 parts of ketiminated product of diethylenetriamine and methyl isobutyl ketone were added and reacted at 120 ° C. for 4 hours, then 480 g of ethylene glycol monobutyl ether was added, and an amino group-containing epoxy resin having a solid content of 80% ( A-1) A solution was obtained. The amino group-containing epoxy resin (A-1) had an amine value of 59 mgKOH / g and a number average molecular weight of 2100.
ブロック化ポリイソシアネート化合物の製造
製造例２
反応容器中に、コスモネートＭ−２００（商品名、三井化学社製、クルードＭＤＩ、ＮＣＯ基含有率 ３１．３％）２７０部、及びメチルイソブチルケトン１２７部を加え７０℃に昇温した。この中にエチレングリコールモノブチルエーテル２３６部を１時間かけて滴下して加え、その後１００℃に昇温し、この温度を保ちながら経時でサンプリングし、赤外線吸収スペクトル測定にて未反応のイソシアネート基の吸収がなくなったことを確認し、樹脂固形分８０％のブロック化ポリイソシアネート化合物（Ｂ−１）溶液を得た。Production of blocked polyisocyanate compound Production Example 2
270 parts of Cosmonate M-200 (trade name, manufactured by Mitsui Chemicals, Inc., Crude MDI, NCO group content 31.3%) and 127 parts of methyl isobutyl ketone were added to the reaction vessel, and the temperature was raised to 70 ° C. 236 parts of ethylene glycol monobutyl ether was added dropwise thereto over 1 hour, then the temperature was raised to 100 ° C., and sampling was performed over time while maintaining this temperature. Absorption of unreacted isocyanate groups by infrared absorption spectrum measurement. A blocked polyisocyanate compound (B-1) solution having a resin solid content of 80% was obtained.
顔料分散用樹脂の製造
製造例３
撹拌機、温度計、滴下ロートおよび還流冷却器を取り付けたフラスコに、ｊＥＲ８２８ＥＬ（商品名、ジャパンエポキシレジン社製エポキシ樹脂、エポキシ当量１９０、数平均分子量３５０）１０１０部に、ビスフェノールＡを３９０部、プラクセル２１２（商品名、ポリカプロラクトンジオール、ダイセル化学工業株式会社、重量平均分子量約１２５０）２４０部及びジメチルベンジルアミン０．２部を加え、１３０℃でエポキシ当量が約１０９０になるまで反応させた。次に、ジメチルエタノールアミン１３４部及び濃度９０％の乳酸水溶液１５０部を加え、９０℃でエポキシ基が消失するまで反応させた。次いで、プロピレングリコールモノメチルエーテルを加えて固形分を調整し、固形分６０％の４級アンモニウム塩基を含有する顔料分散用樹脂を得た。Production of resin for pigment dispersion Production example 3
In a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux cooler, 1010 parts of jER828EL (trade name, epoxy resin manufactured by Japan Epoxy Resin, epoxy equivalent 190, number average molecular weight 350), 390 parts of bisphenol A, 240 parts of Praxel 212 (trade name, polycaprolactone diol, Daicel Chemical Industry Co., Ltd., weight average molecular weight of about 1250) and 0.2 part of dimethylbenzylamine were added and reacted at 130 ° C. until the epoxy equivalent reached about 1090. Next, 134 parts of dimethylethanolamine and 150 parts of a 90% concentrated lactic acid aqueous solution were added, and the reaction was carried out at 90 ° C. until the epoxy groups disappeared. Next, propylene glycol monomethyl ether was added to adjust the solid content to obtain a pigment dispersion resin containing a quaternary ammonium base having a solid content of 60%.
ポリビニル化合物の製造
製造例４
撹拌機、冷却管、滴下ロートおよび窒素ガス導入管を備えた４つ口フラスコにシクロヘキサン１００ｇ及びポリオキシエチレンオレイルエーテル（第一工業製薬社製、商品名「ノイゲンＥＴ１４０Ｅ」、ＨＬＢ＝１４．０）０．５ｇを配合及び撹拌し、６０℃に昇温した。次に、窒素ガス気流下、Ｎ−ビニルアセトアミド３７．４ｇ、２，２′−アゾビス−２−アミジノプロパン２塩酸塩０．０５ｇ、及び脱イオン水２１ｇの混合溶液を３時間かけて滴下した。その後、窒素ガス気流下６０℃にて３時間撹拌して反応を行った。次いで冷却管と４つ口フラスコの間に共沸蒸留管を取り付け、浴温を９０℃に上げて水分を除いた。４０℃まで冷却後、生成物を濾過及び乾燥して固形分１００％にした後に水／ジメチルホルムアミド＝１／１の混合溶媒で希釈して固形分５０％のポリビニル化合物（Ｃ−１）を得た。重量平均分子量は約２００，０００、ＨＳＰのδｈ（水素結合項）は７．９ＭＰａ１／２であった。Production of polyvinyl compound Production example 4
Cyclohexane 100 g and polyoxyethylene oleyl ether (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "Neugen ET140E", HLB = 14.0) in a four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen gas introduction tube. 0.5 g was blended and stirred, and the temperature was raised to 60 ° C. Next, a mixed solution of 37.4 g of N-vinylacetamide, 0.05 g of 2,2'-azobis-2-amidinopropane dihydrochloride and 21 g of deionized water was added dropwise over 3 hours under a nitrogen gas stream. Then, the reaction was carried out by stirring at 60 ° C. for 3 hours under a nitrogen gas stream. Next, an azeotropic distillation tube was attached between the cooling tube and the four-necked flask, and the bath temperature was raised to 90 ° C. to remove water. After cooling to 40 ° C., the product is filtered and dried to 100% solid content, and then diluted with a mixed solvent of water / dimethylformamide = 1/1 to obtain a polyvinyl compound (C-1) having a solid content of 50%. rice field. The weight average molecular weight was about 200,000, and the δh (hydrogen bond term) of HSP was 7.9 MPa 1/2 .
製造例５〜１４
下記表１のモノマー配合とする以外は製造例４と同じ配合及び製造方法により、ポリビニル化合物（Ｃ−２）〜（Ｃ−１１）を製造した。重量平均分子量は約２００，０００であった。Production Examples 5 to 14
Polyvinyl compounds (C-2) to (C-11) were produced by the same formulation and production method as in Production Example 4 except that the monomers were blended in Table 1 below. The weight average molecular weight was about 200,000.
表中の配合量はモノマーの有効成分の値である。
なお、製造例７においては、水／ジメチルホルムアミド＝１／１の混合溶媒ではなく、ジメチルホルムアミド１００％の溶媒で希釈を行った。The blending amount in the table is the value of the active ingredient of the monomer.
In Production Example 7, dilution was carried out with a solvent of 100% dimethylformamide instead of a mixed solvent of water / dimethylformamide = 1/1.
顔料分散ペーストの製造
製造例１５
製造例３で得た固形分６０％の４級アンモニウム塩基を含有する顔料分散用樹脂８．３部（固形分５部）、酸化チタン１４．５部、精製クレー６部、カーボンブラック０．３部、水酸化ビスマス２部、乳酸ビスマス１部、及び脱イオン水２０．３部を加え、ボールミルにて２０時間分散し、固形分５５％の顔料分散ペースト（Ｐ−１）を得た。Production of Pigment Dispersion Paste Production Example 15
8.3 parts (5 parts solid content) of the pigment dispersion resin containing a quaternary ammonium base having a solid content of 60%, 14.5 parts titanium oxide, 6 parts purified clay, and 0.3 carbon black obtained in Production Example 3. 2 parts, 2 parts of bismuth hydroxide, 1 part of bismuth lactate, and 20.3 parts of deionized water were added and dispersed in a ball mill for 20 hours to obtain a pigment dispersion paste (P-1) having a solid content of 55%.
カチオン電着塗料組成物の製造
実施例１
製造例１で得られたアミノ基含有エポキシ樹脂（Ａ−１）８７．５部（固形分７０部）、製造例２で得られたブロック化ポリイソシアネート化合物（Ｂ−１）３７．５部（固形分３０部）を混合し、さらに１０％酢酸１３部を配合して均一に撹拌した後、脱イオン水を強く撹拌しながら約１５分間を要して滴下して固形分３４％のエマルションを得た。
次に、上記エマルション２９４部（固形分１００部）、製造例１５で得た顔料分散ペースト（Ｐ−１）５２．４部、製造例４で得たポリビニル化合物（Ｃ−１）１０部（固形分１部）、及び脱イオン水３４０部を加え撹拌し、固形分２０％のカチオン電着塗料組成物Ｘ−１を製造した。Production of Cationic Electroplated Coating Composition Example 1
87.5 parts (70 parts solid content) of the amino group-containing epoxy resin (A-1) obtained in Production Example 1 and 37.5 parts (B-1) of the blocked polyisocyanate compound (B-1) obtained in Production Example 2. 30 parts of solid content) was mixed, and 13 parts of 10% acetic acid was further mixed and stirred uniformly, and then the deionized water was added dropwise over about 15 minutes while vigorously stirring to obtain an emulsion having a solid content of 34%. Obtained.
Next, 294 parts (solid content 100 parts) of the above emulsion, 52.4 parts of the pigment dispersion paste (P-1) obtained in Production Example 15, and 10 parts (solid) of the polyvinyl compound (C-1) obtained in Production Example 4 1 part) and 340 parts of deionized water were added and stirred to prepare a cationic electrodeposition coating composition X-1 having a solid content of 20%.
実施例２〜１９及び比較例１〜３
下記表２の配合とする以外は実施例１と同じ配合及び製造方法により、カチオン電着塗料組成物Ｘ−２〜Ｘ−２２を製造した。
尚、後述する評価試験（仕上がり性、耐水性、エッジ防食性、付きまわり性）の結果も表中に記載する。本発明のカチオン電着塗料組成物においては、４種類の評価試験の全てで合格することが必要である。Examples 2 to 19 and Comparative Examples 1 to 3
Cationic electrodeposition coating compositions X-2 to X-22 were produced by the same formulation and production method as in Example 1 except for the formulations shown in Table 2 below.
The results of the evaluation tests (finishing property, water resistance, edge corrosion resistance, and wrapping property) described later are also described in the table. In the cationic electrodeposition coating composition of the present invention, it is necessary to pass all four types of evaluation tests.
表中の配合量は固形分の値である。
（注）「アコフロックＮ１００Ｓ」：商品名、ＭＴアクアポリマー社製、ポリアクリルアミド樹脂。The blending amount in the table is the value of solid content.
(Note) "Akovlock N100S": Trade name, manufactured by MT Aquapolymer, polyacrylamide resin.
試験板の作成
化成処理（商品名、パルボンド＃３０２０、日本パーカライジング社製、リン酸亜鉛処理剤）を施した冷延鋼板（１５０ｍｍ（縦）×７０ｍｍ（横）×０．８ｍｍ（厚））を被塗物として、実施例及び比較例で得た各々のカチオン電着塗料組成物を用いて乾燥膜厚１５μｍとなるように電着塗装し、１７０℃で２０分間焼付け乾燥して試験板を得た。Preparation of test plate Cold-rolled steel sheet (150 mm (length) x 70 mm (width) x 0.8 mm (thickness)) subjected to chemical conversion treatment (trade name, Palbond # 3020, manufactured by Nihon Parkerizing Co., Ltd., zinc phosphate treatment agent) As the object to be coated, each cationic electrodeposition coating composition obtained in Examples and Comparative Examples was electrodeposited so as to have a dry film thickness of 15 μm, and baked and dried at 170 ° C. for 20 minutes to obtain a test plate. rice field.
＜仕上がり性（表面粗度）＞
得られた試験板の塗面をサーフテスト３０１（商品名、株式会社ミツトヨ製、表面粗度計）を用いて、表面粗度値（Ｒａ）をカットオフ０．８ｍｍにて測定し、以下の基準で評価した。
評価は、Ａ〜Ｃが合格であり、Ｘが不合格である。
Ａ：表面粗度値（Ｒａ）が、０．２未満、
Ｂ：表面粗度値（Ｒａ）が、０．２以上、かつ０．２５未満、
Ｃ：表面粗度値（Ｒａ）が、０．２５以上、かつ０．３未満、
Ｘ：表面粗度値（Ｒａ）が、０．３以上。<Finishing (surface roughness)>
The coated surface of the obtained test plate was measured with a surface roughness value (Ra) using a surf test 301 (trade name, manufactured by Mitutoyo Co., Ltd., surface roughness meter) with a cutoff of 0.8 mm, and the following Evaluated by criteria.
In the evaluation, A to C pass and X fails.
A: Surface roughness value (Ra) is less than 0.2,
B: The surface roughness value (Ra) is 0.2 or more and less than 0.25.
C: The surface roughness value (Ra) is 0.25 or more and less than 0.3.
X: Surface roughness value (Ra) is 0.3 or more.
＜耐水性＞
得られた試験板の素地に達するように塗膜にカッターナイフでクロスカット傷を入れ、５０℃の温水に８４０時間浸漬し、以下の基準で評価した。
評価は、Ａ〜Ｃが合格であり、Ｘが不合格である。
Ａ：錆及びフクレの最大幅がカット部より片側で１．５ｍｍ以下、
Ｂ：錆及びフクレの最大幅がカット部より片側で１．５ｍｍを超え、かつ２．２ｍｍ以下、
Ｃ：錆及びフクレの最大幅がカット部より片側で２．２ｍｍを超え、かつ３．０ｍｍ以下、
Ｘ：錆及びフクレの最大幅がカット部より片側で３．０ｍｍを超える。<Water resistance>
A cross-cut scratch was made on the coating film with a cutter knife so as to reach the base material of the obtained test plate, and the coating film was immersed in warm water at 50 ° C. for 840 hours and evaluated according to the following criteria.
In the evaluation, A to C pass and X fails.
A: The maximum width of rust and blisters is 1.5 mm or less on one side of the cut part,
B: The maximum width of rust and blisters exceeds 1.5 mm on one side of the cut part and is 2.2 mm or less.
C: The maximum width of rust and blisters exceeds 2.2 mm on one side of the cut part and 3.0 mm or less.
X: The maximum width of rust and blisters exceeds 3.0 mm on one side of the cut portion.
＜エッジ防食性＞
カッター刃（刃角度２０度、長さ１０ｃｍ、リン酸亜鉛処理）に、浴温２８℃で、通電時間を調整し、電着塗装を行って一般面で１５μｍの膜厚になるように試験板を作成した。
次に、これをＪＩＳＺ−２３７１に準じて９６時間耐塩水噴霧試験を行い、エッジ部を以下の基準で評価した。
評価は、Ｓ、Ａ〜Ｃが合格であり、Ｘが不合格である。
Ｓ：錆の発生なし、
Ａ：錆の発生個数が１０個以下／１０ｃｍ、
Ｂ：錆の発生個数が１１〜２５個／１０ｃｍ、
Ｃ：錆の発生個数が２６〜４０個／１０ｃｍ、
Ｘ：錆の発生個数が４１個／１０ｃｍ以上。<Edge corrosion resistance>
The cutter blade (blade angle 20 degrees, length 10 cm, zinc phosphate treatment) is subjected to electrodeposition coating after adjusting the energization time at a bath temperature of 28 ° C, so that the film thickness is 15 μm on the general surface. It was created.
Next, this was subjected to a salt spray resistance test for 96 hours according to JISZ-2371, and the edge portion was evaluated according to the following criteria.
In the evaluation, S, A to C pass, and X fails.
S: No rust,
A: The number of rusts generated is 10 or less / 10 cm,
B: The number of rusts generated is 11 to 25/10 cm,
C: The number of rusts generated is 26-40 / 10 cm,
X: The number of rusts generated is 41/10 cm or more.
＜付きまわり性＞
４枚の鋼板に直径８ｍｍの穴を空け、２ｃｍ間隔で設置した「４枚ボックス法付きまわり性試験の治具」（図１参照）を、図２のように配線した。図２の４枚の鋼板のうち、最も左側の鋼板に向かって左側の面を「Ａ面」、向かって右側の面を「Ｂ面」とする。同様に、左から２番目の鋼板左右の面を、それぞれ、「Ｃ面」及び「Ｄ面」、左から３番目の鋼板左右の面を、それぞれ、「Ｅ面」及び「Ｆ面」、そして最も右側の鋼板左右の面が、それぞれ、「Ｇ面」と「Ｈ面」となる。この中で、Ａ面が「外板」であり、Ｇ面が「内板」となる。
図２の装置において、浴温２８℃、Ａ面と電極との極間距離１０ｃｍ、通電時間３分間にて、外板（Ａ面）乾燥膜厚４０μｍとなる電圧にて電着塗装した。付きまわり性は、内板（Ｇ面）乾燥膜厚で評価した。
評価は、Ａ〜Ｃが合格であり、Ｘが不合格である。
Ａ：Ｇ面（膜厚）が２５μｍ以上で、付きまわり性が非常に優れている。
Ｂ：Ｇ面（膜厚）が２０μｍ以上で、かつ２５μｍ未満で、付きまわり性が良好である。
Ｃ：Ｇ面（膜厚）が１５μｍ以上で、かつ２０μｍ未満で、付きまわり性が標準である。
Ｘ：Ｇ面（膜厚）が１５μｍ未満で、付きまわり性が劣る。
<Aroundness>
A "jig for a turnability test with a 4-sheet box method" (see FIG. 1), in which holes having a diameter of 8 mm were formed in four steel plates and installed at intervals of 2 cm, was wired as shown in FIG. Of the four steel plates shown in FIG. 2, the left side surface facing the leftmost steel plate is referred to as "A side", and the right side surface facing toward the leftmost steel plate is referred to as "B side". Similarly, the left and right surfaces of the second steel plate from the left are "C surface" and "D surface", respectively, and the left and right surfaces of the third steel plate from the left are "E surface" and "F surface", respectively. The left and right surfaces of the rightmost steel sheet are the "G surface" and the "H surface", respectively. Among them, the A side is the "outer plate" and the G side is the "inner plate".
In the apparatus of FIG. 2, electrodeposition coating was performed at a bath temperature of 28 ° C., an electrode distance of 10 cm between the A surface and the electrode, an energization time of 3 minutes, and a voltage at which the outer plate (A surface) had a dry film thickness of 40 μm. The wrapping property was evaluated by the dry film thickness of the inner plate (G surface).
In the evaluation, A to C pass and X fails.
A: The G surface (film thickness) is 25 μm or more, and the wrapping property is very excellent.
B: The G surface (film thickness) is 20 μm or more and less than 25 μm, and the wrapability is good.
C: The G-plane (film thickness) is 15 μm or more and less than 20 μm, and the circumstance is standard.
X: The G surface (film thickness) is less than 15 μm, and the wrapability is inferior.
ポリビニル化合物（Ｃ）
本発明のカチオン電着塗料組成物で用いることができるポリビニル化合物（Ｃ）は、下記式（Ｉ）及び／又は式（ＩＩ）で表されるアミド基含有モノマーを構成成分として有するポリビニル化合物である。
前記ポリビニル化合物（Ｃ）は、
（ｉ）下記式（Ｉ）で表されるモノマーを構成成分として有するポリビニル化合物（Ｃ）、又は
（ｉｉ）式（ＩＩ）で表されるモノマーをポリビニル化合物（Ｃ）の全構成モノマーを基準として４０モル％以上構成成分として有するポリビニル化合物（Ｃ）であってもよい。なかでも、少なくとも１種の下記式（Ｉ）を有することが好ましい。
ＣＨ２＝ＣＨ−ＮＨ−Ｃ（＝Ｏ）−Ｒ・・・（Ｉ）
（式中、Ｒは炭素数１以上の有機基である。）
ＣＨ２＝Ｃ（−Ｒ１）−Ｃ（＝Ｏ）−Ｎ（−Ｒ２）（−Ｒ３）・・・（ＩＩ）
（式中、Ｒ１は水素原子又はメチル基である。Ｒ２及びＲ３は同じでも異なっていてもよく、水素原子又は炭素数１以上の有機基であって、Ｒ２及びＲ３は互いに繋がって環状構造になっていてもよい。また、Ｒ２とＲ３のどちらか一方又は両方が炭素数１以上の有機基である。）
Polyvinyl compound (C)
The polyvinyl compound (C) that can be used in the cationic electrodeposition coating composition of the present invention is a polyvinyl compound having an amide group-containing monomer represented by the following formulas (I) and / or formula (II) as a constituent component. NS.
The polyvinyl compound (C) is
(I) A polyvinyl compound (C) having a monomer represented by the following formula (I) as a constituent component, or
It may be a polyvinyl compound (C) having a monomer represented by the formula (II) in an amount of 40 mol% or more as a constituent component based on all the constituent monomers of the polyvinyl compound (C). Among them, it is preferable to have at least one of the following formulas (I).
CH 2 = CH-NH-C (= O) -R ... (I)
(In the formula, R is an organic group having 1 or more carbon atoms.)
CH 2 = C (-R 1 ) -C (= O) -N (-R 2 ) ( -R 3 ) ... (II)
(In the formula, R 1 is a hydrogen atom or a methyl group. R 2 and R 3 may be the same or different, and are a hydrogen atom or an organic group having 1 or more carbon atoms, and R 2 and R 3 are mutual. It may be connected to form a cyclic structure. Further, either one or both of R 2 and R 3 are organic groups having 1 or more carbon atoms.)
Claims (10)
ＣＨ２＝ＣＨ−ＮＨ−Ｃ（＝Ｏ）−Ｒ・・・（Ｉ）
（式中、Ｒは炭素数１以上の有機基である。）
ＣＨ２＝Ｃ（−Ｒ１）−Ｃ（＝Ｏ）−Ｎ（−Ｒ２）（−Ｒ３）・・・（ＩＩ）
（式中、Ｒ１は水素原子又はメチル基である。Ｒ２及びＲ３は同じでも異なっていてもよく、水素原子又は炭素数１以上の有機基であって、Ｒ２及びＲ３は互いに繋がって環状構造になっていてもよい。また、Ｒ２とＲ３のどちらか一方又は両方が炭素数１以上の有機基である。）。Contains an amino group-containing epoxy resin (A), a blocked polyisocyanate compound (B), and a polyvinyl compound (C) containing a monomer represented by the following formula (I) and / or formula (II) as a constituent component. Cationic electrodeposition coating composition:
CH 2 = CH-NH-C (= O) -R ... (I)
(In the formula, R is an organic group having 1 or more carbon atoms.)
CH 2 = C (-R 1 ) -C (= O) -N (-R 2 ) ( -R 3 ) ... (II)
(In the formula, R 1 is a hydrogen atom or a methyl group. R 2 and R 3 may be the same or different, and are a hydrogen atom or an organic group having 1 or more carbon atoms, and R 2 and R 3 are mutual. They may be connected to form a cyclic structure. Further, either one or both of R 2 and R 3 are organic groups having 1 or more carbon atoms).
A method for producing a coated article, which comprises a step of forming a coating film by the coating method according to claim 9 and then heat-curing.
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