JP2014210856A - Coating composition and coating film forming method - Google Patents
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- JP2014210856A JP2014210856A JP2013087722A JP2013087722A JP2014210856A JP 2014210856 A JP2014210856 A JP 2014210856A JP 2013087722 A JP2013087722 A JP 2013087722A JP 2013087722 A JP2013087722 A JP 2013087722A JP 2014210856 A JP2014210856 A JP 2014210856A
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- 238000000576 coating method Methods 0.000 title claims abstract description 140
- 239000011248 coating agent Substances 0.000 title claims abstract description 139
- 239000008199 coating composition Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000049 pigment Substances 0.000 claims abstract description 81
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000001055 blue pigment Substances 0.000 claims abstract description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 20
- 150000004706 metal oxides Chemical class 0.000 claims description 20
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- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000003748 selenium group Chemical group *[Se]* 0.000 claims description 2
- 239000003973 paint Substances 0.000 description 39
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- 239000000758 substrate Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
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- 239000004640 Melamine resin Substances 0.000 description 10
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
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- -1 Al 2 0 3 Chemical compound 0.000 description 5
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- 239000000123 paper Substances 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 3
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
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- 238000004070 electrodeposition Methods 0.000 description 3
- 238000009503 electrostatic coating Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 0 C[C@]1(C(C(C=CC(C23)c(cc4)c56)=C2C2=CC=C3C5=CCC(C(N)N3*)c6c4C3=O)=N*1)C2=O Chemical compound C[C@]1(C(C(C=CC(C23)c(cc4)c56)=C2C2=CC=C3C5=CCC(C(N)N3*)c6c4C3=O)=N*1)C2=O 0.000 description 2
- 229910019589 Cr—Fe Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910012506 LiSi Inorganic materials 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical class N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 235000019239 indanthrene blue RS Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 235000009854 Cucurbita moschata Nutrition 0.000 description 1
- 240000001980 Cucurbita pepo Species 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910015243 LiMg Inorganic materials 0.000 description 1
- 229910018651 Mn—Ni Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XYOWBKPNPPIQLH-UHFFFAOYSA-N [Na].[Si].[Si].[Si].[Si] Chemical compound [Na].[Si].[Si].[Si].[Si] XYOWBKPNPPIQLH-UHFFFAOYSA-N 0.000 description 1
- WBDVBAABEUKEGA-UHFFFAOYSA-N [Si].[Si].[Si].[Si].[K] Chemical compound [Si].[Si].[Si].[Si].[K] WBDVBAABEUKEGA-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 125000005551 pyridylene group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- 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
- C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
-
- 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
- C09D5/32—Radiation-absorbing paints
-
- C09D7/12—
Landscapes
- Chemical & Material Sciences (AREA)
- Paints Or Removers (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
Abstract
Description
本発明は、漆黒感があって、遮熱性を有し、耐久性に優れ、白濁感がない黒系の色を呈する塗膜を形成可能な塗料組成物及び塗膜形成方法に関するものである。 The present invention relates to a coating composition and a coating film forming method capable of forming a coating film having a jet black color, heat insulation, excellent durability, and no black turbidity.
自動車等の工業製品において、明度が低い黒系の塗色の中でも、漆黒感に優れた高級感を有する塗色として人気が高い塗色となっている。明度が低い塗色を得るためには、カーボンブラック顔料を含有する塗料を塗装する方法が一般的である。しかし、カーボンブラック顔料を含む塗膜は、赤外線を吸収するため、塗装された被塗物の温度が上昇する問題点があった。そのため、カーボンブラック顔料を使用せずに低い明度の塗色を得るためにいくつかの方法が提案されてきた。 In industrial products such as automobiles, among black-based paint colors with low brightness, the paint color is very popular as a paint color having a high-class feeling with excellent jetness. In order to obtain a coating color with low lightness, a method of applying a paint containing a carbon black pigment is generally used. However, since the coating film containing the carbon black pigment absorbs infrared rays, there has been a problem that the temperature of the coated object is increased. Therefore, several methods have been proposed in order to obtain a low-lightness paint color without using a carbon black pigment.
特許文献１は、遮熱性機能と漆黒性を備えた塗膜形成方法に関するものであり、遮熱性塗料、黒色ベース塗料、黒色の染料を含有するカラークリヤ塗料、クリヤ塗料を重ね塗りした積層塗膜を形成する方法が記載されている。特許文献に開示された塗膜形成方法で得られた塗膜は、漆黒性を有し、遮熱性に優れるものであるが、カラークリヤ塗料を塗装する工程を含むため、工数が多くなることやカラークリヤ塗料に含まれる染料の耐候性が不足して、長期間の暴露によって変色が生じる場合があるである問題点があった。 Patent Document 1 relates to a method for forming a coating film having a heat-shielding function and jet blackness, and a heat-shielding paint, a black base paint, a color clear paint containing a black dye, and a multilayer paint film in which a clear paint is repeatedly applied. A method of forming is described. The coating film obtained by the coating film forming method disclosed in the patent document has jet blackness and excellent heat shielding properties, but includes a step of applying a color clear paint, and therefore the man-hour increases. There is a problem that the dye contained in the color clear paint lacks the weather resistance and discoloration may occur due to long-term exposure.
本発明の目的は、漆黒感があって、遮熱性を有し、耐久性に優れ、白濁感がない黒系の色を呈する塗膜を形成可能な塗料組成物及び塗膜形成方法を提供することである。 An object of the present invention is to provide a coating composition and a coating film forming method capable of forming a coating film having a blackish color, having a heat shielding property, excellent durability, and having no black turbidity. That is.
本発明は、
１．赤外線を反射及び／又は透過する黒色顔料及び透明性青色顔料を含む塗料組成物であって、塗装して得られる塗膜のＬ＊ａ＊ｂ＊表色系における明度Ｌ＊が０．１〜７の範囲内である塗料組成物、
２．赤外線を反射及び／又は透過する黒色顔料が、ペリレンブラック顔料であり、透明性青色顔料がアンスラキノン構造を有するスレン系顔料である１項に記載の塗料組成物、
３．さらに半透明の基材に金属酸化物を被覆した光干渉性顔料を含む１項又は２項に記載の塗料組成物、
４．光干渉性顔料のハイライトにおける干渉色のＬ＊Ｃ＊ｈ表色系における色相角度ｈが、１００〜３００の範囲内である３項に記載の塗料組成物、
５．被塗物に１〜４項のいずれか１項に記載の塗料組成物を塗装して得られた塗膜上に、さらにトップクリヤー塗料を塗装する塗膜形成方法
に関する。
The present invention
1. A coating composition containing a black pigment and a transparent blue pigment that reflects and / or transmits infrared rays, and a lightness L * in an L * a * b * color system of a coating film obtained by coating is 0.1 to A coating composition in the range of 7,
2. 2. The coating composition according to item 1, wherein the black pigment that reflects and / or transmits infrared rays is a perylene black pigment, and the transparent blue pigment is a selenium pigment having an anthraquinone structure,
3. 3. The coating composition according to item 1 or 2, further comprising a light interference pigment in which a metal oxide is coated on a translucent substrate.
4). The coating composition according to item 3, wherein the hue angle h in the L * C * h color system of the interference color in the highlight of the light interference pigment is in the range of 100 to 300,
5. It is related with the coating-film formation method which coats a top clear coating material further on the coating film obtained by apply | coating the coating composition of any one of 1-4 to a to-be-coated article.
本発明の塗料組成物は、漆黒感があって、遮熱性を有し、耐久性に優れ、白濁感がない黒系の色を呈する塗膜を形成可能なものであって、特に自動車外板、家電製品等の高級外観を求められている分野に有用なものである。 The coating composition of the present invention has a jet black feeling, has a heat shielding property, is excellent in durability, and can form a coating film exhibiting a black color without white turbidity. It is useful in fields that require a high-grade appearance such as home appliances.
本発明の塗料組成物は、赤外線を反射及び／又は透過する着色顔料を含む。本明細書において、赤外線を反射及び／又は透過する着色顔料とは、波長７８０ｎｍ〜２５００ｎｍの領域において、ＪＩＳ Ｋ５１０１ ４隠ぺい率試験紙法に記載された隠ぺい率試験紙に該着色顔料のみを着色材として含む塗料を塗装して得られた塗膜の白素地上のＪＩＳ Ｋ５６０２に定義された日射反射率が５０％以上又は黒素地上の日射反射率が１０％以上の顔料を意味する。 The coating composition of the present invention includes a color pigment that reflects and / or transmits infrared rays. In the present specification, a colored pigment that reflects and / or transmits infrared rays is a colorant in which only the colored pigment is applied to a cover rate test paper described in JIS K51014 Coverage Rate Test Paper Method in a wavelength range of 780 nm to 2500 nm. Means a pigment having a solar reflectance of 50% or more defined on JIS K5602 on a white substrate or a solar reflectance of 10% or more on a black substrate.
本明細書における具体的な日射反射率の測定方法を以下に説明する。水酸基含有アクリル樹脂（水酸基価１００、数平均分子量２００００）及びメラミン樹脂からなる樹脂成分１００固形分質量部あたり、該着色顔料を１５質量部配合して攪拌混合し、適当な溶媒を用いて希釈して固形分約２５％の有機溶剤型塗料を調製する。隠ぺい率試験紙を平らなガラス板の上に水平に固定し、その上にドクターブレードを使用して、硬化塗膜厚が３０μｍとなるように塗装し、室温約２０℃の実験室に１５分間放置し、その後に熱風乾燥機を使用して１４０℃で３０分間加熱して硬化せしめた塗膜の白素地部分及び黒素地部分の日射反射率を、積分球ＩＳＲ−３１００を搭載した分光光度計ＵＶ−３１００ＰＣ（共に島津製作所社製）を使用して入射角度を８°としたときの日射反射率として定義するものとする。 A specific method for measuring solar reflectance in the present specification will be described below. 15 parts by mass of the colored pigment is mixed per 100 parts by mass of a resin component comprising a hydroxyl group-containing acrylic resin (hydroxyl value 100, number average molecular weight 20000) and melamine resin, and the mixture is stirred and mixed, and diluted with an appropriate solvent. An organic solvent-type paint having a solid content of about 25% is prepared. Cover the opacity test paper horizontally on a flat glass plate, apply it on it using a doctor blade so that the cured coating thickness is 30 μm, and place it in a laboratory at room temperature of about 20 ° C. for 15 minutes. A spectrophotometer equipped with an integrating sphere ISR-3100 is used to measure the solar reflectance of the white base and black base portions of the coating film which has been allowed to stand and then heated and cured at 140 ° C. for 30 minutes using a hot air dryer. It is defined as the solar reflectance when UV-3100PC (both manufactured by Shimadzu Corporation) is used and the incident angle is 8 °.
赤外線を反射及び／又は透過する着色顔料としては具体的には、アゾ系顔料、アニリンブラック、ペリレンブラック等の有機顔料や複合酸化物顔料等を挙げることができる。 Specific examples of the colored pigment that reflects and / or transmits infrared rays include azo pigments, organic pigments such as aniline black and perylene black, composite oxide pigments, and the like.
ペリレン系の顔料としては、特開２００３−４１１４４号公報及び特関２００３−４１１４５号公報に開示のペリレンテトラカルボン酸の酸無水物、特開２００６−３２８２３８号に開示の２−メチル−２，４−ペンタンジオール及び硝酸を加熱反応して得られる黒色顔料、ペリレンテトラカルボン酸のジイミド誘導体、ペリレンジイミノジカルボン酸のジイミド誘導体を焼成処理して得られた黒色ペリレン系顔料や、特開２００７−５２２２９７号公報に開示の式１ａ又は１ｂで表される異性体の１種又は２つの異性体の混合物を含有する黒色顔料を使用することができる。 Examples of perylene pigments include perylene tetracarboxylic acid anhydrides disclosed in JP-A Nos. 2003-411144 and 2003-411145, and 2-methyl-2,4 disclosed in JP-A-2006-328238. A black pigment obtained by heating reaction of pentanediol and nitric acid, a diimide derivative of perylene tetracarboxylic acid, a black perylene pigment obtained by baking a diimide derivative of perylene diiminodicarboxylic acid, and JP2007-522297 Black pigments containing one or a mixture of two isomers of the isomers represented by formula 1a or 1b disclosed in US Pat.
（式中、Ｒ１、Ｒ２は互いに独立にフェニレン、ナフチレンまたはピリジレンであり、これらはそれぞれＣ１〜Ｃ１２−アルキル、Ｃ１〜Ｃ６−アルコキシ、ヒドロキシル、ニトロおよび／またはハロゲンにより一置換または多置換されていてもよく、Ｘはハロゲンであり、ｎは０〜４である）。 Wherein R 1 and R 2 are independently of each other phenylene, naphthylene or pyridylene, which are mono- or polysubstituted by C 1 -C 12 -alkyl, C 1 -C 6 -alkoxy, hydroxyl, nitro and / or halogen, respectively. X is halogen and n is 0-4).
無機顔料としては、Ｃｕ−Ｆｅ−Ｍｎ系、Ｃｕ−Ｃｒ系、Ｃｕ−Ｃｒ―Ｍｎ系、Ｃｕ−Ｃｒ−Ｍｎ−Ｎｉ系、Ｃｕ−Ｃｒ−Ｆｅ系、Ｃｏ−Ｃｒ−Ｆｅ系、Ｍｎ−Ｂｉ系、Ｍｎ−Ｙ系、等の複合酸化物顔料を挙げることができる。 Inorganic pigments include Cu-Fe-Mn, Cu-Cr, Cu-Cr-Mn, Cu-Cr-Mn-Ni, Cu-Cr-Fe, Co-Cr-Fe, and Mn-Bi. And composite oxide pigments such as Mn-Y and Mn-Y.
本発明において、赤外線を反射及び／又は透過する着色顔料は、塗装して得られる塗膜の色調によって、上記から１種類又は複数を選択して使用することができる。 In the present invention, the color pigment that reflects and / or transmits infrared rays can be used by selecting one or more kinds from the above depending on the color tone of the coating film obtained by coating.
本発明の塗料組成物における赤外線を反射及び／又は透過する着色顔料の量は、塗装して得られる塗膜の色調や、仕上がり性の点から、塗料組成物中の樹脂固形分１００質量部に対して、合計で０．０１〜２０質量部の範囲内が好ましく、より好ましくは０．１〜１８質量部の範囲内、特に好ましくは１〜１５質量部の範囲内である。 The amount of the color pigment that reflects and / or transmits infrared rays in the coating composition of the present invention is 100 parts by mass of the resin solid content in the coating composition from the viewpoint of the color tone and finish of the coating film obtained by coating. On the other hand, the total is preferably in the range of 0.01 to 20 parts by mass, more preferably in the range of 0.1 to 18 parts by mass, and particularly preferably in the range of 1 to 15 parts by mass.
本発明の塗料組成物は、塗装して得られる塗膜の白濁感を減じる点から、透明性青色顔料を使用する。透明性青色顔料とは、以下に示す透明性着色顔料の中で、青色の顔料を意味する。 The coating composition of the present invention uses a transparent blue pigment from the viewpoint of reducing the cloudiness of the coating film obtained by painting. The transparent blue pigment means a blue pigment among the transparent colored pigments shown below.
透明性着色顔料とは具体的には、塗料中の樹脂固形分１００質量部に基づいて顔料量が１０質量部となるように配合して塗料化し、硬化塗膜厚が３０μｍとなるように平滑なＰＴＦＥ板に塗装し、硬化、剥離した塗膜の曇り度（ヘイズ）が、１〜１０の範囲内であるものとして定義することができる。測定は、ＪＩＳ Ｋ７１３６：プラスチック−透明材料のヘーズの求め方に準じて測定することができ、本明細書においては、濁度計ＣＯＨ−３００Ａ（商品名、日本電色工業社製）にて測定した数値として定義するものとする。 Specifically, the transparent coloring pigment is blended so that the pigment amount becomes 10 parts by mass based on 100 parts by mass of the resin solid content in the paint, and is made smooth so that the cured coating thickness becomes 30 μm. It can be defined that the haze of the coating film coated, cured, and peeled on a PTFE plate is in the range of 1-10. The measurement can be performed according to JIS K7136: How to determine haze of plastic-transparent material. In this specification, it is measured with a turbidimeter COH-300A (trade name, manufactured by Nippon Denshoku Industries Co., Ltd.). Shall be defined as a numerical value.
また、本明細書において、青色の顔料とは、塗料中の樹脂固形分１００質量部に基づいて顔料量が２０質量部となるように配合して塗料化し、硬化塗膜厚が３０μｍとなるように予めＮ−７グレー色の中塗り塗膜が形成された塗板に塗装し、乾燥硬化した塗膜に４５度の角度から照射した光を、正反射光に対して４５度の角度で受光した分光反射率から計算して得られたＬ＊Ｃ＊ｈ表色系における色相角度ｈ２２５〜３１５の範囲内であるものとする。本発明の塗料組成物においては、塗装して得られる塗膜の漆黒性の点から。色相角度ｈが、２９０〜３１０のものを使用することが特に好ましい。 Further, in the present specification, the blue pigment is blended so that the pigment amount is 20 parts by mass based on 100 parts by mass of the resin solid content in the paint, so that the cured coating thickness is 30 μm. In addition, light applied to a coating plate on which an N-7 gray intermediate coating film had been previously formed and irradiated to the dried and cured coating film at an angle of 45 degrees was received at an angle of 45 degrees with respect to specular reflection light. It is assumed that the hue angle is in the range of h225 to 315 in the L * C * h color system obtained by calculation from the spectral reflectance. In the coating composition of this invention, from the point of jet blackness of the coating film obtained by painting. It is particularly preferable to use a hue angle h of 290 to 310.
本発明の塗料組成物における透明性青色顔料としては、銅フタロシアニン系の顔料や、アンスラキノン構造を有するスレン系顔料を使用することができる。特にスレン系顔料としては、次式で表されるインダンスロンブルー顔料（ＰｉｇｍｅｎｔＢｌｕｅ ６０）を使用することが、塗装して得られる塗膜の色調の点から好ましい。 As the transparent blue pigment in the coating composition of the present invention, a copper phthalocyanine pigment or a selenium pigment having an anthraquinone structure can be used. In particular, it is preferable to use an indanthrone blue pigment (Pigment Blue 60) represented by the following formula as a selenium pigment from the viewpoint of the color tone of a coating film obtained by painting.
本発明の塗料組成物における透明性青色顔料の含有量は、塗装して得られる塗膜の色調の点から、塗料組成物中の樹脂固形分１００質量部に対して、合計で０．０１〜５質量部の範囲内が好ましく、より好ましくは０．２〜４質量部の範囲内、特に好ましくは０．３〜３質量部の範囲内である。 The content of the transparent blue pigment in the coating composition of the present invention is 0.01 to a total of 100 parts by mass of the resin solid content in the coating composition from the viewpoint of the color tone of the coating film obtained by coating. It is preferably in the range of 5 parts by mass, more preferably in the range of 0.2 to 4 parts by mass, and particularly preferably in the range of 0.3 to 3 parts by mass.
本発明の塗料組成物は、さらに半透明の基材に金属酸化物を被覆した光干渉性顔料を含んでいてもよい。 The coating composition of the present invention may further contain a light interference pigment in which a translucent substrate is coated with a metal oxide.
光干渉性顔料とは、マイカ、人工マイカ、ガラス、酸化鉄、酸化アルミニウムや各種金属等鱗片状基材の表面に、二酸化チタンや酸化鉄等の基材とは屈折率が異なる金属酸化物が被覆された光輝性顔料である。具体的には、下記に示す金属酸化物被覆マイカ顔料、金属酸化物被覆アルミナフレーク顔料、金属酸化物被覆ガラスフレーク顔料、金属酸化物被覆シリカフレーク顔料等を挙げることができる。 Light interference pigments are mica, artificial mica, glass, iron oxide, aluminum oxide, metal oxides and other metal oxides that have a refractive index different from that of the substrate such as titanium dioxide and iron oxide. It is a bright pigment coated. Specific examples include metal oxide-coated mica pigments, metal oxide-coated alumina flake pigments, metal oxide-coated glass flake pigments, metal oxide-coated silica flake pigments described below.
金属酸化物被覆マイカ顔料は、天然マイカ又は人工マイカを基材とし、基材表面に金属酸化物が被覆した顔料である。天然マイカとは、鉱石のマイカ（雲母）を粉砕した鱗片状基材であり、人工マイカとは、ＳｉＯ２、ＭｇＯ、Ａｌ２０３、Ｋ２ＳｉＦ６、Ｎａ２ＳｉＦ６等の工業原料を加熱し、約１５００℃の高温で熔融し、冷却して結晶化させて合成したものであり、天然のマイカと比較した場合において、不純物が少なく、大きさや厚さが均一なものである。具体的には、フッ素金雲母（ＫＭｇ３ＡｌＳｉ３Ｏ１０Ｆ２）、カリウム四ケイ素雲母（ＫＭｇ２５ＡｌＳｉ４Ｏ１０Ｆ２）、ナトリウム四ケイ素雲母（ＮａＭｇ２５ＡｌＳｉ４Ｏ１０Ｆ２）、Ｎａテニオライト（ＮａＭｇ２ＬｉＳｉ４Ｏ１０Ｆ２）、ＬｉＮａテニオライト（ＬｉＭｇ２ＬｉＳｉ４Ｏ１０Ｆ２）等が知られている。被覆される金属酸化物としては、酸化チタンや酸化鉄を挙げることができる。被覆する厚さによって、干渉色を発現することができるものである。 The metal oxide-coated mica pigment is a pigment having natural mica or artificial mica as a base material and a metal oxide coated on the surface of the base material. Natural mica is a scaly substrate obtained by crushing ore mica (mica), and artificial mica is made of industrial raw materials such as SiO 2 , MgO, Al 2 0 3 , K 2 SiF 6 , Na 2 SiF 6, etc. It is synthesized by heating, melting at a high temperature of about 1500 ° C., cooling and crystallizing, and has less impurities and a uniform size and thickness when compared with natural mica. Specifically, fluorine phlogopite mica (KMg 3 AlSi 3 O 10 F 2 ), potassium tetrasilicon mica (KMg 25 AlSi 4 O 10 F 2 ), sodium tetrasilicon mica (NaMg 25 AlSi 4 O 10 F 2 ), Na Teniolite (NaMg 2 LiSi 4 O 10 F 2 ), LiNa teniolite (LiMg 2 LiSi 4 O 10 F 2 ) and the like are known. Examples of the metal oxide to be coated include titanium oxide and iron oxide. Depending on the coating thickness, an interference color can be developed.
金属酸化物被覆アルミナフレーク顔料は、アルミナフレークを基材とし、基材表面に金属酸化物が被覆した顔料である。アルミナフレークとは、鱗片状（薄片状）酸化アルミニウムを意味し、無色透明なものである。酸化アルミニウム単一成分である必要はなく、他の金属の酸化物を含有するものであってもよい。被覆される金属酸化物としては、酸化チタンや酸化鉄を挙げることができる。被覆する厚さによって、干渉色を発現することができるものである。 The metal oxide-coated alumina flake pigment is a pigment having alumina flake as a base material and a metal oxide coated on the surface of the base material. Alumina flake means scaly (flaky) aluminum oxide and is colorless and transparent. It does not need to be a single component of aluminum oxide, and may contain oxides of other metals. Examples of the metal oxide to be coated include titanium oxide and iron oxide. Depending on the coating thickness, an interference color can be developed.
金属酸化物被覆ガラスフレーク顔料とは、鱗片状のガラス基材に金属酸化物を被覆したものであって、基材表面が平滑なため、強い光の反射が生じて粒子感を発現する。被覆する金属酸化物としては、特に制限されるものではないが、酸化チタンや酸化鉄が知られている。 The metal oxide-coated glass flake pigment is a glass substrate coated with a metal oxide, and since the surface of the substrate is smooth, strong light reflection occurs and expresses a particle feeling. Although it does not restrict | limit especially as a metal oxide to coat | cover, Titanium oxide and iron oxide are known.
金属酸化物被覆シリカフレーク顔料は、表面が平滑で且つ厚さが均一な基材である鱗片状シリカを、基材とは屈折率が異なる金属酸化物で被覆したものである。 The metal oxide-coated silica flake pigment is obtained by coating scaly silica, which is a substrate having a smooth surface and a uniform thickness, with a metal oxide having a refractive index different from that of the substrate.
上記光干渉性顔料は、分散性や耐水性、耐薬品性、耐候性等を向上させるための表面処理が施されたものであってもよい。 The light interference pigment may be subjected to a surface treatment for improving dispersibility, water resistance, chemical resistance, weather resistance, and the like.
上記光干渉性顔料の大きさは、平均粒子径が５〜５０μｍの範囲内のものを使用することが、塗装された塗膜の仕上がり性や干渉色の発現の点から好ましく、より好ましくは粒子径が７〜３５μｍの範囲内のものである。厚さは０．０５〜７．０μｍの範囲内のものを使用することが好ましい。ここでいう粒子径は、マイクロトラック粒度分布測定装置 ＭＴ３３００（商品名、日機装社製）を用いてレーザー回折散乱法によって測定した体積基準粒度分布のメジアン径を意味する。厚さは、該光干渉性顔料を含む塗膜断面を顕微鏡にて観察して厚さを画像処理ソフトを使用して測定し、１００個以上の測定値の平均値として定義するものとする。 As the size of the light interference pigment, it is preferable to use a pigment having an average particle diameter in the range of 5 to 50 μm from the viewpoint of the finish of the coated film and the expression of interference color, more preferably particles. The diameter is in the range of 7 to 35 μm. It is preferable to use a thickness in the range of 0.05 to 7.0 μm. The particle diameter here means the median diameter of the volume-based particle size distribution measured by a laser diffraction scattering method using a Microtrac particle size distribution measuring device MT3300 (trade name, manufactured by Nikkiso Co., Ltd.). The thickness is defined as an average value of 100 or more measured values by observing a cross section of the coating film containing the light interference pigment with a microscope and measuring the thickness using image processing software.
光干渉性顔料を用いる場合、塗装して得られる塗膜のハイライト付近で生じる濁りを抑制でき、ハイライトに干渉色を発現させることで変化を持たせる点から、ハイライトにおける干渉色のＬ＊Ｃ＊ｈ表色系における色相角度ｈが、１００〜３００の範囲内のものを使用することが好ましく、より好ましくは１３０°〜２７０°の範囲内である。Ｌ＊Ｃ＊ｈ表色系とは、１９７６年に国際照明委員会で規定され、ＪＩＳ Ｚ ８７２９にも採用されているＬ＊ａ＊ｂ＊表色系をベースに考案された表色系であって、ｈは色相角度を表わし、色度図において赤方向の軸を０°として、反時計方向に移動した角度である。 When using a light interference pigment, the turbidity generated in the vicinity of the highlight of the coating film obtained by coating can be suppressed, and the interference color L in the highlight can be changed by expressing the interference color in the highlight. The hue angle h in the * C * h color system is preferably in the range of 100 to 300, more preferably in the range of 130 ° to 270 °. The L * C * h color system is a color system designed based on the L * a * b * color system specified by the International Commission on Illumination in 1976 and adopted in JIS Z 8729. H represents a hue angle, and is an angle moved counterclockwise with the red axis as 0 ° in the chromaticity diagram.
光干渉性顔料のハイライトにおける色相角度とは具体的には、塗料組成物中に、光干渉性顔料のみを着色材として含む塗料を塗装して得られた塗膜に４５°の角度から光を照射して、正反射光に対して１５°の方向において測色して得られた分光反射率に基づいて計算した数値を意味する。 Specifically, the hue angle in the highlight of the light-interfering pigment is the light from the angle of 45 ° to the coating film obtained by coating the paint composition containing only the light-interfering pigment as a colorant in the paint composition. Is a numerical value calculated based on the spectral reflectance obtained by measuring the color in the direction of 15 ° with respect to the regular reflected light.
本明細書において、光干渉性顔料のハイライトにおける干渉色とは、水酸基含有アクリル樹脂（水酸基価１００、数平均分子量２００００）及びメラミン樹脂からなる樹脂成分１００固形分質量部あたり、光干渉性顔料を１５質量部配合して攪拌混合し、溶媒を添加して塗装に適正な粘度に希釈して得られた固形分約２５％の有機溶剤型塗料を、予め黒色（Ｎ−２）の塗膜を形成した塗板上に硬化塗膜として１８μｍの膜厚となるようにエアスプレー塗装し、室温にて１５分間放置し、ついで、未硬化塗面にクリヤー塗料（ルーガベーククリヤー、関西ペイント製、商品名、アクリル樹脂・アミノ樹脂系、有機溶剤型）を硬化塗膜として、３５μｍとなるようにエアスプレー塗装し、さらに室温にて１５分間放置し、その後に熱風乾燥機を使用して１４０℃で３０分加熱して硬化乾燥せしめて得られた塗膜をＸ−Ｒｉｔｅ社製のＭＡ−６８ＩＩ（商品名、多角度分光光度計）を使用して、正反射光に対して１５°で受光した分光反射率に基づいて測定した測色値で定義するものとする。 In this specification, the interference color in the highlight of a light interference pigment is a light interference pigment per 100 parts by mass of a resin component consisting of a hydroxyl group-containing acrylic resin (hydroxyl value 100, number average molecular weight 20000) and a melamine resin. An organic solvent-type paint having a solid content of about 25% obtained by adding a solvent and diluting to an appropriate viscosity for coating is added in advance to a black (N-2) coating film. Air spray coating is applied to the coated plate with a thickness of 18 μm as a cured coating film, and it is allowed to stand at room temperature for 15 minutes, and then the clear coating is applied to the uncured coating surface (Lugabake Clear, manufactured by Kansai Paint Co., Ltd. Name, acrylic resin / amino resin type, organic solvent type) as a cured coating film, air sprayed to 35 μm, left at room temperature for 15 minutes, and then used a hot air dryer Then, the coating film obtained by heating at 140 ° C. for 30 minutes and curing and drying was applied to specularly reflected light using MA-68II (trade name, multi-angle spectrophotometer) manufactured by X-Rite. The colorimetric value measured based on the spectral reflectance received at 15 ° is defined.
本発明の塗料組成物において、光干渉性顔料を使用する場合、その含有量は、塗装して得られる塗膜の仕上がり性やの点から、塗料組成物中の樹脂固形分１００質量部に対して、合計で１〜２０質量部の範囲内が好ましく、より好ましくは２〜１８質量部の範囲内、特に好ましくは３〜１５質量部の範囲内である。 In the coating composition of the present invention, when a light interference pigment is used, its content is based on 100 parts by mass of the resin solid content in the coating composition from the viewpoint of the finish of the coating film obtained by coating. The total content is preferably in the range of 1 to 20 parts by mass, more preferably in the range of 2 to 18 parts by mass, and particularly preferably in the range of 3 to 15 parts by mass.
本発明の塗料組成物には、通常、ビヒクルとして、樹脂成分を含有することができる。樹脂成分としては、具体的には、水酸基などの架橋性官能基を有する、アクリル樹脂、ポリエステル樹脂、アルキド樹脂、ウレタン樹脂などの基体樹脂と、必要に応じてメラミン樹脂、尿素樹脂、ポリイソシアネ−ト化合物（ブロック体も含む）などの架橋剤とを併用したものが挙げられ、これらは有機溶剤及び／又は水などの溶媒に溶解または分散して使用される。 The coating composition of the present invention can usually contain a resin component as a vehicle. Specifically, the resin component includes a base resin such as an acrylic resin, a polyester resin, an alkyd resin, or a urethane resin having a crosslinkable functional group such as a hydroxyl group, and a melamine resin, a urea resin, or a polyisocyanate as necessary. A combination of a crosslinking agent such as a compound (including a block body) is used, and these are used by being dissolved or dispersed in a solvent such as an organic solvent and / or water.
さらに、本発明の塗料組成物には、必要に応じて、水あるいは有機溶剤等の溶媒、顔料分散剤、沈降防止剤、硬化触媒、消泡剤、酸化防止剤、紫外線吸収剤等の各種添加剤、体質顔料などを適宜配合することができる。 Furthermore, various additives such as a solvent such as water or an organic solvent, a pigment dispersant, an antisettling agent, a curing catalyst, an antifoaming agent, an antioxidant, and an ultraviolet absorber are added to the coating composition of the present invention as necessary. An agent, extender, etc. can be appropriately blended.
本発明の塗料組成物は、前述の成分を混合分散せしめることによって調製される。塗装時の固形分含有率を、塗料組成物に基づいて、１２〜５０質量％、好ましくは１５〜３０質量％に、また、２０℃における粘度を１５〜２０秒／フォ−ドカップ＃３に調整しておくことが好ましい。 The coating composition of the present invention is prepared by mixing and dispersing the aforementioned components. The solid content at the time of painting is adjusted to 12 to 50% by mass, preferably 15 to 30% by mass based on the coating composition, and the viscosity at 20 ° C. is adjusted to 15 to 20 seconds / ford cup # 3. It is preferable to keep it.
本発明の塗料組成物は、静電塗装、エアスプレー、エアレススプレーなどの方法で塗装することができ、その膜厚は硬化塗膜に基づいて１０〜４５μｍの範囲内とするのが、塗膜の平滑性の点から好ましい。本発明の塗料組成物の塗膜は通常、約７０〜約１５０℃の温度で架橋硬化させることができる。 The coating composition of the present invention can be applied by a method such as electrostatic coating, air spraying, airless spraying, and the film thickness is within the range of 10 to 45 μm based on the cured coating film. From the viewpoint of smoothness. The coating film of the coating composition of the present invention can usually be crosslinked and cured at a temperature of about 70 to about 150 ° C.
本明細書の塗料組成物は、塗装して得られる塗膜のＬ＊ａ＊ｂ＊表色系における明度Ｌ＊が０．１〜７の範囲内である。本明細書において塗料組成物を塗装して得られる塗膜の明度とは、予めグレー色（Ｎ−６）の塗膜を形成した塗板上に、該塗料組成物を塗装に適正な粘度に希釈して、硬化塗膜として１８μｍの膜厚となるようにエアスプレー塗装し、室温にて１５分間放置し、ついで、未硬化塗面にクリヤー塗料（ルーガベ−ククリヤー、関西ペイント製、商品名、アクリル樹脂・アミノ樹脂系、有機溶剤型）を硬化塗膜として、３５μｍとなるようにエアスプレー塗装し、さらに室温にて１５分間放置し、その後に熱風乾燥機を使用して１４０℃で３０分加熱して硬化乾燥せしめて得られた塗膜をＸ−Ｒｉｔｅ社製のＭＡ−６８ＩＩ（商品名、多角度分光光度計）を使用して、正反射光に対して２５°で受光した分光反射率に基づいて計算した数値で定義するものとする。 In the coating composition of the present specification, the lightness L * in the L * a * b * color system of the coating film obtained by painting is in the range of 0.1-7. In the present specification, the lightness of the coating film obtained by applying the coating composition refers to diluting the coating composition to a viscosity suitable for coating on a coating plate on which a gray (N-6) coating film has been formed in advance. Then, it was air spray coated to a film thickness of 18 μm as a cured coating film, left at room temperature for 15 minutes, and then a clear paint (Lugabe-Kuclear, Kansai Paint, trade name, acrylic on the uncured coating surface) (Resin / amino resin system, organic solvent type) as a cured coating, air sprayed to 35 μm, left at room temperature for 15 minutes, and then heated at 140 ° C. for 30 minutes using a hot air dryer Spectral reflectance of the coating film obtained by curing and drying using MA-68II (trade name, multi-angle spectrophotometer) manufactured by X-Rite Co., Ltd. at 25 ° with respect to specular reflection light. Defined by a numerical value calculated based on And things.
本発明の塗膜形成方法は、被塗物に上記塗料組成物を塗装して得られた塗膜上に、さらにトップクリヤー塗料を塗装する方法に関するものである。 The coating film forming method of the present invention relates to a method for further applying a top clear coating material on a coating film obtained by applying the coating composition to an object to be coated.
本発明の塗膜形成方法において、被塗物としては、鉄、亜鉛、アルミニウム等の金属やこれらを含む合金、及びこれらの金属によるメッキまたは蒸着が施された成型物、コンクリートやスレート等の建材ならびに、ガラス、プラスチックや発泡体などによる成型物等を挙げることができる。これら素材に応じて適宜、脱脂処理や表面処理して被塗物とすることができる。さらに、上記素材や各種処理を施された素材に下塗り塗膜や中塗り塗膜を形成させて被塗物とすることもでき、これらのものが特に好ましい。 In the coating film forming method of the present invention, the object to be coated includes metals such as iron, zinc, and aluminum, alloys containing these, and molded products plated or vapor-deposited with these metals, and building materials such as concrete and slate. In addition, a molded article made of glass, plastic, foam, or the like can be given. Depending on these materials, it can be appropriately subjected to degreasing treatment or surface treatment to obtain an article to be coated. Furthermore, it is also possible to form an undercoating film or an intermediate coating film on the above-mentioned material or a material that has been subjected to various treatments to form an article to be coated, and these are particularly preferable.
上記下塗り塗膜とは、素材表面を隠蔽したり、素材に防食性及び防錆性などを付与するために形成されるものであり、下塗り塗料を塗装し、乾燥、硬化することによって得ることができる。この下塗り塗料種としては特に限定されるものではなく、例えば、電着塗料、溶剤型プライマー等を挙げることができる。 The undercoat film is formed to conceal the surface of the material or impart anticorrosion and rustproofness to the material, and can be obtained by applying an undercoat paint, drying and curing. it can. The type of the undercoat paint is not particularly limited, and examples thereof include an electrodeposition paint and a solvent-type primer.
また、上記中塗り塗膜とは、下塗り塗膜を隠蔽したり、付着性や耐チッピング性などを付与するために形成されるものであり、乾燥硬化した下塗り塗膜又は未硬化の下塗り塗膜上に、中塗り塗料を塗装し、乾燥、硬化することによって得ることができる。中塗り塗料種は、特に限定されるものではなく、既知のものを使用でき、例えば、熱硬化性樹脂組成物及び着色顔料を必須成分とする有機溶剤系又は水系の中塗り塗料を好ましく使用できる。 The intermediate coating film is formed to conceal the undercoat film or impart adhesion, chipping resistance, etc., and is a dry-cured undercoat film or an uncured undercoat film. It can be obtained by applying an intermediate coating on top, drying and curing. The type of intermediate coating is not particularly limited, and known ones can be used. For example, an organic solvent-based or water-based intermediate coating containing a thermosetting resin composition and a color pigment as essential components can be preferably used. .
本発明の塗膜形成方法においては、適用される鋼板等の日射による温度上昇を低減する点から反射率が高い中塗り塗膜を形成可能な中塗塗料を適用することが好ましい。具体的には、明度が高い塗膜を形成可能なものであり、カーボンブラック顔料の含有率が塗料中の樹脂固形分１００質量部に対して０.５質量部以下の塗料が好ましい。また中塗塗料に白色酸化チタン顔料以外の着色顔料を配合する場合には、赤外線を反射及び／又は透過する着色顔料を用いることが好ましい。 In the method for forming a coating film of the present invention, it is preferable to apply an intermediate coating material capable of forming an intermediate coating film having a high reflectivity from the viewpoint of reducing temperature rise due to solar radiation of the applied steel sheet or the like. Specifically, it is possible to form a coating film with high brightness, and a coating material having a carbon black pigment content of 0.5 parts by mass or less with respect to 100 parts by mass of resin solid content in the coating is preferable. Moreover, when mix | blending coloring pigments other than a white titanium oxide pigment with an intermediate coating, it is preferable to use the coloring pigment which reflects and / or permeate | transmits infrared rays.
また、被塗物として、下塗り塗膜あるいは中塗り塗膜を形成されたものを用いる場合においては、下塗り塗膜あるいは中塗り塗膜を加熱し、架橋硬化後に本発明の塗料組成物を塗装することができる。あるいは、下塗り塗膜及び／又は中塗り塗膜が未硬化の状態で、塗装することもできる。 In the case where an undercoating film or an intermediate coating film is used as the object to be coated, the undercoating film or the intermediate coating film is heated, and the coating composition of the present invention is applied after crosslinking and curing. be able to. Alternatively, the undercoating film and / or the intermediate coating film can be applied in an uncured state.
本発明の塗膜形成方法においては、被塗物に上記塗料組成物を塗装して得られた塗膜上にさらにトップクリヤー塗料を１層もしくは２層以上塗装して、トップクリヤー塗膜を形成させる。 In the coating film forming method of the present invention, a top clear coating film is formed by further coating one or more top clear coatings on the coating film obtained by coating the coating composition with the coating composition. Let
本発明の塗膜形成方法におけるトップクリヤー塗料は、樹脂成分および溶剤を主成分とし、さらに必要に応じてその他の塗料用添加剤などを配合してなる無色もしくは有色の透明塗膜を形成する液状塗料である。 The top clear coating in the method for forming a coating film of the present invention is a liquid that forms a colorless or colored transparent coating film comprising a resin component and a solvent as main components, and further blending with other coating additives as required. It is a paint.
本発明方法におけるトップクリヤー塗料としては、従来公知のものを制限なく使用することができる。例えば、基体樹脂及び架橋剤を含有する液状もしくは粉体状の塗料組成物が適用できる。基体樹脂の例としては、水酸基、カルボキシル基、シラノ−ル基、エポキシ基などの架橋性官能基を含有する、アクリル樹脂、ポリエステル樹脂、アルキド樹脂、フッ素樹脂、ウレタン樹脂、シリコン含有樹脂などが挙げられる。架橋剤としては、前記基体樹脂の官能基と反応しうるメラミン樹脂、尿素樹脂、ポリイソシアネート化合物、ブロックポリイソシアネート化合物、エポキシ化合物又は樹脂、カルボキシル基含有化合物又は樹脂、酸無水物、アルコキシシラン基含有化合物又は樹脂等が挙げられる。また、必要に応じて、水や有機溶剤等の溶媒、硬化触媒、消泡剤、紫外線吸収剤、レオロジーコントロール剤、酸化防止剤、表面調整剤等の添加剤を適宜配合することができる。 As the top clear paint in the method of the present invention, a conventionally known one can be used without limitation. For example, a liquid or powdery coating composition containing a base resin and a crosslinking agent can be applied. Examples of the base resin include acrylic resin, polyester resin, alkyd resin, fluororesin, urethane resin, and silicon-containing resin containing a crosslinkable functional group such as a hydroxyl group, a carboxyl group, a silanol group, and an epoxy group. It is done. As a crosslinking agent, melamine resin, urea resin, polyisocyanate compound, block polyisocyanate compound, epoxy compound or resin, carboxyl group-containing compound or resin, acid anhydride, alkoxysilane group-containing, which can react with the functional group of the base resin Examples thereof include compounds or resins. Further, if necessary, additives such as a solvent such as water and an organic solvent, a curing catalyst, an antifoaming agent, an ultraviolet absorber, a rheology control agent, an antioxidant, and a surface conditioner can be appropriately blended.
上記トップクリヤー塗料には、透明性を損なわない範囲内において、着色顔料や染料を適時配合することができる。着色顔料や染料としては、インク用、塗料用として従来公知の顔料や染料を１種あるいは２種以上を組み合わせて配合することができる。その添加量は、適宜決定されて良いが、クリヤー塗膜中の樹脂固形分１００質量部に対して、３０質量部以下、好ましくは０.１〜１０質量部である。 In the top clear coating, a color pigment or a dye can be blended in a timely manner within a range not impairing transparency. As the color pigments and dyes, conventionally known pigments and dyes for inks and paints can be used alone or in combination of two or more. The amount of addition may be determined as appropriate, but is 30 parts by mass or less, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the clear coating film.
上記トップクリヤー塗料は、静電塗装、エアスプレー、エアレススプレーなどの方法で塗装することができ、その膜厚は硬化塗膜に基づいて５〜４０μｍの範囲内とするのが好ましい。トップクリヤー塗料の塗膜それ自体は約７０〜１５０℃の温度で架橋硬化させることができる。 The top clear coating can be applied by electrostatic coating, air spraying, airless spraying or the like, and the film thickness is preferably in the range of 5 to 40 μm based on the cured coating film. The top clear coating itself can be crosslinked and cured at a temperature of about 70-150 ° C.
本発明の塗膜形成方法においては、本発明の塗料組成物を塗装後、加熱し、乾燥硬化後に、その塗膜上にトップクリヤー塗料を塗装して加熱し、乾燥硬化させるいわゆる２Ｃ２Ｂ工程であっても良いが、該塗料組成物を塗装後にその未硬化の状態でトップクリヤー塗料を塗装して、その後に加熱し、これらを同時に硬化せしめるいわゆる２Ｃ１Ｂ工程で、複層塗膜を得ることもできる。 The coating film forming method of the present invention is a so-called 2C2B process in which the coating composition of the present invention is applied, heated, dried and cured, and then the top clear coating is applied on the coated film, heated, and dried and cured. However, a multi-layer coating film can also be obtained by the so-called 2C1B process in which the top clear paint is applied in an uncured state after the coating composition is applied, and then heated to cure them simultaneously. .
以下、実施例及び比較例を挙げて本発明をさらに具体的に説明する。ただし、本発明はこれらの実施例のみに限定されるものではない。なお、「部」及び「％」はいずれも質量基準によるものである。
次に、実施例を挙げて、本発明をより具体的に説明する。
（製造例１）水酸基含有アクリル樹脂の製造
温度計、サーモスタット、撹拌器、還流冷却器及び滴下装置を備えた反応容器にエチレングリコールモノエチルエーテルアセテート４０部を仕込み、撹拌混合し、１３５℃に昇温した。次いで下記のモノマー／重合開始剤の混合物を３時間かけて、同温度に保持した反応容器内に滴下し、滴下終了後１時間熟成を行なった。その後、エチレングリコールモノエチルエーテルアセテート１０部、２，２‘−アゾビス（２−メチルプロピオニトリル）０．６部からなる混合物を同温度に保持した１時間３０分かけて滴下し、さらに２時間熟成した。次にエチレングリコールモノエチルエーテルアセテートを減圧下で留去し、水酸基価５４ｍｇＫＯＨ／ｇ、数平均分子量５０，０００、樹脂固形分６５質量％の水酸基含有アクリル樹脂を得た。ここで数平均分子量とは、ゲル浸透クロマトグラフィー（ＧＰＣ）によって標準ポリスチレンの検量線を用いて測定したものを意味する。
（着色顔料の白素地上の日射反射率測定）
実施例及び比較例に使用する着色顔料各々の白素地上の日射反射率を以下の要領で測定し、結果を表１に示した。
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to only these examples. “Part” and “%” are based on mass.
Next, an Example is given and this invention is demonstrated more concretely.
(Production Example 1) Production of hydroxyl group-containing acrylic resin 40 parts of ethylene glycol monoethyl ether acetate was charged into a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and dropping device, stirred and mixed, and the temperature was raised to 135 ° C. Warm up. Subsequently, the following monomer / polymerization initiator mixture was dropped into a reaction vessel maintained at the same temperature over 3 hours, and aging was performed for 1 hour after the completion of the dropping. Thereafter, a mixture of 10 parts of ethylene glycol monoethyl ether acetate and 0.6 parts of 2,2′-azobis (2-methylpropionitrile) was added dropwise over 1 hour 30 minutes maintained at the same temperature, and further 2 hours. Aged. Next, ethylene glycol monoethyl ether acetate was distilled off under reduced pressure to obtain a hydroxyl group-containing acrylic resin having a hydroxyl value of 54 mgKOH / g, a number average molecular weight of 50,000 and a resin solid content of 65% by mass. Here, the number average molecular weight means that measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.
(Measurement of solar reflectance of colored pigments on white ground)
The solar reflectance on the white substrate of each of the color pigments used in Examples and Comparative Examples was measured in the following manner, and the results are shown in Table 1.
水酸基含有アクリル樹脂（水酸基価１００、数平均分子量２００００）及びメラミン樹脂からなる樹脂成分１００固形分質量部あたり、該着色顔料を１５質量部配合して攪拌混合し、塗装に適正な粘度に希釈して固形分約２５％の有機溶剤型塗料を調製する。ＪＩＳ Ｋ５１０１ ４隠ぺい率試験紙法に記載された隠ぺい率試験紙を平らなガラス板の上に水平に固定し、その上にドクターブレードを使用して、硬化塗膜厚が３０μｍとなるように塗装し、室温約２０℃の実験室に１５分間放置し、その後に熱風乾燥機を使用して１４０℃で３０分間加熱して硬化せしめた塗膜の白素地部分の日射反射率として、積分球ＩＳＲ−３１００を搭載した分光光度計ＵＶ−３１００ＰＣ（共に島津製作所社製）を使用して入射角度を８°としたときのＪＩＳ Ｋ５６０２に定義された反射率を測定した。
（着色顔料の色相角度ｈ測定）
実施例及び比較例に使用する着色顔料の色相角度ｈを以下の要領で測定し、結果を表１に示した。
15 parts by mass of the coloring pigment is mixed per 100 parts by mass of a resin component comprising a hydroxyl group-containing acrylic resin (hydroxyl value 100, number average molecular weight 20000) and melamine resin, and the mixture is stirred and mixed. An organic solvent-type paint having a solid content of about 25% is prepared. Cover the opacity test paper described in JIS K5101 4 Coverage Test Paper Method horizontally on a flat glass plate, and apply a doctor blade on it so that the cured coating thickness is 30 μm. Integrating sphere ISR as the solar reflectance of the white base portion of the coating film, which was allowed to stand in a laboratory at room temperature of about 20 ° C. for 15 minutes and then heated and cured at 140 ° C. for 30 minutes using a hot air dryer. Using a spectrophotometer UV-3100PC (both manufactured by Shimadzu Corporation) equipped with -3100, the reflectance defined in JIS K5602 was measured when the incident angle was 8 °.
(Measurement of hue angle h of colored pigment)
The hue angle h of the color pigment used in Examples and Comparative Examples was measured as follows, and the results are shown in Table 1.
製造例１で得られた水酸基含有アクリル樹脂７５部、ユーバン２８−６０（商品名、ブチルエーテル化メラミン樹脂、三井化学社製）２５部からなる樹脂成分１００部（固形分）あたり、測定に供する顔料を１５部配合して攪拌混合し、溶剤を添加して塗装に適正な粘度に希釈して得られた塗料を、予め黒色（Ｎ−２）の塗膜を形成した塗板上に硬化塗膜として１８μｍの膜厚となるようにエアスプレー塗装し、室温にて１５分間放置し、ついで、未硬化塗面にクリヤー塗料（ルーガベーククリヤー、関西ペイント製、商品名、アクリル樹脂・アミノ樹脂系、有機溶剤型）を硬化塗膜として、３５μｍとなるようにエアスプレー塗装し、さらに室温にて１５分間放置し、その後に熱風乾燥機を使用して１４０℃で３０分加熱して硬化乾燥せしめて得られた塗膜をＸ−Ｒｉｔｅ社製のＭＡ−６８ＩＩ（商品名、多角度分光光度計）を使用して、正反射光に対して４５°で受光した分光反射率に基づいて測定したＬ＊Ｃ＊ｈ表色系における色相角度ｈで示した。
（着色顔料のヘイズ測定）
製造例１で得られた水酸基含有アクリル樹脂７５部、ユーバン２８−６０（商品名、ブチルエーテル化メラミン樹脂、三井化学社製）２５部からなる樹脂成分１００部（固形分）あたり、測定に供する顔料を１５部配合して攪拌混合し、溶剤を添加して塗装に適正な粘度に希釈して得られた塗料を、予め溶剤脱脂されたＯＨＰシートに硬化塗膜として１８μｍの膜厚となるようにエアスプレー塗装し、室温にて１５分間放置し、その後に熱風乾燥機を使用して１４０℃で３０分加熱して硬化乾燥せしめて得られた塗膜のヘイズ（曇り度）を、「ＣＯＨ−３００Ａ」（商品名、日本電色工業社製の色差・濁度測定機）使用して測定し、結果を表１に示した。
（鱗片状光輝性顔料の干渉色測定）
実施例及び比較例に使用する鱗片状光輝性顔料の干渉色を以下の要領で測定し、結果を表１に示した。
Pigment to be used for measurement per 100 parts (solid content) of resin component consisting of 75 parts of hydroxyl group-containing acrylic resin obtained in Production Example 1 and 25 parts of Uban 28-60 (trade name, butyl etherified melamine resin, manufactured by Mitsui Chemicals) 15 parts is mixed with stirring, and a paint obtained by adding a solvent and diluting to an appropriate viscosity for coating is applied as a cured coating film on a coating plate on which a black (N-2) coating film has been formed in advance. Air spray coating to a film thickness of 18 μm and let stand at room temperature for 15 minutes, then clear paint (Lugabake Clear, manufactured by Kansai Paint, trade name, acrylic resin / amino resin system, organic Solvent type) as a cured coating film, air-sprayed to a thickness of 35 μm, left at room temperature for 15 minutes, and then heated and dried at 140 ° C. for 30 minutes using a hot air dryer. Using the MA-68II (trade name, multi-angle spectrophotometer) manufactured by X-Rite, the coating film obtained was measured based on the spectral reflectance received at 45 ° with respect to the regular reflection light. The hue angle is indicated by h in the L * C * h color system.
(Measurement of color pigment haze)
Pigment to be used for measurement per 100 parts (solid content) of resin component consisting of 75 parts of hydroxyl group-containing acrylic resin obtained in Production Example 1 and 25 parts of Uban 28-60 (trade name, butyl etherified melamine resin, manufactured by Mitsui Chemicals) 15 parts is mixed and stirred and mixed, and the paint obtained by adding a solvent and diluting to an appropriate viscosity for coating is applied to a solvent-degreased OHP sheet in advance so as to have a film thickness of 18 μm as a cured coating film. The haze (cloudiness) of the coating film obtained by air spray coating and leaving at room temperature for 15 minutes, followed by heating and drying at 140 ° C. for 30 minutes using a hot air drier is expressed as “COH−”. 300A "(trade name, a color difference / turbidity measuring machine manufactured by Nippon Denshoku Industries Co., Ltd.).
(Measurement of interference color of scaly glitter pigment)
The interference color of the scaly glitter pigment used in Examples and Comparative Examples was measured in the following manner, and the results are shown in Table 1.
製造例１で得られた水酸基含有アクリル樹脂７５部、ユーバン２８−６０（商品名、ブチルエーテル化メラミン樹脂、三井化学社製）２５部からなる樹脂成分１００部（固形分）あたり、鱗片状光輝性顔料を１５部配合して攪拌混合し、溶剤を添加して塗装に適正な粘度に希釈して得られた塗料を、予め黒色（Ｎ−２）の塗膜を形成した塗板上に硬化塗膜として１８μｍの膜厚となるようにエアスプレー塗装し、室温にて１５分間放置し、ついで、未硬化塗面にクリヤー塗料（ルーガベーククリヤー、関西ペイント製、商品名、アクリル樹脂・アミノ樹脂系、有機溶剤型）を硬化塗膜として、３５μｍとなるようにエアスプレー塗装し、さらに室温にて１５分間放置し、その後に熱風乾燥機を使用して１４０℃で３０分加熱して硬化乾燥せしめて得られた塗膜をＸ−Ｒｉｔｅ社製のＭＡ−６８ＩＩ（商品名、多角度分光光度計）を使用して、正反射光に対して１５°で受光した分光反射率に基づいて測定したＬ＊Ｃ＊ｈ表色系における色相角度ｈで示した。 Scale-like glitter per 100 parts (solid content) of a resin component comprising 75 parts of a hydroxyl group-containing acrylic resin obtained in Production Example 1 and 25 parts of Uban 28-60 (trade name, butyl etherified melamine resin, manufactured by Mitsui Chemicals, Inc.) 15 parts of the pigment is mixed and stirred and mixed, and the paint obtained by adding a solvent and diluting to an appropriate viscosity for coating is cured on the coating plate on which a black (N-2) coating film has been formed in advance. Air spray coating to a film thickness of 18 μm, and let stand at room temperature for 15 minutes, then clear paint (Lugabake Clear, manufactured by Kansai Paint, trade name, acrylic resin / amino resin system, Organic solvent type) as a cured coating film, air sprayed to 35 μm, left at room temperature for 15 minutes, and then heated and dried at 140 ° C. for 30 minutes using a hot air dryer. The coating film obtained was measured using MA-68II (trade name, multi-angle spectrophotometer) manufactured by X-Rite, based on the spectral reflectance received at 15 ° with respect to the regular reflection light. The hue angle is indicated by h in the L * C * h color system.
実施例１〜７、比較例１〜９
製造例１で得られた水酸基含有アクリル樹脂７５部、ユーバン２８−６０（商品名、ブチルエーテル化メラミン樹脂、三井化学社製）２５部からなる樹脂成分１００部（固形分）あたり、着色顔料等の色材を表２に示す比率で配合して攪拌混合し、塗装に適正な粘度に希釈して、固形分約２５％の有機溶剤型塗料を調製し、実施例１〜７及び比較例１、２に使用する塗料組成物を作成した。
（試験板の作成）
基材の調整
脱脂及びりん酸亜鉛処理した鋼板（ＪＩＳＧ３１４１、大きさ１５０×７５×０．８ｍｍ）にカチオン電着塗料「エレクロンＧＴ−１０ＨＴ」（商品名：関西ペイント株式会社製、エポキシ樹脂ポリアミン系カチオン樹脂に硬化剤としてブロックポリイソシアネ−ト化合物を使用したもの）を硬化塗膜に基づいて膜厚２０μｍになるように電着塗装し、１７０℃で２０分加熱して架橋硬化させて電着塗膜を得た。
Examples 1-7, Comparative Examples 1-9
For 100 parts of resin component (solid content) consisting of 75 parts of the hydroxyl group-containing acrylic resin obtained in Production Example 1 and 25 parts of Uban 28-60 (trade name, butyl etherified melamine resin, manufactured by Mitsui Chemicals, Inc.) Color materials were blended in the ratios shown in Table 2, stirred and mixed, diluted to an appropriate viscosity for coating, and an organic solvent-type paint having a solid content of about 25% was prepared. Examples 1 to 7 and Comparative Example 1 The coating composition used for 2 was prepared.
(Creation of test plate)
Cationic electrodeposition paint “ELECRON GT-10HT” (trade name: manufactured by Kansai Paint Co., Ltd., epoxy resin polyamine system) on steel plate (JISG3141, size 150 × 75 × 0.8 mm) subjected to adjustment degreasing and zinc phosphate treatment of the base material A cationic resin using a block polyisocyanate compound as a curing agent) is electrodeposited so as to have a film thickness of 20 μm based on the cured coating film, and heated at 170 ° C. for 20 minutes to be crosslinked and cured to be electrically charged. A coated film was obtained.
得られた電着塗面に、中塗塗料「ルーガベーク中塗り白Ｎ−４．５」（商品名：関西ペイント株式会社製、ポリエステル樹脂・メラミン樹脂系、有機溶剤型）をエアスプレーにて硬化塗膜に基づいて膜厚３０μｍになるように塗装し、１４０℃で３０分加熱して架橋硬化させて、中塗塗膜を形成した塗板を基材とした。
塗装
（１）で調整した基材に実施例及び比較例で調製した塗料組成物をそれぞれＲＥＡガンを用いて、ブ−ス温度２５℃、湿度７５％の条件で、硬化塗膜として、２５μｍとなるように塗装し、室温にて１５分間放置し、ついで、これらの未硬化塗面にクリヤー塗料（ルーガベーククリヤー、関西ペイント製、商品名、アクリル樹脂・アミノ樹脂系、有機溶剤型）をミニベル型回転式静電塗装機を用いて、ブース温度２５℃、湿度７５％の条件で硬化塗膜として、２５〜３５μｍとなるように塗装した。塗装後、室温にて１５分間放置した後に、熱風循環式乾燥炉内を使用して、１４０℃で３０分間加熱し、複層塗膜を同時に乾燥硬化せしめて試験板を得た。
（３）明度の測定
（２）で作成した塗板の明度を測定した。測定は、Ｘ−Ｒｉｔｅ社製のＭＡ−６８ＩＩ（商品名、多角度分光光度計）を使用して行ない、正反射光に対して２５°で受光した分光反射率に基づいて計算したＬ＊ａ＊ｂ＊表色系における明度Ｌ＊、ａ＊及びｂ＊を表２に示した。なお、ａ＊及びｂ＊は各々の数値（絶対値）が小さいほど彩度が低く、漆黒感が高いこと及び白濁感がないことを示す。
On the obtained electrodeposition coating surface, an intermediate coating “Lugabake Intermediate Coating White N-4.5” (trade name: manufactured by Kansai Paint Co., Ltd., polyester resin / melamine resin type, organic solvent type) is cured by air spray. Based on the film, it was coated to a film thickness of 30 μm, heated at 140 ° C. for 30 minutes to be crosslinked and cured, and a coated plate on which an intermediate coating film was formed was used as a base material.
The coating composition prepared in Examples and Comparative Examples was applied to the base material prepared in the coating (1), using a REA gun, respectively, at 25 ° C. and 75% humidity as a cured coating film at 25 μm. Then, leave it at room temperature for 15 minutes, and then apply a clear paint (Lugabake Clear, manufactured by Kansai Paint, trade name, acrylic resin / amino resin type, organic solvent type) to these uncured surfaces. Using a mold rotary electrostatic coating machine, the coating film was coated to a thickness of 25 to 35 μm as a cured coating film under conditions of a booth temperature of 25 ° C. and a humidity of 75%. After coating, the sample was allowed to stand at room temperature for 15 minutes, and then heated in a hot-air circulating drying oven at 140 ° C. for 30 minutes to simultaneously dry and cure the multilayer coating film to obtain a test plate.
(3) Measurement of brightness The brightness of the coated plate prepared in (2) was measured. The measurement was performed using MA-68II (trade name, multi-angle spectrophotometer) manufactured by X-Rite, and L * a calculated based on the spectral reflectance received at 25 ° with respect to the regular reflection light. The lightness L *, a * and b * in the * b * color system are shown in Table 2. In addition, a * and b * show that saturation is so low that each numerical value (absolute value) is small, a jet black feeling is high, and there is no cloudiness.
（４）目視による意匠性評価
作成した試験板を人工太陽灯（セリック社製、色温度６５００Ｋ）で照明し、試験板の照明に対する角度を変えて観察して、意匠性を以下に示す基準で評価した。評価は、色彩開発に３年以上従事するデザイナー２名と技術者３名の計５名が行ない、平均点を採用した。
作成した塗板を、人工太陽灯（セリック社製、色温度６５００Ｋ）で照明し、試験板の照明に対する角度を変えて観察して、ハイライト（正反射光近傍）やシェード（スカシ）の意匠性を目視にて評価し、結果を表２に示した。
４：漆黒感が高く、濁りがない。
３：漆黒感があり、濁りがない。
２：漆黒感が低く、濁りが少しある。
１：漆黒感がなく、濁りがある。
（５）遮熱性評価
１辺が４０ｃｍのダンボール箱上部に７０ｍｍ四方の正方形の穴をあけたものを、室温約２０℃の実験室に３０分間静置した。意匠性評価に使用した試験板を、７５ｍｍ×７５ｍｍの大きさに切断して、裏に熱電対のセンサーをセロハンテープで固定した塗板を、
前記穴をふさぐように静置した。４０ｃｍの距離から、ＨＡＬＯＧＥＮ ＬＩＧＨＴ（ＬＰＬ１５００）を照射し、１５分後に塗板裏面の温度を測定し、結果を表１に示した。
(4) Evaluation of design properties by visual observation The prepared test plate is illuminated with an artificial sun lamp (manufactured by Celic, color temperature 6500K), and the angle of the test plate with respect to the illumination is changed and observed. evaluated. The evaluation was conducted by a total of 5 designers and 3 engineers engaged in color development for 3 years or more, and the average score was adopted.
Illuminate the created coated plate with an artificial sunlamp (Ceric, color temperature 6500K), and observe it by changing the angle with respect to the illumination of the test plate, and design characteristics of highlights (near specular reflection light) and shades (squash) Were visually evaluated and the results are shown in Table 2.
4: High jetness and no turbidity.
3: There is a jet black feeling and no turbidity.
2: Jetness is low and there is a little turbidity.
1: There is no jet black feeling and there is turbidity.
(5) Evaluation of heat shielding properties A 70 mm square hole formed in the upper part of a corrugated cardboard box having a side of 40 cm was left in a laboratory at room temperature of about 20 ° C. for 30 minutes. A test plate used for design evaluation was cut into a size of 75 mm × 75 mm, and a coated plate with a thermocouple sensor fixed on the back with a cellophane tape,
It left still so that the said hole might be plugged up. HALOGEN LIGHT (LPL1500) was irradiated from a distance of 40 cm, and the temperature on the back surface of the coated plate was measured after 15 minutes. The results are shown in Table 1.
本発明の塗料組成物及び塗膜形成方法は、各種工業製品、特に自動車車体の外板に適用できる。 The coating composition and the method for forming a coating film of the present invention can be applied to various industrial products, in particular, the outer plate of an automobile body.
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| WO2021224232A1 (en) | 2020-05-04 | 2021-11-11 | Basf Coatings Gmbh | Coating systems with increased jetness of black and improved color |
| KR20220058022A (en) * | 2020-10-30 | 2022-05-09 | 국방과학연구소 | The infrared low emissivity paint material compositions containing organic solvent based conducting polymer and silver nano wire complex and manufacturing method thereof |
| WO2023031222A1 (en) | 2021-08-30 | 2023-03-09 | Basf Coatings Gmbh | Dark primer coatings with high lidar reflectivity |
| US11808833B2 (en) | 2016-10-28 | 2023-11-07 | Ppg Industries Ohio, Inc. | Coatings for increasing near-infrared detection distances |
| US11809933B2 (en) | 2018-11-13 | 2023-11-07 | Ppg Industries Ohio, Inc. | Method of detecting a concealed pattern |
| US12001034B2 (en) | 2019-01-07 | 2024-06-04 | Ppg Industries Ohio, Inc. | Near infrared control coating, articles formed therefrom, and methods of making the same |
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| JP2016137693A (en) * | 2015-01-29 | 2016-08-04 | マツダ株式会社 | Decorative laminate |
| US11808833B2 (en) | 2016-10-28 | 2023-11-07 | Ppg Industries Ohio, Inc. | Coatings for increasing near-infrared detection distances |
| US11977154B2 (en) | 2016-10-28 | 2024-05-07 | Ppg Industries Ohio, Inc. | Coatings for increasing near-infrared detection distances |
| US11809933B2 (en) | 2018-11-13 | 2023-11-07 | Ppg Industries Ohio, Inc. | Method of detecting a concealed pattern |
| US12001034B2 (en) | 2019-01-07 | 2024-06-04 | Ppg Industries Ohio, Inc. | Near infrared control coating, articles formed therefrom, and methods of making the same |
| KR20210009957A (en) * | 2019-07-18 | 2021-01-27 | 국방과학연구소 | High weatherability infrared low emissivity paint material compositions |
| KR102269267B1 (en) * | 2019-07-18 | 2021-06-25 | 국방과학연구소 | High weatherability infrared low emissivity paint material compositions |
| WO2021224232A1 (en) | 2020-05-04 | 2021-11-11 | Basf Coatings Gmbh | Coating systems with increased jetness of black and improved color |
| KR20220058022A (en) * | 2020-10-30 | 2022-05-09 | 국방과학연구소 | The infrared low emissivity paint material compositions containing organic solvent based conducting polymer and silver nano wire complex and manufacturing method thereof |
| KR102499541B1 (en) | 2020-10-30 | 2023-02-14 | 국방과학연구소 | The infrared low emissivity paint material compositions containing organic solvent based conducting polymer and silver nano wire complex and manufacturing method thereof |
| WO2023031222A1 (en) | 2021-08-30 | 2023-03-09 | Basf Coatings Gmbh | Dark primer coatings with high lidar reflectivity |
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