JP2023150168A - Coating composition, method for producing coated metal article, and coated metal article - Google Patents
Coating composition, method for producing coated metal article, and coated metal article Download PDFInfo
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- JP2023150168A JP2023150168A JP2022059125A JP2022059125A JP2023150168A JP 2023150168 A JP2023150168 A JP 2023150168A JP 2022059125 A JP2022059125 A JP 2022059125A JP 2022059125 A JP2022059125 A JP 2022059125A JP 2023150168 A JP2023150168 A JP 2023150168A
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- Prior art keywords
- coating composition
- coating
- pigment
- mass
- resin
- Prior art date
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- 239000008199 coating composition Substances 0.000 title claims abstract description 61
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 46
- 239000002184 metal Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000049 pigment Substances 0.000 claims abstract description 71
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 45
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims description 49
- 239000011248 coating agent Substances 0.000 claims description 44
- 239000003822 epoxy resin Substances 0.000 claims description 32
- 229920000647 polyepoxide Polymers 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 15
- 229920003180 amino resin Polymers 0.000 claims description 10
- 239000011247 coating layer Substances 0.000 claims description 2
- 239000004606 Fillers/Extenders Substances 0.000 abstract description 12
- 239000010408 film Substances 0.000 description 43
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 38
- 239000000243 solution Substances 0.000 description 31
- 239000003795 chemical substances by application Substances 0.000 description 27
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
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- 238000002360 preparation method Methods 0.000 description 4
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- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
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- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
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- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- IONSZLINWCGRRI-UHFFFAOYSA-N n'-hydroxymethanimidamide Chemical compound NC=NO IONSZLINWCGRRI-UHFFFAOYSA-N 0.000 description 1
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PYUYQYBDJFMFTH-WMMMYUQOSA-N naphthol red Chemical compound CCOC1=CC=CC=C1NC(=O)C(C1=O)=CC2=CC=CC=C2\C1=N\NC1=CC=C(C(N)=O)C=C1 PYUYQYBDJFMFTH-WMMMYUQOSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
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- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
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- 239000013615 primer Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
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- 238000004544 sputter deposition Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
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- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
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- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
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Images
Landscapes
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、基材の表面、特に金属基材に塗膜を形成するための塗料組成物、金属塗装物の製造方法および金属塗装物に関するものである。 The present invention relates to a coating composition for forming a coating film on the surface of a substrate, particularly a metal substrate, a method for producing a metal coating, and a metal coating.
屋根材、外装材、サイディング材、シャッター、雨戸等の建材、エアコンの屋内外機器、冷蔵庫、洗濯機等の家電製品、ドアパネルやルーフパネル等の自動車用品、事務機器、家具等の多くの用途において、構造材として用いられる金属については、この金属を用いて製造される製品や部品に対して高い耐久性や美観が要求されることから、その表面を塗料組成物で塗装することが行われている。 In many applications such as roofing materials, exterior materials, siding materials, building materials such as shutters and rain shutters, indoor and outdoor air conditioners, home appliances such as refrigerators and washing machines, automobile supplies such as door panels and roof panels, office equipment, and furniture. Regarding metals used as structural materials, products and parts manufactured using these metals are required to have high durability and aesthetics, so the surfaces of these metals are painted with paint compositions. There is.
そして、このような金属の塗装については、金属基材に中塗り塗料によるプライマー層を設けその上に上塗り塗装を施すことが一般に行われている（特許文献１、２）。
When painting such metals, it is common practice to provide a primer layer of intermediate paint on the metal base material and apply a top coat thereon (
ここで上塗り塗料は、熱硬化型の液体塗料や粉体塗料が採用されることが多いため、塗膜全体としての金属基材との付着性（金属基材／プライマー層間及びプライマー／上塗り塗膜層間）が求められている。また、金属の腐食を防止するため厚膜の形成も求められるが、これらの課題の解決はいまだ十分であるとは言えなかった。 Here, the top coat paint is often a thermosetting liquid paint or powder paint, so the adhesion of the entire paint film to the metal base material (metal base material / primer layer and primer / top coat film) interlayer) is required. Furthermore, it is necessary to form a thick film to prevent metal corrosion, but these problems have not yet been sufficiently resolved.
本発明の目的は、金属基材（特には鉄、非鉄金属）との優れた付着性を有し、厚膜化が可能である塗料組成物を提供することにある。 An object of the present invention is to provide a coating composition that has excellent adhesion to metal substrates (especially iron and non-ferrous metals) and can be formed into a thick film.
本発明の目的は、下記によって達成された。
１． 少なくとも、水酸基含有樹脂（Ａ）、架橋剤（Ｂ）および顔料（Ｃ）を含む塗料組成物であって、該顔料（Ｃ）は、少なくとも鱗片状顔料（Ｃ１）および該鱗片状顔料（Ｃ１）以外の体質顔料（Ｃ２）を含み、該塗料組成物の２５℃におけるせん断速度０．１ｓ－１の粘度（Ｘ）とせん断速度１００ｓ－１の粘度（Ｙ）の比（Ｘ／Ｙ）が１０～１５０である塗料組成物。
２． 前記顔料（Ｃ）の含有量は、前記塗料組成物の固形分に対して、２０～７０質量％である前記１記載の塗料組成物。
３． 前記（Ｃ１）と（Ｃ２）の合計量に対する（Ｃ１）の質量割合が、４０～９２．５質量％である前記１または２記載の塗料組成物。
４． 前記架橋剤(Ｂ)がアミノ樹脂である前記１～３いずれかに記載の塗料組成物。
５． さらにエポキシ樹脂（Ｄ）を含有する前記１～４いずれかに記載の塗料組成物。
６． 前記エポキシ樹脂（Ｄ）の含有量は、前記水酸基含有樹脂（Ａ）、前記架橋剤（Ｂ）および前記エポキシ樹脂（Ｄ）の合計量に対して、１～５０質量％である前記５に記載の塗料組成物。
７． 金属基材に、請求項１～６いずれかに記載の塗料組成物を塗装した後、完全硬化する前に上塗り塗料を塗装する金属塗装物の製造方法。
８． 金属基材、該基材に隣接して前記１～６いずれかの塗料組成物からなる塗布層を有する金属塗装物。
The objects of the invention were achieved by the following.
1. A coating composition containing at least a hydroxyl group-containing resin (A), a crosslinking agent (B), and a pigment (C), the pigment (C) comprising at least a scaly pigment (C1) and a scaly pigment (C1). The ratio (X/Y) of the viscosity (X) at a shear rate of 0.1 s -1 to the viscosity (Y) at a shear rate of 100 s -1 at 25° C. is 10. ~150 coating composition.
2. The coating composition according to
3. 3. The coating composition according to 1 or 2 above, wherein the mass ratio of (C1) to the total amount of (C1) and (C2) is 40 to 92.5% by mass.
4. 4. The coating composition according to any one of 1 to 3 above, wherein the crosslinking agent (B) is an amino resin.
5. 5. The coating composition according to any one of 1 to 4 above, further comprising an epoxy resin (D).
6. 5. The content of the epoxy resin (D) is 1 to 50% by mass based on the total amount of the hydroxyl group-containing resin (A), the crosslinking agent (B), and the epoxy resin (D). paint composition.
7. A method for producing a metal coated article, which comprises coating a metal substrate with the coating composition according to any one of
8. A metal coated article having a metal base material and a coating layer made of any of the
本発明によれば、金属基材との優れた付着性を有し、厚膜化が可能である塗料組成物を提供することができる。 According to the present invention, it is possible to provide a coating composition that has excellent adhesion to metal substrates and can be formed into a thick film.
以下、本発明の塗料組成物、金属塗装物の製造方法および金属塗装物を詳細に説明するが、これらに限定されるものではない。 The coating composition, the method for producing a metal coated article, and the metal coated article of the present invention will be described in detail below, but the present invention is not limited thereto.
＜塗料組成物＞
本発明の塗料組成物は、少なくとも、水酸基含有樹脂（Ａ）、架橋剤（Ｂ）および顔料（Ｃ）を含む塗料組成物であって、該顔料（Ｃ）は少なくとも鱗片状顔料（Ｃ１）および該鱗片状顔料（Ｃ１）以外の体質顔料（Ｃ２）を含み、該塗料組成物の２５℃におけるせん断速度０．１ｓ－１の粘度（Ｘ）とせん断速度１００ｓ－１の粘度（Ｙ）の比（Ｘ／Ｙ）が１０～１５０である、ことを特徴とする。
<Coating composition>
The coating composition of the present invention is a coating composition containing at least a hydroxyl group-containing resin (A), a crosslinking agent (B), and a pigment (C), wherein the pigment (C) includes at least a scaly pigment (C1) and The ratio of the viscosity (X) at a shear rate of 0.1 s -1 to the viscosity (Y) at a shear rate of 100 s -1 at 25°C of the coating composition containing an extender pigment (C2) other than the flaky pigment (C1) It is characterized in that (X/Y) is 10 to 150.
＜水酸基含有樹脂（Ａ）＞
水酸基含有樹脂（Ａ）としては、例えば、水酸基含有ポリエステル樹脂（Ａ１）や水酸基含有（メタ）アクリル樹脂（Ａ２）が挙げられる。
<Hydroxy group-containing resin (A)>
Examples of the hydroxyl group-containing resin (A) include hydroxyl group-containing polyester resin (A1) and hydroxyl group-containing (meth)acrylic resin (A2).
水酸基含有樹脂（Ａ）は、水酸基価１～２００ｍｇＫＯＨ/ｇのものを適宜選択することができ、３０～１５０ｍｇＫＯＨ/ｇが好ましい。水酸基含有樹脂の重量平均分子量は４０００～１０００００であり、好ましくは８０００～８００００である。水酸基含有樹脂の数平均分子量は１０００～２００００であり、好ましくは１５００～１００００である。ガラス転移温度（Ｔｇ）は１～１００℃であり、好ましくは１０～８０℃である。 The hydroxyl group-containing resin (A) can be appropriately selected from those with a hydroxyl value of 1 to 200 mgKOH/g, preferably 30 to 150 mgKOH/g. The weight average molecular weight of the hydroxyl group-containing resin is 4,000 to 100,000, preferably 8,000 to 80,000. The number average molecular weight of the hydroxyl group-containing resin is 1,000 to 20,000, preferably 1,500 to 10,000. The glass transition temperature (Tg) is 1 to 100°C, preferably 10 to 80°C.
本発明における水酸基価は、試料１ｇ中の水酸基を無水酢酸で完全にアセチル化した後、それを中和するのに要する水酸化カリウムのｍｇ数である。 The hydroxyl value in the present invention is the number of mg of potassium hydroxide required to completely acetylate hydroxyl groups in 1 g of a sample with acetic anhydride and then neutralize it.
本発明における数平均分子量は、ＳＥＣ法（サイズ排除クロマトグラフィー）により測定される標準ポリスチレン換算の数平均分子量である。またＴｇは、ＤＳＣによって測定できる。 The number average molecular weight in the present invention is a standard polystyrene equivalent number average molecular weight measured by the SEC method (size exclusion chromatography). Moreover, Tg can be measured by DSC.
≪水酸基含有ポリエステル樹脂（Ａ１）≫
本発明で使用できる水酸基含有ポリエステル樹脂として、多価アルコールと多塩基酸とから公知のエステル化法により得られる種々のポリエステル樹脂を挙げることができる。
≪Hydroxyl group-containing polyester resin (A1)≫
As the hydroxyl group-containing polyester resin that can be used in the present invention, there can be mentioned various polyester resins obtained from a polyhydric alcohol and a polybasic acid by a known esterification method.
多価アルコールとして、エチレングリコール、ジエチレングリコール、プロピレングリコール、ネオペンチルグリコール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、水添ビスフェノール、ビスフェノールＡのエチレンオキサイド付加物又はプロピレンオキサイド付加物、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、ペンタエリスリトール等を挙げることができる。 As the polyhydric alcohol, ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, or Examples include propylene oxide adducts, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
多塩基酸として、無水フタル酸、イソフタル酸、テレフタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、アゼライン酸、セバチン酸、無水マレイン酸、フマール酸、無水トリメリット酸、無水ピロメリット酸等を挙げることができ、さらに、必要に応じて、安息香酸、ｐ－ターシャリーブチル安息香酸等の一塩基酸を併用することもできる。 Examples of polybasic acids include phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, azelaic acid, sebacic acid, maleic anhydride, fumaric acid, trimellitic anhydride, pyromellitic anhydride, etc. Furthermore, if necessary, a monobasic acid such as benzoic acid or p-tert-butylbenzoic acid may be used in combination.
上記の水酸基含有ポリエステル樹脂（Ａ１）は、単独で用いることができるほか、必要により、２種以上を併用して使用することもできる。 The above hydroxyl group-containing polyester resin (A1) can be used alone or, if necessary, two or more types can be used in combination.
≪水酸基含有（メタ）アクリル樹脂（Ａ２）≫
本発明で使用できる水酸基含有（メタ）アクリル樹脂（Ａ２）は、例えば、水酸基を含有する（メタ）アクリレートモノマー１種以上と、水酸基を含有しない（メタ）アクリレートモノマー１種以上との共重合体が挙げられる。
≪Hydroxyl group-containing (meth)acrylic resin (A2)≫
The hydroxyl group-containing (meth)acrylic resin (A2) that can be used in the present invention is, for example, a copolymer of one or more hydroxyl group-containing (meth)acrylate monomers and one or more hydroxyl group-free (meth)acrylate monomers. can be mentioned.
必要に応じて、他の重合性不飽和モノマーを共重合させたものであってもよい。なお、ここで、（メタ）アクリレートモノマーとは、アクリレートまたはメタクリレートを意味する。 If necessary, it may be copolymerized with other polymerizable unsaturated monomers. In addition, (meth)acrylate monomer here means acrylate or methacrylate.
水酸基を含有する（メタ）アクリレートモノマーとしては、特に限定されないが、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等の（メタ）アクリル酸と２価アルコールとのモノエステル化物や、分子末端が水酸基であるポリオキシエチレン鎖を有する（メタ）アクリレート等が挙げられる。 The (meth)acrylate monomer containing a hydroxyl group is not particularly limited, but examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl Examples include monoesterified products of (meth)acrylic acid and dihydric alcohol such as (meth)acrylate, and (meth)acrylate having a polyoxyethylene chain with a hydroxyl group at the molecular terminal.
水酸基を含有しない（メタ）アクリレートモノマーとしては、特に限定されないが、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート等のアルキル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、シクロドデシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート等の脂環式（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート等の芳香族系（メタ）アクリレート、（アリル（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、グリシジル（メタ）アクリレート等が挙げられる。 Examples of (meth)acrylate monomers that do not contain hydroxyl groups include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate. ) acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, ) acrylate, alkyl (meth)acrylates such as tridecyl (meth)acrylate and octadecyl (meth)acrylate, alicyclic rings such as cyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate. Aromatic (meth)acrylates such as formula (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, (allyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycidyl (meth)acrylate, ) acrylate, etc.
共重合させてもよい他の重合性不飽和モノマーとしては、特に限定されないが、例えば、スチレン、α－メチルスチレン、ビニルトルエン等のビニル基含有芳香族化合物や、酢酸ビニル等のビニル基含有化合物、（メタ）アクリル酸等が挙げられる。 Other polymerizable unsaturated monomers that may be copolymerized are not particularly limited, but include, for example, vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, and vinyltoluene, and vinyl group-containing compounds such as vinyl acetate. , (meth)acrylic acid, and the like.
水酸基含有（メタ）アクリル樹脂（Ａ２）は、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 The hydroxyl group-containing (meth)acrylic resin (A2) may be used alone or in combination of two or more types.
＜架橋剤（Ｂ）＞
水酸基含有樹脂（Ａ）に対して使用できる架橋剤としては、例えば、アミノ樹脂およびポリイソシアネート化合物（好ましくはブロック化ポリイソシアネート化合物）が好適に挙げられる。
<Crosslinking agent (B)>
Suitable crosslinking agents that can be used for the hydroxyl group-containing resin (A) include, for example, amino resins and polyisocyanate compounds (preferably blocked polyisocyanate compounds).
架橋剤は、塗料組成物の固形分に対して、０．５～１５質量％であることが好ましく、さらには２～１０質量％であることが好ましい。架橋剤は、市販品を好適に使用することができる。また、架橋剤は、反応させる樹脂の種類に応じて適宜選択されるものであるが、二種以上を組み合わせて用いてもよい。 The amount of the crosslinking agent is preferably 0.5 to 15% by mass, more preferably 2 to 10% by mass, based on the solid content of the coating composition. As the crosslinking agent, commercially available products can be suitably used. Further, the crosslinking agent is appropriately selected depending on the type of resin to be reacted, but two or more types may be used in combination.
≪アミノ樹脂≫
アミノ樹脂としては、硬化触媒の存在下又は非存在下において、樹脂の水酸基と反応して樹脂を硬化することができるものであればよく、特には限定されないが、好適なものとしてメラミン樹脂、ベンゾグアナミン樹脂、尿素樹脂等が挙げられ、この中でもメラミン樹脂が好ましい。
≪Amino resin≫
The amino resin may be any resin that can react with the hydroxyl group of the resin to cure the resin in the presence or absence of a curing catalyst, and is not particularly limited, but suitable examples include melamine resin and benzoguanamine. Examples include resins, urea resins, etc., and among these, melamine resins are preferred.
メラミン樹脂は、例えば、メラミン、ベンゾグアナミン、アセトグアナミン等のアミノ成分と、アセトアルデヒド、ホルムアルデヒド、パラホルムアルデヒド等のアルデヒドとの反応によって得られる樹脂や、アルデヒドがアミノ成分に付加した部分を、メチルアルコール、エチルアルコール、ｎ－プロピルアルコール、ｎ－ブチルアルコール、ｉ－プロピルアルコール、ｉ－ブチルアルコール等のアルコールによって、エーテル化した樹脂等が挙げられる。 Melamine resins include, for example, resins obtained by reacting amino components such as melamine, benzoguanamine, and acetoguanamine with aldehydes such as acetaldehyde, formaldehyde, and paraformaldehyde, and resins obtained by reacting amino components such as melamine, benzoguanamine, and acetoguanamine, and resins obtained by reacting aldehydes with aldehydes such as methyl alcohol and ethyl alcohol. Examples include resins etherified with alcohols such as alcohol, n-propyl alcohol, n-butyl alcohol, i-propyl alcohol, and i-butyl alcohol.
≪ポリイソシアネート化合物≫
ポリイソシアネート化合物としては、硬化触媒の存在下又は非存在下において、樹脂の水酸基と反応して樹脂を硬化することができるものであればよく、特に限定されるものではなく、好適なものとしてポリイソシアネート化合物の遊離イソシアネート基をブロック化剤によってブロック化してなる化合物（いわゆるブロック化イソシアネート化合物）が挙げられる。
≪Polyisocyanate compound≫
The polyisocyanate compound is not particularly limited as long as it can react with the hydroxyl group of the resin to cure the resin in the presence or absence of a curing catalyst, and preferred examples include polyisocyanate compounds. Examples include compounds obtained by blocking the free isocyanate groups of an isocyanate compound with a blocking agent (so-called blocked isocyanate compounds).
ポリイソシアネート化合物の具体例としては、ヘキサメチレンジイソシアネート若しくはトリメチルヘキサメチレンジイソシアネート等の脂肪族ジイソシアネート類、水素添加キシリレンジイソシアネート若しくはイソホロンジイソシアネート等の環状脂肪族ジイソシアネート類、トリレンジイソシアネート若しくは４，４’－ジフェニルメタンジイソシアネート等の芳香族ジイソシアネート類等の有機ジイソシアネートそれ自体、又はこれらの各有機ジイソシアネートと多価アルコール、低分子量ポリエステル樹脂もしくは水等との付加物、あるいは上記した各有機ジイソシアネート同士の環化重合体、さらにはイソシアネート・ビウレット体等を挙げることができる。 Specific examples of polyisocyanate compounds include aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate, cycloaliphatic diisocyanates such as hydrogenated xylylene diisocyanate or isophorone diisocyanate, tolylene diisocyanate or 4,4'-diphenylmethane. Organic diisocyanates themselves such as aromatic diisocyanates such as diisocyanates, adducts of each of these organic diisocyanates with polyhydric alcohols, low molecular weight polyester resins, water, etc., or cyclized polymers of the above-mentioned organic diisocyanates, Further examples include isocyanate biuret and the like.
また、イソシアネート基をブロックするブロック化剤としては、例えばフェノール、クレゾール、キシレノール等のフェノール系、ε－カプロラクタム、δ－バレロラクタム、γ-ブチロラクタム、β-プロピオラクタム等のラクタム系、メタノール、エタノール、ｎ－又はｉ－プロピルアルコール、ｎ－，ｉ－又はｔ－ブチルアルコール、エチレングリコールモノメチルエーテル、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モノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、ベンジルアルコール等のアルコール系、ホルムアミドキシム、アセトアルドキシム、アセトキシム、メチルエチルケトキシム、ジアセチルモノオキシム、ベンゾフェノンオキシム、シクロヘキサンオキシム等のオキシム系、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、アセチルアセトン等の活性メチレン系等のブロック化剤を好適に使用することができる。 In addition, examples of blocking agents that block isocyanate groups include phenols such as phenol, cresol, and xylenol, lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam, methanol, and ethanol. , n- or i-propyl alcohol, n-, i- or t-butyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, Alcohols such as benzyl alcohol, formamidoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetylmonoxime, benzophenone oxime, oximes such as cyclohexane oxime, dimethyl malonate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, acetylacetone A blocking agent such as an active methylene-based blocking agent such as the above can be suitably used.
そして、これらポリイソシアネート化合物と上記ブロック化剤とを混合することによって容易に上記ポリイソシアネート化合物のフリーのイソシアネート基をブロックすることができる。 By mixing these polyisocyanate compounds with the blocking agent, free isocyanate groups of the polyisocyanate compounds can be easily blocked.
＜その他の樹脂＞
本発明の塗料組成物には、付着性改良のためエポキシ樹脂（Ｄ）を含有することができる。
<Other resins>
The coating composition of the present invention may contain an epoxy resin (D) to improve adhesion.
≪エポキシ樹脂（Ｄ）≫
本発明のエポキシ樹脂（Ｄ）としては、ビスフェノール型、およびフェノールノボラック型に代表される一般的なエポキシ樹脂を用いることができる。エポキシ樹脂の市販品としては、商品名「ｊＥＲ♯８２８」（ビスフェノールＡ型液状エポキシ樹脂、エポキシ当量１８４～１９４、分子量約３８０、三菱ケミカル社製）、「ｊＥＲ♯８３４」（ビスフェノールＡ型固形エポキシ樹脂、エポキシ当量２３０～２７０、分子量約４７０、三菱ケミカル社製）、「ｊＥＲ♯１００１」（ビスフェノールＡ型固形エポキシ樹脂、エポキシ当量４５０～５００、分子量約９００、三菱ケミカル社製）、「ｊＥＲ♯１００４」（ビスフェノールＡ型固形エポキシ樹脂、エポキシ当量８７５～９７５、分子量約１６００、三菱ケミカル社製）、「ｊＥＲ♯１００７」（ビスフェノールＡ型固形エポキシ樹脂、エポキシ当量１７５０～２２００、分子量約２９００、三菱ケミカル社製）、「ｊＥＲ♯８０７」（ビスフェノールＦ型液状エポキシ樹脂、エポキシ当量１６０～１７５、分子量約３３０、三菱ケミカル社製）商品名「ｊＥＲ♯１５４」（フェノールノボラック型エポキシ樹脂、エポキシ当量１７６～１８０、分子量約５４０、三菱ケミカル社製）、商品名「ＹＲ－４５０」（ゴム変性エポキシ樹脂、エポキシ当量４００～５００、分子量約８００～１０００、東都化成社製）等が挙げられる。
≪Epoxy resin (D)≫
As the epoxy resin (D) of the present invention, common epoxy resins typified by bisphenol type and phenol novolak type can be used. Commercially available epoxy resins include the product name "jER#828" (bisphenol A type liquid epoxy resin, epoxy equivalent 184-194, molecular weight about 380, manufactured by Mitsubishi Chemical Corporation), "jER#834" (bisphenol A type solid epoxy resin), Resin, epoxy equivalent 230-270, molecular weight approx. 470, manufactured by Mitsubishi Chemical), “jER#1001” (bisphenol A solid epoxy resin, epoxy equivalent 450-500, molecular weight approx. 900, manufactured by Mitsubishi Chemical), “jER# 1004'' (bisphenol A type solid epoxy resin, epoxy equivalent weight 875-975, molecular weight approximately 1600, manufactured by Mitsubishi Chemical Corporation), ``jER#1007'' (bisphenol A type solid epoxy resin, epoxy equivalent weight 1750-2200, molecular weight approximately 2900, manufactured by Mitsubishi Chemical Corporation) Chemical Co., Ltd.), "jER#807" (bisphenol F type liquid epoxy resin, epoxy equivalent weight 160-175, molecular weight approximately 330, Mitsubishi Chemical Co., Ltd.) product name "jER#154" (phenol novolac type epoxy resin, epoxy equivalent weight 176) ~180, molecular weight approximately 540, manufactured by Mitsubishi Chemical Corporation), and trade name "YR-450" (rubber modified epoxy resin, epoxy equivalent weight 400 to 500, molecular weight approximately 800 to 1000, manufactured by Toto Kasei Co., Ltd.).
本発明に用いられるエポキシ樹脂（Ｄ）は上記エポキシ樹脂に限定されるものではなく、一般に市販されているその他のエポキシ樹脂等も使用することができる。 The epoxy resin (D) used in the present invention is not limited to the above-mentioned epoxy resins, and other commercially available epoxy resins can also be used.
本発明のエポキシ樹脂（Ｄ）は、付着性の点からエポキシ当量が１００～３０００のものが好ましい。また塗膜の付着性の点からより好ましくは、１５０～１０００である。 The epoxy resin (D) of the present invention preferably has an epoxy equivalent of 100 to 3,000 from the viewpoint of adhesion. Further, from the viewpoint of adhesion of the coating film, it is more preferably 150 to 1000.
エポキシ樹脂（Ｄ）は、塗膜物性や塗装作業性の点から数平均分子量（ＳＥＣによるポリスチレン換算）が２００～５０００のものが好ましく、より好ましくは３００～２０００である。 The epoxy resin (D) preferably has a number average molecular weight (polystyrene equivalent by SEC) of 200 to 5,000, more preferably 300 to 2,000, from the viewpoint of coating film properties and coating workability.
本発明のエポキシ樹脂（Ｄ）は、水酸基含有樹脂（Ａ）、前記架橋剤（Ｂ）およびエポキシ樹脂（Ｄ）の合計量に対して、１～５０質量％であることが好ましく、２～３０質量％であることがより好ましい。本発明のエポキシ樹脂（Ｄ）は、単独で用いてもよく、２種以上を併用してもよい。 The epoxy resin (D) of the present invention preferably accounts for 1 to 50% by mass, and preferably 2 to 30% by mass, based on the total amount of the hydroxyl group-containing resin (A), the crosslinking agent (B), and the epoxy resin (D). It is more preferable that it is mass %. The epoxy resin (D) of the present invention may be used alone or in combination of two or more.
＜顔料（Ｃ）＞
本発明の顔料（Ｃ）は、少なくとも鱗片状顔料（Ｃ１）および該鱗片状顔料（Ｃ１）以外の体質顔料（Ｃ２）を含み、場合により鱗片状顔料（Ｃ１）および体質顔料（Ｃ２）以外の顔料を含んでもよい。
<Pigment (C)>
The pigment (C) of the present invention contains at least a scale-like pigment (C1) and an extender pigment (C2) other than the scale-like pigment (C1), and optionally contains a scale-like pigment (C1) and an extender pigment (C2) other than the scale-like pigment (C1). It may also contain pigments.
顔料（Ｃ）の含有量は、塗料組成物の固形分に対して、２０～７０質量％であることが好ましく、さらには４０～７０質量％であることが好ましい。鱗片状顔料（Ｃ１）の含有量は、塗料組成物の固形分に対して、１０～４０質量％であることが好ましい。 The content of pigment (C) is preferably 20 to 70% by mass, more preferably 40 to 70% by mass, based on the solid content of the coating composition. The content of the scaly pigment (C1) is preferably 10 to 40% by mass based on the solid content of the coating composition.
また、鱗片状顔料（Ｃ１）と該鱗片状顔料（Ｃ１）以外の体質顔料（Ｃ２）の合計量（Ｃ１＋Ｃ２）に対する（Ｃ１）の含有量の割合は、４０～９２．５質量％であることが好ましい。 Further, the content ratio of (C1) to the total amount (C1+C2) of the scale pigment (C1) and the extender pigment (C2) other than the scale pigment (C1) shall be 40 to 92.5% by mass. is preferred.
鱗片状顔料（Ｃ１）を含むことにより、乾燥膜厚６０μｍ以上になるよう塗装した場合においても、基材（特にはアルミニウムやステンレスなどの非鉄金属）および上塗り塗膜との付着性に優れる。 By including the scaly pigment (C1), it has excellent adhesion to the base material (particularly non-ferrous metals such as aluminum and stainless steel) and the top coat even when it is coated to a dry film thickness of 60 μm or more.
≪鱗片状顔料（Ｃ１）≫
発明の鱗片状顔料（Ｃ１）は、箔のような薄く平らな形状をした顔料であり、その具体例としては、亜鉛、ニッケル、クロム、錫、銅、銀、白金、金、アルミニウム等の金属顔料や、ガラスフレーク、タルク、マイカ、カオリンクレー、雲母状酸化鉄等が挙げられるが、中でもガラスフレーク、タルク、マイカ、カオリンクレーが好ましく、タルクがより好ましい。
<<Scaly pigment (C1)>>
The scaly pigment (C1) of the invention is a thin, flat pigment like a foil, and specific examples include metals such as zinc, nickel, chromium, tin, copper, silver, platinum, gold, and aluminum. Examples include pigments, glass flakes, talc, mica, kaolin clay, mica-like iron oxide, etc. Among them, glass flakes, talc, mica, and kaolin clay are preferred, and talc is more preferred.
なお、金属顔料には、ステンレス等の合金の顔料も含まれる。また、例えばタルクやマイカは、酸化チタン等の金属酸化物で表面処理されていてもよい。これら鱗片状顔料（Ｃ１）は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 Note that metal pigments also include pigments made of alloys such as stainless steel. Further, for example, talc or mica may be surface-treated with a metal oxide such as titanium oxide. These scaly pigments (C1) may be used alone or in combination of two or more.
アスペクト比は、付着性を向上させる観点から、２～１００であることが好ましく、３～５０であることがより好ましく、５～４０であることがさらに好ましい。そして平均粒子径が０．５～５０μｍであることが好ましく、１～３０μｍであることが好ましい。平均粒子径は、投影した面の最も長い径を、アスペクト比とは、粒子の最長径と最短径の比率をいい電子顕微鏡写真による１００個の粒子での平均値をいう。 From the viewpoint of improving adhesion, the aspect ratio is preferably 2 to 100, more preferably 3 to 50, and even more preferably 5 to 40. The average particle diameter is preferably 0.5 to 50 μm, more preferably 1 to 30 μm. The average particle diameter refers to the longest diameter of a projected surface, and the aspect ratio refers to the ratio of the longest diameter to the shortest diameter of a particle, and refers to the average value of 100 particles as determined by an electron micrograph.
≪該鱗片状顔料（Ｃ１）以外の体質顔料（Ｃ２）≫
本発明の塗料組成物は、鱗片状顔料以外（Ｃ１）の体質顔料（Ｃ２）を含むものである。鱗片状顔料（Ｃ１）以外の体質顔料（Ｃ２）（以下単に、体質顔料（Ｃ２）ともいう）を鱗片状顔料以外（Ｃ１）と共に含むことにより、本発明の塗料組成物を塗装した後に上塗り塗料を塗装して作製される塗装体の外観が良好で、さらに基材および上塗り塗膜との付着性に優れる。
≪Extender pigment (C2) other than the scaly pigment (C1)≫
The coating composition of the present invention contains an extender pigment (C2) other than the scaly pigment (C1). By including an extender pigment (C2) other than the flaky pigment (C1) (hereinafter also simply referred to as an extender pigment (C2)) together with the pigment other than the flaky pigment (C1), a top coat can be applied after applying the coating composition of the present invention. The coated body produced by coating has a good appearance and has excellent adhesion to the base material and top coat.
体質顔料（Ｃ２）は、公知の材料が使用でき、炭酸カルシウム、硫酸バリウム、アルミナ、ミョウバン、白土、水酸化マグネシウム、および酸化マグネシウムなどが挙げられるが、中でも炭酸カルシウム、硫酸バリウムが好ましく、硫酸バリウムがより好ましい。 For the extender pigment (C2), known materials can be used, such as calcium carbonate, barium sulfate, alumina, alum, clay, magnesium hydroxide, and magnesium oxide, among which calcium carbonate and barium sulfate are preferred, and barium sulfate is preferred. is more preferable.
≪（Ｃ１）、（Ｃ２）以外の顔料≫
本発明の塗料組成物は、鱗片状顔料（Ｃ１）および体質顔料（Ｃ２）以外の機能を有する顔料として、防錆顔料、着色顔料を含むことができる。
<<Pigments other than (C1) and (C2)>>
The coating composition of the present invention can contain a rust preventive pigment and a colored pigment as pigments having functions other than the scale pigment (C1) and the extender pigment (C2).
［防錆顔料］
防錆顔料としては、公知の材料が使用でき、例えば、亜鉛粉末、酸化亜鉛、メタホウ酸バリウム、珪酸カルシウム、リン酸アルミニウム、縮合リン酸アルミニウム、トリポリリン酸アルミニウム、リン酸亜鉛、亜リン酸亜鉛、亜リン酸カリウム、亜リン酸カルシウム、亜リン酸アルミニウム、リン酸亜鉛カルシウム、リン酸亜鉛アルミニウム、リンモリブデン酸亜鉛、リンモリブデン酸アルミニウム、リン酸マグネシウム、バナジン酸／ リン酸混合顔料等が挙げられる。
[Rust prevention pigment]
Known materials can be used as the antirust pigment, such as zinc powder, zinc oxide, barium metaborate, calcium silicate, aluminum phosphate, condensed aluminum phosphate, aluminum tripolyphosphate, zinc phosphate, zinc phosphite, Examples include potassium phosphite, calcium phosphite, aluminum phosphite, zinc calcium phosphate, zinc aluminum phosphate, zinc phosphomolybdate, aluminum phosphomolybdate, magnesium phosphate, and vanadate/phosphoric acid mixed pigments.
本発明の塗料組成物において、固形分中における防錆顔料の含有量は、１～１５質量％であることが好ましい。これら防錆顔料は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 In the coating composition of the present invention, the content of the antirust pigment in the solid content is preferably 1 to 15% by mass. These antirust pigments may be used alone or in combination of two or more.
［着色顔料］
着色顔料としては、酸化チタン、ベンガラ、黄色酸化鉄、カーボンブラック、等の無機着色顔料や、フタロシアニンブルー、フタロシアニングリーン、ナフトールレッド、キナクリドンレッド、ベンズイミダゾロンイエロー、ハンザイエロー、ベンズイミダゾロンオレンジ、およびジオキサジンバイオレット等の有機着色顔料が挙げられる。
[Colored pigment]
Coloring pigments include inorganic coloring pigments such as titanium oxide, red iron oxide, yellow iron oxide, and carbon black, as well as phthalocyanine blue, phthalocyanine green, naphthol red, quinacridone red, benzimidazolone yellow, Hansa yellow, benzimidazolone orange, and Examples include organic coloring pigments such as dioxazine violet.
本発明の塗料組成物において、固形分中における着色顔料の含有量は、１～２５質量％であることが好ましい。これら顔料は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。 In the coating composition of the present invention, the content of colored pigment in the solid content is preferably 1 to 25% by mass. These pigments may be used alone or in combination of two or more.
＜せん断速度＞
本発明の塗料組成物は、せん断速度０．１ｓ－１の粘度（Ｘ）が０．１～１００Ｐａ・ｓであり、かつせん断速度１，０００ｓ－１の粘度（Ｙ）が０．０１～１Ｐａ・ｓであることが好ましい。粘度はレオメーター（ＴＡインスツルメンツ社製レオメーターＡＲＥＳ）を用い、液温を２５℃に調整した後測定される。
<Shear rate>
The coating composition of the present invention has a viscosity (X) of 0.1 to 100 Pa·s at a shear rate of 0.1 s -1 and a viscosity (Y) of 0.01 to 1 Pa at a shear rate of 1,000 s -1 . - It is preferable that it is s. The viscosity is measured using a rheometer (Rheometer ARES manufactured by TA Instruments) after adjusting the liquid temperature to 25°C.
本発明においては、鱗片状顔料（Ｃ１）と体質顔料（Ｃ２）との組み合わせによってせん断速度を調整することができることを見出した。さらにこの組み合わせは、金属基材への付着性も向上させる。 In the present invention, it has been found that the shear rate can be adjusted by combining the scale pigment (C1) and the extender pigment (C2). Furthermore, this combination also improves adhesion to metal substrates.
＜その他の添加剤＞
本発明の塗料組成物には、塗料業界で通常使用される添加剤、例えば、表面調整剤、湿潤剤、分散剤、乳化剤、粘性制御剤、増粘剤、沈降防止剤、皮張り防止剤、たれ防止剤、消泡剤、色分かれ防止剤、レベリング剤、乾燥剤、可塑剤、殺虫剤、光安定化剤、紫外線吸収剤、帯電防止剤、シランカップリング剤、溶剤および導電性付与剤等を目的に応じて適宜配合することができる。
<Other additives>
The coating composition of the present invention includes additives commonly used in the coating industry, such as surface conditioners, wetting agents, dispersants, emulsifiers, viscosity control agents, thickeners, anti-settling agents, anti-skinning agents, Anti-sag agents, anti-foaming agents, anti-color separation agents, leveling agents, desiccants, plasticizers, insecticides, light stabilizers, ultraviolet absorbers, antistatic agents, silane coupling agents, solvents, conductivity imparting agents, etc. can be appropriately blended depending on the purpose.
≪粘性制御剤≫
本発明の塗料組成物は、２５℃におけるせん断速度０．１ｓ－１の粘度（Ｘ）とせん断速度１００ｓ－１の粘度（Ｙ）の比（Ｘ／Ｙ）が１０～１５０に調整するために粘性制御剤を補助的に用いることができる。
≪Viscosity control agent≫
The coating composition of the present invention has a ratio (X/Y) of viscosity (X) at a shear rate of 0.1 s -1 to viscosity (Y) at a shear rate of 100 s -1 at 25°C to be adjusted to 10 to 150. Viscosity control agents can be used supplementarily.
粘性制御剤としては、一般にチクソトロピー性を示すものを含有でき、例えば、脂肪酸アマイドの膨潤分散体、アマイド系脂肪酸、長鎖ポリアミノアマイドの燐酸塩等のポリアマイド系粘性制御剤、酸化ポリエチレンのコロイド状膨潤分散体等のポリエチレン系粘性制御剤、有機酸スメクタイト粘土、モンモリロナイト等の有機ベントナイト系粘性制御剤等を粘性制御剤として挙げることができる。耐水性および厚膜塗装性を向上させる点から、無機系粘性制御剤（例えば、有機ベントナイト系粘性制御剤など）と有機系粘性制御剤（例えば、ポリアマイド系粘性制御剤、ポリエチレン系粘性制御剤など）を組み合わせることが好ましい。 The viscosity control agent can generally include those exhibiting thixotropy, such as swelling dispersions of fatty acid amide, amide fatty acids, polyamide viscosity control agents such as phosphates of long-chain polyaminoamides, and colloidal swelling of polyethylene oxide. Examples of the viscosity control agent include polyethylene viscosity control agents such as dispersions, organic acid smectite clays, and organic bentonite viscosity control agents such as montmorillonite. In order to improve water resistance and thick film coating properties, inorganic viscosity control agents (e.g. organic bentonite viscosity control agents, etc.) and organic viscosity control agents (e.g. polyamide viscosity control agents, polyethylene viscosity control agents, etc.) are used. ) is preferably combined.
粘性制御剤は、塗料組成物の固形分中の０．１～２．５質量％であることが好ましい。 The viscosity control agent preferably accounts for 0.1 to 2.5% by mass of the solid content of the coating composition.
≪シランカップリング剤≫
本発明の塗料組成物は、シランカップリング剤を含有してもよい。シランカップリング剤としては、ビニル基、エポキシ基、アクリル基、イソシアネート基等の反応性基を有するものが好ましく、特にエポキシ基を有するものが好ましい。具体的には、信越シリコーン社製、東レ・ダウコーニング社製等の市販のシランカップリング剤を使用することができる。
≪Silane coupling agent≫
The coating composition of the present invention may contain a silane coupling agent. As the silane coupling agent, one having a reactive group such as a vinyl group, an epoxy group, an acrylic group, an isocyanate group, etc. is preferable, and one having an epoxy group is particularly preferable. Specifically, commercially available silane coupling agents such as those manufactured by Shin-Etsu Silicone and Dow Corning Toray can be used.
シランカップリング剤の含有量は、塗料組成物の固形分中０～５．０質量％であり、０．５～３．０質量％であることが好ましい。 The content of the silane coupling agent is 0 to 5.0% by mass, preferably 0.5 to 3.0% by mass, based on the solid content of the coating composition.
≪溶剤≫
本発明の塗料組成物は、溶剤を使用してもよい。溶剤としては、特に限定なく使用することができるが、例えばトルエン、キシレン等の炭化水素類、メチルエチルケトン、ジイソブチルケトン等のケトン類、酢酸エチル、酢酸ブチル、セロソルブアセテート等のエステル、２－エチルヘキサノール等のアルコール類が挙げられる。本発明においては、炭化水素類、アルコール類を好ましく使用することができる。
≪Solvent≫
The coating composition of the present invention may contain a solvent. The solvent can be used without particular limitation, but includes, for example, hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone and diisobutyl ketone, esters such as ethyl acetate, butyl acetate, and cellosolve acetate, and 2-ethylhexanol. Examples include alcohols. In the present invention, hydrocarbons and alcohols can be preferably used.
＜金属基材＞
本発明の塗料組成物を適用するのが好ましい金属基材としては、特に限定されるものではないが、その形状は、例えば板状、シート状、箔状等である。また、該基材を構成する金属としては、鉄鋼、亜鉛めっき鋼、ステンレス鋼、マグネシウム合金、アルミニウム、アルミニウム合金等が挙げられ、中でも、鉄鋼が好ましい。
<Metal base material>
The metal substrate to which the coating composition of the present invention is preferably applied is not particularly limited, but its shape is, for example, plate-like, sheet-like, foil-like, etc. Further, examples of the metal constituting the base material include steel, galvanized steel, stainless steel, magnesium alloy, aluminum, aluminum alloy, etc., and among them, steel is preferable.
さらに、上記金属基材としては、各種表面処理、例えば酸化処理が施されてもよい。一例として、アルマイト処理、リン酸塩処理、クロメート処理、ノンクロメート処理等の方法でアルミニウムに酸化処理を施した基材を用いることができる。 Furthermore, the metal base material may be subjected to various surface treatments, such as oxidation treatment. As an example, a base material in which aluminum is oxidized by a method such as alumite treatment, phosphate treatment, chromate treatment, or non-chromate treatment can be used.
なお、金属基材には、金属薄膜を表面に備える各種プラスチック基材（その形状は、例えば３次元の構造を持つ筐体およびフィルム等がある）も含まれる。金属の成膜には、蒸着、スパッタ、メッキ法等が利用できる。金属薄膜としては、アルミニウム、錫、亜鉛、金、銀、白金、ニッケル等の金属の薄膜が挙げられる。 Note that the metal base material also includes various plastic base materials having a metal thin film on the surface (the shapes thereof include, for example, a case having a three-dimensional structure, a film, etc.). Vapor deposition, sputtering, plating, etc. can be used to form a metal film. Examples of the metal thin film include thin films of metals such as aluminum, tin, zinc, gold, silver, platinum, and nickel.
＜上塗り塗料＞
金属基材に、本発明の塗料組成物を塗装した後、高い耐久性や美観を付与するなどの目的で上塗り塗料を塗装してもよい。
<Top coat paint>
After coating a metal substrate with the coating composition of the present invention, a top coat may be applied for the purpose of imparting high durability and aesthetic appearance.
上記上塗り塗料には、主溶媒として有機溶剤を用いる有機溶剤系塗料、主溶媒として水を用いる水系塗料、無溶剤系塗料、粉体塗料の各種エナメル又はクリア塗料等の従来から公知の各種塗料が利用可能である。 The above-mentioned top coat paints include various conventionally known paints such as organic solvent paints that use an organic solvent as the main solvent, water-based paints that use water as the main solvent, solvent-free paints, and powder paints such as various enamels or clear paints. Available.
上記上塗り塗料は、塗膜形成性能を有する樹脂および硬化剤等を含有するものが好ましく使用できる。塗膜形成性能を有する樹脂と硬化剤の組み合わせとしては、例えば、水酸基含有樹脂とアミノ樹脂の組み合わせ、水酸基含有樹脂とポリイソシアネート系硬化剤（ブロック化されたポリイソシアネートであってもよい。）の組み合わせ、カルボキシル基含有樹脂とβ－ヒドロキシアクリルアミドの組み合わせなどが挙げられる。 As the above-mentioned top coating, one containing a resin having coating film-forming performance, a curing agent, etc. can be preferably used. Combinations of resins and curing agents that have coating film-forming performance include, for example, combinations of hydroxyl group-containing resins and amino resins, hydroxyl group-containing resins and polyisocyanate-based curing agents (blocked polyisocyanates may also be used). Examples include combinations of carboxyl group-containing resins and β-hydroxyacrylamide.
上記水酸基含有樹脂としては、例えば、水酸基含有アルキド樹脂、水酸基含有アクリル樹脂、水酸基含有ポリエステル樹脂、水酸基含有フッ素樹脂が挙げられる。これらの水酸基含有樹脂は一部が変性されていてもよい。 Examples of the hydroxyl group-containing resin include hydroxyl group-containing alkyd resins, hydroxyl group-containing acrylic resins, hydroxyl group-containing polyester resins, and hydroxyl group-containing fluororesins. These hydroxyl group-containing resins may be partially modified.
上記カルボキシル基含有樹脂としては、カルボキシル基含有アルキド樹脂、カルボキシル基含有アクリル樹脂、カルボキシル基含有ポリエステル樹脂、カルボキシル基含有フッ素樹脂が挙げられる。これらのカルボキシル基含有樹脂は一部が変性されていてもよい。 Examples of the carboxyl group-containing resin include carboxyl group-containing alkyd resins, carboxyl group-containing acrylic resins, carboxyl group-containing polyester resins, and carboxyl group-containing fluororesins. These carboxyl group-containing resins may be partially modified.
上記上塗り塗料中において、上記硬化剤成分の含有量は、上塗り塗料を十分に硬化させることができる量であれば良い。硬化剤成分がアミノ樹脂である場合、水酸基含有樹脂／アミノ樹脂の質量比＝９５／５～３５／６５の範囲で調製されることが好ましい。なお、アミノ樹脂は自己架橋も起こすため、アミノ樹脂が当量より多く含まれていても塗膜の形成に寄与する。 The content of the curing agent component in the top coat may be any amount that can sufficiently cure the top coat. When the curing agent component is an amino resin, it is preferable that the mass ratio of hydroxyl group-containing resin/amino resin is in the range of 95/5 to 35/65. In addition, since amino resin also causes self-crosslinking, even if the amino resin is contained in an amount larger than the equivalent amount, it contributes to the formation of a coating film.
また、ポリイソシアネート系硬化剤を使用する場合、水酸基とＮＣＯ基のモル比（ＯＨ／ＮＣＯ）＝０．８～１．２で調整されることが好ましい。β－ヒドロキシアクリルアミドを硬化剤として使用する場合、カルボキシル基と水酸基のモル比（ＣＯＯＨ／ＯＨ）＝０．８～１．２で調整されることが好ましい。 Furthermore, when using a polyisocyanate curing agent, it is preferable to adjust the molar ratio of hydroxyl groups to NCO groups (OH/NCO) to 0.8 to 1.2. When β-hydroxyacrylamide is used as a curing agent, the molar ratio of carboxyl groups to hydroxyl groups (COOH/OH) is preferably adjusted to 0.8 to 1.2.
＜金属塗装物の製造方法＞
本発明の金属塗装物の製造方法は、金属基材である被塗物上に、本発明の塗料組成物をプライマー塗料として被塗布物に塗装した後、上塗塗料組成物を塗装し、積層塗膜を形成する。
<Method for producing metal coated objects>
The method for producing a metal-coated article of the present invention involves applying the coating composition of the present invention as a primer coating onto an article to be coated, which is a metal base material, and then applying a top coat composition to the article to be coated. Forms a film.
上塗塗料組成物については、プライマー塗料の塗装物が十分に乾燥又は硬化させた後に塗装してもよいし、プライマー塗料の塗装物が未乾燥または未硬化の完全硬化する前の状態で塗装してもよい。上塗塗料組成物を塗装し、積層塗膜を形成した後、乾燥および硬化反応を完結させ、最終目的物である積層塗装物を形成する。 The top coat composition may be applied after the primer coating has sufficiently dried or hardened, or it may be applied while the primer coating is undried or uncured, but before it is completely cured. Good too. After the top coating composition is applied to form a laminated coating film, drying and curing reactions are completed to form the final objective layered coating.
本発明においては、プライマー塗料の塗装物を十分に乾燥又は硬化させた後に、粉体塗料を塗装した場合においても、塗膜外観に優れる積層塗装物を得ることができる。 In the present invention, even when a powder coating is applied after the primer coating has been sufficiently dried or cured, a multilayer coating with an excellent coating appearance can be obtained.
本発明の塗料組成物および上塗塗料組成物を塗装してプライマー塗膜および上塗塗膜を製造するにあたっては、通常の塗装方法を適用することができる。 In producing a primer coating film and a top coating film by coating the coating composition and topcoat coating composition of the present invention, a conventional coating method can be applied.
例えば、例えば、ディッピング法、静電塗装法、スピンコート法、フローコート法、ロールコート法、スプレーコート法、ブレードコート法及びエアーナイフコート法等が挙げられる。これらの中でも、膜厚の制御が容易であるとの観点から、スプレーコート法及びロールコート法が好ましい。 Examples include a dipping method, an electrostatic coating method, a spin coating method, a flow coating method, a roll coating method, a spray coating method, a blade coating method, and an air knife coating method. Among these, the spray coating method and the roll coating method are preferred from the viewpoint of easy control of the film thickness.
本発明の塗料組成物を塗装して得られるプライマー塗膜の膜厚は所望の用途により変化するが、１０～８０μｍが好ましい。また、上塗塗料組成物を塗装して得られる上塗塗膜の膜厚は所望の用途により変化するが、１０～８０μｍが好ましい。 The thickness of the primer coating obtained by applying the coating composition of the present invention varies depending on the desired use, but is preferably 10 to 80 μm. Further, the thickness of the top coat film obtained by applying the top coat composition varies depending on the desired use, but is preferably 10 to 80 μm.
プライマー塗膜や上塗塗膜の膜厚をそれぞれ上記範囲に設定することにより、積層塗膜の防食性、層間付着性及び塗膜外観を優れたものとすることができる。 By setting the film thicknesses of the primer coating film and the top coating film within the above-mentioned ranges, the multilayer coating film can have excellent corrosion resistance, interlayer adhesion, and coating film appearance.
最終目的物である積層塗装物を作製するにあたり、プライマー塗膜や上塗塗膜の乾燥および硬化反応を完結させるために焼付け（加熱乾燥）を行うことが好ましい。プライマー塗膜の焼付条件については、１００～２００℃で５～９０分加熱乾燥することが好ましい。 When producing a multilayer coated product, which is the final object, it is preferable to perform baking (heat drying) in order to complete the drying and curing reaction of the primer coating film and the top coating film. Regarding the baking conditions for the primer coating, it is preferable to heat and dry at 100 to 200°C for 5 to 90 minutes.
上塗塗膜の焼付条件については、１００～２００℃で５～９０分加熱乾燥することが好ましい。また、プライマー塗膜と上塗塗膜とを積層塗膜として同時に最終的に硬化反応させる場合は、１００～２００℃で５～９０分加熱乾燥することが好ましい。 Regarding the baking conditions for the top coat, it is preferable to heat and dry at 100 to 200°C for 5 to 90 minutes. Further, when the primer coating film and the top coating film are to be finally cured simultaneously as a laminated coating film, it is preferable to heat dry at 100 to 200° C. for 5 to 90 minutes.
以下に、実施例を挙げて本発明をさらに詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。なお、断りの無い限り２３℃、５０%ＲＨ雰囲気下で測定した。 EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to the Examples below. Note that unless otherwise specified, measurements were made at 23° C. and in a 50% RH atmosphere.
＜１．ポリエステル樹脂溶液Ａの製造方法＞
攪拌機、温度計、還流冷却器、脱水装置及び窒素ガス導入管等の備わった反応容器に、トリメチロールプロパン５部、ネオペンチルグリコール２２部、無水フタル酸１３部、イソフタル酸１３部、アジピン酸１０部、及びキシレン３部を入れ、窒素雰囲気下で加熱攪拌し、２４０℃で反応混合物の樹脂酸価が８ｍｇＫＯＨ／ｇになるまで反応を行った後、冷却した。次に、得られた反応混合物中にキシレン３４部を入れ、混合して加熱残分６０％、水酸基価７３ｍｇＫＯＨ／ｇ、及び数平均分子量３２００、重量平均分子量３００００のポリエステル樹脂の樹脂溶液Ａを得た。
<1. Method for producing polyester resin solution A>
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dehydrator, a nitrogen gas inlet pipe, etc., 5 parts of trimethylolpropane, 22 parts of neopentyl glycol, 13 parts of phthalic anhydride, 13 parts of isophthalic acid, and 10 parts of adipic acid were added. 1 part and 3 parts of xylene were added, heated and stirred under a nitrogen atmosphere, and the reaction was carried out at 240° C. until the resin acid value of the reaction mixture became 8 mgKOH/g, and then cooled. Next, 34 parts of xylene was added to the obtained reaction mixture and mixed to obtain a resin solution A of a polyester resin with a heating residue of 60%, a hydroxyl value of 73 mgKOH/g, and a number average molecular weight of 3200 and a weight average molecular weight of 30000. Ta.
＜２．プライマー塗料組成物１（比較例１）の調製＞
容器に、ポリエステル樹脂溶液Ａを３２．２質量部、メラミン樹脂溶液を３．８質量部、タルク（Ｃ１－１）を２１．７質量部、酸化チタンを１２．６質量部、トリポリリン酸アルミニウム５．２質量部、エポキシ樹脂溶液を１．６５質量部、粘性調整剤溶液Ｅ１を０．５質量部、粘性調整剤溶液Ｅ２を０．５２質量部、粘性調整剤溶液Ｅ３を５．２質量部、シリコーン系表面調整剤溶液を０．１質量部、シランカップリング剤（ＫＢＭ－４０３）を１．０５質量部、キシレン１０．３３質量部、イソブチルアルコール５．１５質量部を順次仕込み、公知の製造方法により、プライマー塗料組成物１を調製した。
<2. Preparation of primer paint composition 1 (comparative example 1)>
In a container, 32.2 parts by mass of polyester resin solution A, 3.8 parts by mass of melamine resin solution, 21.7 parts by mass of talc (C1-1), 12.6 parts by mass of titanium oxide, and 5 parts by mass of aluminum tripolyphosphate. .2 parts by mass, 1.65 parts by mass of epoxy resin solution, 0.5 parts by mass of viscosity modifier solution E1, 0.52 parts by mass of viscosity modifier solution E2, 5.2 parts by mass of viscosity modifier solution E3. , 0.1 parts by mass of a silicone surface conditioner solution, 1.05 parts by mass of a silane coupling agent (KBM-403), 10.33 parts by mass of xylene, and 5.15 parts by mass of isobutyl alcohol were sequentially charged, and a known method was prepared.
＜３．プライマー塗料組成物２～１８の調製＞
プライマー塗料組成物１の原料配合を、表１～表４の配合に変更する以外は、実施例１と同様の製造方法により、プライマー塗料組成物２～１８（実施例１～１３、比較例２～５）を調製した。
<3. Preparation of
表１～表４に記載の原料は次の通りである。
１）ポリエステル樹脂溶液Ａ（上述の製造方法により調製される。）
２）メラミン樹脂溶液（ブチル化メラミン樹脂のイソブチルアルコール／キシレン混合溶液、商品名：メラン ２８４Ａ、昭和電工マテリアルズ社製、不揮発分６０質量％）
３）タルク（Ｃ１－１）（商品名：ＭＳ－Ｋ、日本タルク社製、白色度９３％、平均粒子径Ｄ５０：１６μｍ（レーザー回折法）、吸油量２５ｍｌ／１００ｇ）
４）タルク（Ｃ１－２）（商品名：シムゴン、日本タルク社製、白色度８３％、平均粒子径Ｄ５０：８μｍ（レーザー回折法）、吸油量３５ｍｌ／１００ｇ）
５）タルク（Ｃ１－３）（商品名：ＲＡ、日本タルク社製、白色度９１％、平均粒子径Ｄ５０：１４μｍ（レーザー回折法）、吸油量２６ｍｌ／１００ｇ）
The raw materials listed in Tables 1 to 4 are as follows.
1) Polyester resin solution A (prepared by the above manufacturing method)
2) Melamine resin solution (mixed solution of butylated melamine resin in isobutyl alcohol/xylene, trade name: Melan 284A, manufactured by Showa Denko Materials Co., Ltd., nonvolatile content 60% by mass)
3) Talc (C1-1) (trade name: MS-K, manufactured by Nippon Talc Co., Ltd., whiteness 93%, average particle diameter D50: 16 μm (laser diffraction method), oil absorption 25 ml/100 g)
4) Talc (C1-2) (trade name: Simgon, manufactured by Nippon Talc Co., Ltd., whiteness 83%, average particle diameter D50: 8 μm (laser diffraction method), oil absorption 35 ml/100 g)
5) Talc (C1-3) (trade name: RA, manufactured by Nippon Talc Co., Ltd., whiteness 91%, average particle diameter D50: 14 μm (laser diffraction method), oil absorption 26 ml/100 g)
６）沈降性硫酸バリウム（商品名：沈降性硫酸バリウム１００、堺化学工業社製、平均粒子径０．５μｍ、吸油量１５ｍｌ／１００ｇ）
７）炭酸カルシウム（商品名：サンライトＳＬ－１０００、竹原化学社製、平均粒子径３μｍ、吸油量２０ｍｌ／１００ｇ）
８）酸化チタン（商品名：ＴＩＴＯＮＥ Ｒ－５Ｎ、堺化学工業社製）
９）カーボンブラック（商品名：ＭＡ１００、三菱ケミカル社製）
１０）トリポリリン酸二水素アルミニウム（商品名：Ｋ－Ｗｈｉｔｅ Ｇ１０５、テイカ社製、表面を亜鉛化合物で処理したトリポリリン酸２水素アルミニウム）
6) Precipitated barium sulfate (trade name: Precipitated barium sulfate 100, manufactured by Sakai Chemical Industry Co., Ltd., average particle size 0.5 μm, oil absorption 15 ml/100 g)
7) Calcium carbonate (product name: Sunlight SL-1000, manufactured by Takehara Chemical Co., Ltd.,
8) Titanium oxide (product name: TITONE R-5N, manufactured by Sakai Chemical Industry Co., Ltd.)
9) Carbon black (product name: MA100, manufactured by Mitsubishi Chemical Corporation)
10) Aluminum dihydrogen tripolyphosphate (Product name: K-White G105, manufactured by Teika, aluminum dihydrogen tripolyphosphate whose surface has been treated with a zinc compound)
１１）エポキシ樹脂溶液Ｄ１（三菱ケミカル社製エポキシ樹脂ＪＥＲ１００１のキシレン溶液（不揮発分７０質量％）
１２）粘性調整剤溶液Ｅ１（楠本化成社製ディスパロン４２００（酸化ポリエチレン）のキシレン溶液、不揮発分２０質量％）
１３）粘性調整剤溶液Ｅ２（商品名：共栄社化学社製、高級脂肪酸アマイドのキシレン／エタノール／メタノール混合溶液、不揮発分１０質量％）
１４）粘性調整剤溶液Ｅ３（ＥＬＥＭＥＮＴＩＳ社製ＢＥＮＴＯＮＥ ３４（有機ベントナイト）のキシレン／メタノール混合溶剤、不揮発分１０質量％）
１５）表面調整剤溶液（信越シリコーン社製ＫＦ－６９（シリコーンオイル）のキシレン溶液、不揮発分１質量％）
11) Epoxy resin solution D1 (xylene solution of epoxy resin JER1001 manufactured by Mitsubishi Chemical Corporation (nonvolatile content 70% by mass)
12) Viscosity modifier solution E1 (xylene solution of Disparon 4200 (polyethylene oxide) manufactured by Kusumoto Kasei Co., Ltd., non-volatile content 20% by mass)
13) Viscosity modifier solution E2 (trade name: manufactured by Kyoeisha Chemical Co., Ltd., xylene/ethanol/methanol mixed solution of higher fatty acid amide, non-volatile content 10% by mass)
14) Viscosity modifier solution E3 (xylene/methanol mixed solvent of BENTONE 34 (organic bentonite) manufactured by ELEMENTIS, non-volatile content 10% by mass)
15) Surface conditioner solution (xylene solution of KF-69 (silicone oil) manufactured by Shin-Etsu Silicone Co., Ltd.,
＜４－１．上塗塗料組成物（艶有り）の調製＞
容器に、アクリル樹脂溶液（商品名：アクリディック４４－１２７、ＤＩＣ社製、不揮発分５０質量％、Ｔｇ３５℃、水酸基価（固形分）７０）を３５質量部、メラミン樹脂溶液（ブチル化メラミン樹脂のイソブチルアルコール／キシレン混合溶液、商品名：メラン ２８４Ａ、昭和電工マテリアルズ社製、不揮発分６０質量％）を１０質量部、エポキシ樹脂溶液（三菱ケミカル社製エポキシ樹脂ＪＥＲ１００１のキシレン溶液（不揮発分６０質量％））を２質量部、酸化チタン（商品名：ＴＩＴＯＮＥ Ｒ－５Ｎ、堺化学工業社製）を３４．８５質量部、赤色酸化鉄（Ｓｉｃｏｔｒａｎｓ Ｒｅｄ Ｌ２８１７，ＢＡＳＦ社製）を０．１質量部、カーボンブラック（商品名：ＭＡ１００、三菱ケミカル社製）を０．０５質量部、炭酸カルシウム（商品名：サンライトＳＬ－１０００、竹原化学社製）を５質量部、シランカップリング剤（商品名：ＫＢＭ－４０３、信越化学工業社製）を０．５質量部、表面調整剤溶液（信越シリコーン社製ＫＦ－６９（シリコーンオイル）のキシレン溶液、不揮発分１質量％）を０．２質量部、イプゾール１００（出光興産社製溶剤）を９．３質量部、イソブチルアルコール３質量部を順次仕込み、公知の製造方法により、上塗塗料組成物（艶有り）を調製した。
<4-1. Preparation of top coating composition (glossy)>
In a container, 35 parts by mass of acrylic resin solution (trade name: Acrydic 44-127, manufactured by DIC Corporation, nonvolatile content 50% by mass, Tg 35°C, hydroxyl value (solid content) 70), melamine resin solution (butylated melamine resin) 10 parts by mass of isobutyl alcohol/xylene mixed solution, trade name: Melan 284A, manufactured by Showa Denko Materials Co., Ltd., nonvolatile content 60%), 10 parts by mass of epoxy resin solution (xylene solution of epoxy resin JER1001 manufactured by Mitsubishi Chemical Corporation (nonvolatile content 60%) 2 parts by mass of titanium oxide (trade name: TITONE R-5N, manufactured by Sakai Chemical Industry Co., Ltd.), 0.1 parts by mass of red iron oxide (Sicotrans Red L2817, manufactured by BASF) 0.05 parts by mass of carbon black (product name: MA100, manufactured by Mitsubishi Chemical Corporation), 5 parts by mass of calcium carbonate (product name: Sunlight SL-1000, manufactured by Takehara Chemical Co., Ltd.), silane coupling agent (product name: 0.5 parts by mass of KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd., and 0.2 parts by mass of surface conditioner solution (xylene solution of KF-69 (silicone oil) manufactured by Shin-Etsu Silicone Co., Ltd., non-volatile content: 1% by mass). 9.3 parts by mass of Ipsol 100 (solvent manufactured by Idemitsu Kosan Co., Ltd.) and 3 parts by mass of isobutyl alcohol were sequentially charged to prepare a top coating composition (glossy) by a known manufacturing method.
＜４－２．上塗塗料組成物（艶なし）の調製＞
容器に、アクリル樹脂溶液（商品名：アクリディック４４－１２７、ＤＩＣ社製、不揮発分５０質量％、Ｔｇ３５℃、水酸基価（固形分）７０）を３５質量部、メラミン樹脂溶液（ブチル化メラミン樹脂のイソブチルアルコール／キシレン混合溶液、商品名：メラン ２８４Ａ、昭和電工マテリアルズ社製、不揮発分６０質量％）を１０質量部、エポキシ樹脂溶液（三菱ケミカル社製エポキシ樹脂ＪＥＲ１００１のキシレン溶液（不揮発分６０質量％））を２質量部、酸化チタン（商品名：ＴＩＴＯＮＥ Ｒ－５Ｎ、堺化学工業社製）を３４．８５質量部、赤色酸化鉄（Ｓｉｃｏｔｒａｎｓ Ｒｅｄ Ｌ２８１７，ＢＡＳＦ社製）を０．１質量部、カーボンブラック（商品名：ＭＡ１００、三菱ケミカル社製）を０．０５質量部、炭酸カルシウム（商品名：サンライトＳＬ－１０００、竹原化学社製）を５質量部、シランカップリング剤（商品名：ＫＢＭ－４０３、信越化学工業社製）を０．５質量部、表面調整剤溶液（信越シリコーン社製ＫＦ－６９（シリコーンオイル）のキシレン溶液、不揮発分１質量％）を０．２質量部、イプゾール１００（出光興産社製溶剤）を６．８質量部、イソブチルアルコール３質量部、シリカ（ＳＹＬＯＩＤ Ｃ９０６、ＷＲグレース社製、平均粒子径６μｍ）２．５質量部を順次仕込み、公知の製造方法により、上塗塗料組成物（艶なし）を調製した。
<4-2. Preparation of top coating composition (non-glossy)>
In a container, 35 parts by mass of acrylic resin solution (trade name: Acrydic 44-127, manufactured by DIC Corporation, nonvolatile content 50% by mass, Tg 35°C, hydroxyl value (solid content) 70), melamine resin solution (butylated melamine resin) 10 parts by mass of isobutyl alcohol/xylene mixed solution, trade name: Melan 284A, manufactured by Showa Denko Materials Co., Ltd., nonvolatile content 60%), 10 parts by mass of epoxy resin solution (xylene solution of epoxy resin JER1001 manufactured by Mitsubishi Chemical Corporation (nonvolatile content 60%) 2 parts by mass of titanium oxide (trade name: TITONE R-5N, manufactured by Sakai Chemical Industry Co., Ltd.), 0.1 parts by mass of red iron oxide (Sicotrans Red L2817, manufactured by BASF) 0.05 parts by mass of carbon black (product name: MA100, manufactured by Mitsubishi Chemical Corporation), 5 parts by mass of calcium carbonate (product name: Sunlight SL-1000, manufactured by Takehara Chemical Co., Ltd.), silane coupling agent (product name: 0.5 parts by mass of KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd., and 0.2 parts by mass of surface conditioner solution (xylene solution of KF-69 (silicone oil) manufactured by Shin-Etsu Silicone Co., Ltd., non-volatile content: 1% by mass). 1 part, 6.8 parts by mass of Ipsol 100 (solvent manufactured by Idemitsu Kosan Co., Ltd.), 3 parts by mass of isobutyl alcohol, and 2.5 parts by mass of silica (SYLOID C906, manufactured by WR Grace Co., Ltd., average particle diameter 6 μm) were sequentially charged. A top coating composition (non-glossy) was prepared according to the manufacturing method.
＜５－１．複層塗膜形成塗板の作成＞
（実施例１（プライマー塗料３）の複層塗膜形成塗板の作成）
下記の工程１～工程３によって、実施例１の複層塗膜形成塗板（本発明の積層塗装物に該当する）を作製した。
<5-1. Creation of multi-layer paint film forming coating plate>
(Creation of multi-layer coating film forming coating plate of Example 1 (Primer paint 3))
A multilayer coating film-forming coated plate of Example 1 (corresponding to the laminated coated product of the present invention) was produced by the following
工程１：冷間圧延鋼板（大きさ０．８×７０×１５０ｍｍ、パルボンド＃３０２０）にプライマー塗料組成物１を用い、乾燥膜厚が６０μｍになるようにスプレー塗装にて垂直塗装、２５℃で５分間セッティングしプライマー塗膜を形成した。
工程２：次いでプライマー塗膜上に、上塗塗料組成物１を用い、乾燥膜厚が３０μｍになるようにスプレー塗装にてウエットオンウエットで垂直塗装をして、上塗塗膜を形成した。
工程３：工程１～工程２によって得られた積層塗膜を、２５℃で１０分間セッティングした後、１５０℃で２０分間加熱乾燥（焼き付け）させて実施例１の複層塗膜形成塗板（積層塗装物）を得た。
Step 1: Using
Step 2: Next,
Step 3: The laminated coating film obtained in
（実施例２～１３、比較例１～５）
工程１のプライマー塗料組成物と工程２の上塗塗料組成物を表に示す組み合わせとする以外は、実施例１と同様にして、複層塗膜形成塗板を作製した。
また、各プライマー塗料について、上塗塗料組成物１と塗装した塗板と上塗塗料組成物２を塗装した塗板をそれぞれ作製した。
(Examples 2 to 13, Comparative Examples 1 to 5)
A multilayer coated plate was prepared in the same manner as in Example 1, except that the primer paint composition in
Furthermore, for each primer paint, a coated plate coated with
＜５－２：光沢値評価のための基準塗板作成＞
下記の方法によって、光沢値評価のための基準塗板Ａ、Ｂを作製した。
冷間圧延鋼板（大きさ０．８×７０×１５０ｍｍ、パルボンド＃３０２０）に上塗塗料組成物（艶有）を用い、乾燥膜厚が３０μｍになるようにスプレー塗装し、２５℃で１０分間セッティングし、その後、１５０℃で２０分間加熱乾燥（焼き付け）することにより、基準塗板Ａを作製した。
<5-2: Creation of standard coated plate for gloss value evaluation>
Standard coated plates A and B for gloss value evaluation were prepared by the following method.
Spray coat a cold rolled steel plate (size 0.8 x 70 x 150 mm, Palbond #3020) using a top coating composition (glossy) to a dry film thickness of 30 μm, and set at 25°C for 10 minutes. Then, the reference coated plate A was prepared by heating and drying (baking) at 150° C. for 20 minutes.
また、上塗塗料組成物（艶有）の代わりに、上塗塗料組成物（艶なし）を用い、上述の方法と同様の方法により、基準塗板Ｂを作製した。 In addition, a reference coated plate B was produced in the same manner as described above, using a top coat composition (non-glossy) instead of the top coat composition (glossy).
＜６．性能評価＞
下記の評価を行った。結果を表５～８に示す。
≪レオロジー評価≫
実施例１～１３及び比較例１～５のプライマー塗料について、レオメーター（ＴＡインスツルメンツ社製レオメーターＡＲＥＳ）を用い、液温を２５℃に調整した後、各々のプライマー塗料の２５℃におけるせん断速度０．１ｓ－１の粘度（Ｘ）とせん断速度１００ｓ－１の粘度（Ｙ）をそれぞれ測定し、その比（Ｘ／Ｙ）を算出した。粘度の単位はＰａ・ｓである。
<6. Performance evaluation>
The following evaluation was performed. The results are shown in Tables 5-8.
≪Rheology evaluation≫
For the primer paints of Examples 1 to 13 and Comparative Examples 1 to 5, after adjusting the liquid temperature to 25°C using a rheometer (Rheometer ARES manufactured by TA Instruments), the shear rate at 25°C of each primer paint was measured. The viscosity (X) at a shear rate of 0.1 s -1 and the viscosity (Y) at a shear rate of 100 s -1 were measured, and the ratio (X/Y) was calculated. The unit of viscosity is Pa·s.
＜評価結果＞
・Ｘ／Ｙが１０未満では、厚膜塗装（膜厚６０μｍ）を行った際、たれやすい状態であった。
・Ｘ／Ｙが１０～１５０では、問題なく、厚膜塗装（膜厚６０μｍ）を行うことができた。
・Ｘ／Ｙが１５０超では、静置している状態の塗料の流動性が低く、塗装がしにくい状態であった。
<Evaluation results>
- When X/Y was less than 10, it was easy to sag when thick film coating (film thickness 60 μm) was performed.
- When X/Y was 10 to 150, thick film coating (film thickness 60 μm) could be performed without any problem.
- When X/Y exceeds 150, the fluidity of the paint in a standing state is low, making it difficult to paint.
≪塗板の光沢値測定≫
実施例１～１３、比較例１～５の複層塗膜形成塗板、基準塗板Ａ、基準塗板Ｂについて、「ＶＧ７０００」（商品名、日本電色工業株式会社製)によって２０°光沢及び６０°光沢の値をそれぞれ測定した。
複層塗膜形成塗板の光沢値と、基準塗板の光沢値との差が１０以下（好ましくは７以下）であれば、プライマー塗膜の外観が良好であると判定した。
≪Measurement of gloss value of painted plate≫
The multilayer coating plates of Examples 1 to 13 and Comparative Examples 1 to 5, standard coating plate A, and standard coating plate B were coated with 20° gloss and 60° gloss using "VG7000" (trade name, manufactured by Nippon Denshoku Kogyo Co., Ltd.). The gloss value was measured for each.
If the difference between the gloss value of the coated plate on which the multilayer coating film was formed and the gloss value of the reference coated plate was 10 or less (preferably 7 or less), it was determined that the primer coating had a good appearance.
≪防食性の評価≫
実施例１～１３、比較例１～５の複層塗膜形成塗板をＪＩＳ Ｋ５６００ ７－１：１９９９に規定されている耐中性塩水噴霧性試験に供した。２４０時間保管し、取り出した後の剥離箇所の錆の状態を評価した。
○：カット線からの片側最大錆幅 ３．０ｍｍ以下。
△：カット線からの片側最大錆幅 ３．０～５．０ｍｍ。
×：カット線からの片側最大錆幅 ５．０ｍｍ以上。
≪Evaluation of corrosion resistance≫
The multilayer coated plates of Examples 1 to 13 and Comparative Examples 1 to 5 were subjected to a neutral salt spray resistance test specified in JIS K5600 7-1:1999. After being stored for 240 hours and taken out, the state of rust at the peeled portion was evaluated.
○: Maximum rust width on one side from the cut line is 3.0 mm or less.
△: Maximum rust width on one side from the cut line 3.0 to 5.0 mm.
×: Maximum rust width on one side from the cut line is 5.0 mm or more.
≪付着性の評価≫
ＪＩＳ Ｋ ５６００－５－６：１９９９に準じて各複層塗膜に１ｍｍ×１ｍｍのゴバン目１００個を作り、その面に粘着テープを貼着し、急激に剥した後に、残ったゴバン目塗膜の数を評価した。剥離個所が被塗物とプライマー塗膜の層間であるものは、基材付着性において残存しなかったとして評価した。剥離個所が複層塗膜の層間であるものは、基材付着性において残存したが層間付着性において残存しなかったとして評価した。
○：残存個数／全体個数＝１００個／１００個。
△：残存個数／全体個数＝９０個～９９個／１００個。
×：残存個数／全体個数＝８９個以下／１００個。
≪Evaluation of adhesion≫
In accordance with JIS K 5600-5-6:1999, 100 goblets of 1 mm x 1 mm are made on each multilayer coating film, adhesive tape is pasted on that surface, and after abruptly peeling off, the remaining goblin marks are removed. The number of membranes was evaluated. If the peeled off area was between the coated object and the primer coating, it was evaluated that no residue remained in terms of adhesion to the substrate. When the peeled area was between the layers of a multilayer coating film, it was evaluated as having remained in terms of substrate adhesion but not in terms of interlayer adhesion.
○: Remaining number/total number = 100 pieces/100 pieces.
△: Remaining number/total number = 90 to 99/100.
×: Remaining number/total number = 89 or less/100.
上記の通り本発明は、金属基材との優れた付着性を有し、厚膜化が可能である塗料組成物であることが判る。 As described above, it can be seen that the present invention is a coating composition that has excellent adhesion to metal substrates and can be formed into a thick film.
１ 基材
２ 本発明の塗料組成物による塗膜
３ 上塗塗膜
1
Claims (8)
A metal coated article comprising a metal base material and a coating layer comprising the coating composition according to any one of claims 1 to 6 adjacent to the base material.
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| JP2014047272A (en) * | 2012-08-31 | 2014-03-17 | Kansai Paint Co Ltd | Multicomponent type organic solvent based coating composition for undercoating and repair coating method using the same |
| WO2015012290A1 (en) * | 2013-07-25 | 2015-01-29 | 日本ファインコーティングス株式会社 | Coating composition, coating film, and coated steel plate |
| JP2018069185A (en) * | 2016-10-31 | 2018-05-10 | 日本ペイント・インダストリアルコ−ティングス株式会社 | Multilayer coating film forming method and coating material composition |
| JP2018123227A (en) * | 2017-01-31 | 2018-08-09 | 大日本塗料株式会社 | Two-component reactive curable type aqueous coating material composition for top coating, and multlayer film formation method and coated body using the same |
| JP2019085463A (en) * | 2017-11-02 | 2019-06-06 | 関西ペイント株式会社 | Multicomponent-based primer composition |
| JP2019172895A (en) * | 2018-03-29 | 2019-10-10 | 株式会社カネカ | Epoxy resin composition for paint |
| JP2020059824A (en) * | 2018-10-11 | 2020-04-16 | 日本ペイント株式会社 | Coating composition |
| JP2020180245A (en) * | 2019-04-26 | 2020-11-05 | Ａｇｃ株式会社 | Powder dispersion liquid, manufacturing method of laminate, laminate and manufacturing method of printed circuit board |
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