JPH1133485A - Two-tone finish coating method - Google Patents
Two-tone finish coating methodInfo
- Publication number
- JPH1133485A JPH1133485A JP19541297A JP19541297A JPH1133485A JP H1133485 A JPH1133485 A JP H1133485A JP 19541297 A JP19541297 A JP 19541297A JP 19541297 A JP19541297 A JP 19541297A JP H1133485 A JPH1133485 A JP H1133485A
- Authority
- JP
- Japan
- Prior art keywords
- coating
- paint
- resin
- coated
- colored
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 139
- 239000005002 finish coating Substances 0.000 title claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 103
- 229920005989 resin Polymers 0.000 claims abstract description 48
- 239000011347 resin Substances 0.000 claims abstract description 48
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000004070 electrodeposition Methods 0.000 claims abstract description 10
- 235000019646 color tone Nutrition 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 4
- 239000003973 paint Substances 0.000 claims description 117
- 238000004040 coloring Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 12
- 239000003960 organic solvent Substances 0.000 description 19
- 239000000049 pigment Substances 0.000 description 18
- 229920000877 Melamine resin Polymers 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- 239000005056 polyisocyanate Substances 0.000 description 16
- 229920001228 polyisocyanate Polymers 0.000 description 16
- 239000004640 Melamine resin Substances 0.000 description 13
- 229920001225 polyester resin Polymers 0.000 description 13
- 239000004645 polyester resin Substances 0.000 description 13
- 239000010410 layer Substances 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 239000007921 spray Substances 0.000 description 11
- 239000003431 cross linking reagent Substances 0.000 description 9
- 239000003822 epoxy resin Substances 0.000 description 9
- 239000000945 filler Substances 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- 238000005507 spraying Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920000178 Acrylic resin Polymers 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 238000009503 electrostatic coating Methods 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 description 4
- -1 acid amide compounds Chemical class 0.000 description 4
- 229920000180 alkyd Polymers 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000008442 polyphenolic compounds Chemical class 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZPANWZBSGMDWON-UHFFFAOYSA-N 1-[(2-hydroxynaphthalen-1-yl)methyl]naphthalen-2-ol Chemical compound C1=CC=C2C(CC3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 ZPANWZBSGMDWON-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229920003270 Cymel® Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- VYGUBTIWNBFFMQ-UHFFFAOYSA-N [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical group [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O VYGUBTIWNBFFMQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、自動車車体外板部
を2トーン仕上げする新規な塗装方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel coating method for two-tone finishing of an outer panel of an automobile body.
【0002】[0002]
【従来の技術】自動車車体外板部の上部と下部を色調が
異なる2種の着色塗料を用いて塗り分けて、2トーンに
仕上げる塗装方法はすでに公知である。例えば、電着塗
料を塗装し、加熱硬化してなる自動車車体の外板におい
て、その下部は主として走行中に跳ね上げられた砂利や
小石等があたり易く、それによって塗膜が部分的に剥離
することがあるので、それを防止するために、その部分
に塩化ビニル樹脂系耐チッピング性塗料をあらかじめ塗
装してから、外板部の全面に中塗塗料を塗装し、さらに
外板部の下部に第一の着色塗料を塗装した後に、加熱し
て、これらの塩化ビニル樹脂系塗料、中塗塗料及び第一
の着色塗料からなる3層塗膜を同時に硬化せしめ、つい
で下部をマスキングしてから、上部に第二の着色塗料及
びクリヤ塗料を塗装した後に、加熱して、これらの第二
の着色塗料及びクリヤ塗料からなる2層塗膜を同時に硬
化せしめて、2トーンに仕上げることが行われている。2. Description of the Related Art There are already known coating methods in which an upper part and a lower part of an outer panel portion of an automobile body are separately applied using two kinds of coloring paints having different color tones to achieve a two-tone finish. For example, in the outer plate of an automobile body that is coated with an electrodeposition paint and then cured by heating, the lower portion thereof is easily hit by gravel or pebbles that are mainly jumped up during traveling, thereby partially peeling off the coating film. In order to prevent this, apply a vinyl chloride resin-based chipping-resistant paint in advance to that part, apply an intermediate coating paint on the entire surface of the outer plate, and further apply a After applying one colored paint, it is heated to simultaneously cure the three-layer paint film composed of the vinyl chloride resin paint, the intermediate paint and the first colored paint, and then the lower part is masked and then the upper part is coated. After the second colored paint and the clear paint are applied, heating is performed to simultaneously cure the two-layer coating film composed of the second colored paint and the clear paint, thereby completing the two-tone paint.
【0003】しかしながら、自動車車体の下部部分にお
いて、塩化ビニル樹脂系塗料、中塗塗料及び第一の着色
塗料をそれぞれ未硬化の状態で塗り重ねた後、加熱して
これらの3層塗膜を同時に硬化せしめると、該着色塗料
塗膜の光沢が低下し、しかも該塗膜中に含まれるメタリ
ック顔料の配向性が乱れて、仕上り外観が劣り、さら
に、該塩化ビニル樹脂系塗料の使用のため塗面の平滑性
が十分でなく、仕上り外観が低下する等の欠陥を有して
いる。However, in the lower part of the vehicle body, a vinyl chloride resin-based coating, an intermediate coating and a first colored coating are each applied in an uncured state, and then heated to simultaneously cure these three-layer coatings. If it does, the gloss of the colored paint film is reduced, and the orientation of the metallic pigment contained in the paint film is disturbed, and the finished appearance is poor. Has insufficient defects, such as insufficient finished smoothness.
【0004】[0004]
【発明が解決しようとする課題】本発明の目的は、自動
車車体外板部に仕上り外観や耐チッピング性等のすぐれ
た塗膜を形成できる2トーン仕上げ塗装方法を提供する
ことにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a two-tone finish coating method capable of forming a coating film having excellent finish appearance and chipping resistance on an outer panel of an automobile body.
【0005】[0005]
【課題を解決するための手段】本発明者は、自動車車体
外板部の上部と下部を塗り分けて2トーンに仕上げる場
合における上記従来の塗装方法における種々の欠陥を解
消するべく鋭意研究した。その結果、該塗装方法におい
て、特に、下部に塩化ビニル樹脂系耐チッピング性塗料
を塗装してから、さらに該塗面にポリウレタン樹脂系耐
チッピング性塗料を塗装することにより、第一の着色塗
料塗膜の光沢の低下、メタリック顔料を含む場合におけ
るその配向性の乱れ、塩化ビニル系樹脂塗料による平滑
性の低下等を、いずれも効果的に防止でき、自動車車体
外板部に仕上り外観や耐チッピング性等のすぐれた塗膜
を形成でき、上記目的が達成できることを見出し、これ
に基づいて、本発明を完成するに至った。SUMMARY OF THE INVENTION The inventor of the present invention has made intensive studies to solve the various deficiencies in the above-mentioned conventional coating method in the case where the upper and lower portions of the outer body portion of an automobile body are separately painted to achieve two tones. As a result, in the coating method, in particular, by coating a vinyl chloride resin-based chipping-resistant paint on the lower part and then further applying a polyurethane resin-based chipping-resistant paint on the coated surface, the first colored paint coating is applied. It can effectively prevent the decrease in the gloss of the film, the disorder of its orientation when a metallic pigment is contained, and the decrease in the smoothness due to the vinyl chloride resin paint. It has been found that a coating film having excellent properties and the like can be formed and the above object can be achieved, and based on this, the present invention has been completed.
【0006】すなわち、本発明は、色調が異なる2種の
着色塗料を用いて2トーンに仕上げる自動車車体外板部
の塗装方法であって、該外板部の全面に電着塗料を塗装
し、加熱硬化した後、砂利や小石があたり易い部分に、
塩化ビニル樹脂系耐チッピング性塗料及びポリウレタン
樹脂系耐チッピング性塗料を塗装し、ついで該外板部の
全面に中塗塗料を塗装してから、該外板部の下部に第一
の着色塗料を塗装し、加熱してこれらの4層塗膜を同時
に硬化させた後、該外板部の上部のみに第二の着色塗料
及びクリヤ塗料を塗装し、加熱して上部のこれら2層塗
膜を同時に硬化させることを特徴とする2トーン仕上げ
塗装方法に係る。That is, the present invention relates to a method for coating an outer panel of an automobile body in which a two-tone finish is obtained by using two kinds of colored coatings having different color tones. After heat hardening, gravel and pebbles are easy to hit,
A vinyl chloride resin-based chipping-resistant paint and a polyurethane resin-based chipping-resistant paint are applied, then an intermediate coating is applied over the entire outer panel, and then a first colored coating is applied to a lower portion of the outer panel. After heating and simultaneously curing these four-layer coatings, a second colored paint and a clear paint are applied only to the upper part of the outer panel, and heated to simultaneously apply these two-layer coatings on the upper part. The present invention relates to a two-tone finish coating method characterized by curing.
【0007】[0007]
【発明の実施の形態】以下に、本発明塗装方法につい
て、さらに具体的に説明する。BEST MODE FOR CARRYING OUT THE INVENTION The coating method of the present invention will be described below more specifically.
【0008】本発明塗装法における被塗物は、自動車車
体であり、特に金属製の自動車車体が好適である。本発
明における自動車車体外板部は、車体の外側に位置して
いる部分であり、例えばロッカー、ドア、フェンダー、
エプロン、ボンネットフード、ルーフ、トランクリッド
等が挙げられる。また、走行中に跳ね上げられた砂利や
小石等が当たりやすい車体の部分は、例えばロッカー、
ドアの下部、フェンダーの下部、エプロン等があげられ
る。また、車体外板部の下部は、目的とする2トーン仕
上げの意匠性を考慮して決定されるが、例えばロッカ
ー、ドアの下部、フェンダーの下部、エプロン等が挙げ
られる。更に、車体外板部の上部は、下部より上の部分
であり、例えばドアの上部、フェンダーの上部、ボンネ
ットフード等が挙げられる。The object to be coated in the coating method of the present invention is an automobile body, and a metal automobile body is particularly suitable. The vehicle body outer panel portion in the present invention is a portion located outside the vehicle body, for example, a locker, a door, a fender,
Aprons, hoods, roofs, trunk lids, and the like. In addition, the part of the car body that is easily hit by gravel, pebbles, etc.
The lower part of a door, the lower part of a fender, an apron, etc. are mentioned. Further, the lower portion of the vehicle body outer panel portion is determined in consideration of a design property of a desired two-tone finish, and examples thereof include a locker, a lower portion of a door, a lower portion of a fender, and an apron. Further, the upper portion of the vehicle body outer plate portion is a portion above the lower portion, and includes, for example, an upper portion of a door, an upper portion of a fender, a hood, and the like.
【0009】上記被塗物に塗装する電着塗料は、防錆
性、付着性等を向上させるためのものであり、カチオン
電着塗料が好適である。The electrodeposition paint applied to the object to be coated is for improving rust prevention, adhesion and the like, and a cationic electrodeposition paint is preferred.
【0010】カチオン電着塗料としては、それ自体既知
のものを使用することができ、架橋性官能基を有するア
クリル樹脂又はエポキシ樹脂にアミノ基を導入したカチ
オン性高分子化合物があげられ、これを有機酸又は無機
酸等で中和することによって水溶化又は水分散化せし
め、さらに架橋剤としてのブロックポリイソシアネート
等を配合したものが好適である。[0010] As the cationic electrodeposition paint, those known per se can be used, and examples thereof include cationic polymer compounds in which an amino group is introduced into an acrylic resin or an epoxy resin having a crosslinkable functional group. It is preferable to use water or water dispersed by neutralization with an organic acid or an inorganic acid or the like, and further blend a blocked polyisocyanate or the like as a crosslinking agent.
【0011】これらのカチオン電着塗料の浴中に、自動
車車体(被塗物)を陰極として浸漬し、電着塗装が行わ
れ、膜厚は硬化塗膜を基準にして通常10〜50μmの
範囲が好ましく、140〜220℃で、10〜40分加
熱して塗膜を架橋硬化することができる。An automobile body (object to be coated) is immersed in a bath of these cationic electrodeposition paints as a cathode to perform electrodeposition coating, and the film thickness is usually in the range of 10 to 50 μm based on the cured coating film. Preferably, the coating film can be crosslinked and cured by heating at 140 to 220 ° C for 10 to 40 minutes.
【0012】本発明塗装法において、塩化ビニル樹脂系
耐チッピング性塗料及びポリウレタン樹脂系耐チッピン
グ性塗料の塗装部位は、電着塗装し加熱硬化させてなる
自動車車体の外板部であって、走行中に跳ね上げられた
砂利や小石等が当たりやすい車体の部分である。また、
これらの耐チッピング性塗料の塗装部位と後記する第一
の着色塗料を塗装する部位とは一致させる必要はなく、
耐チッピング性塗料は上記のように小石等が当たりやす
い部分に塗装し、一方、第一着色塗料の塗装部位は目的
とする2トーン仕上げの意匠性を考慮して決定される。In the coating method of the present invention, the coating portion of the vinyl chloride resin-based chipping-resistant paint and the polyurethane resin-based chipping-resistant paint is an outer plate portion of an automobile body obtained by electrodeposition coating and heating and curing. It is the part of the car body that is easily hit by gravel, pebbles, etc., which have been flipped up inside. Also,
It is not necessary to match the parts to be coated with these chipping-resistant paints and the parts to be coated with the first colored paint described below,
As described above, the chipping-resistant paint is applied to a portion where pebbles or the like are likely to hit, while the application site of the first colored paint is determined in consideration of the design property of the intended two-tone finish.
【0013】塩化ビニル樹脂系塗料は、主として走行中
に跳ね上げられた小石等があたって塗膜が部分的に剥離
するのを防止するために塗装する塗料であり、耐チッピ
ング性にすぐれた塗膜を形成することが好ましく、具体
的には、塩化ビニル樹脂、充填剤及び可塑剤を含有し、
さらに必要に応じて有機溶剤、安定剤等を配合してなる
熱可塑性の液状塗料があげられる。The vinyl chloride resin paint is a paint which is mainly applied to prevent the paint film from being partially peeled off by pebbles or the like which are flipped up during traveling and has excellent chipping resistance. It is preferable to form a film, specifically, containing a vinyl chloride resin, a filler and a plasticizer,
Further, there may be mentioned a thermoplastic liquid paint containing an organic solvent, a stabilizer and the like as required.
【0014】塩化ビニル樹脂は、塩化ビニルを主成分と
し、さらに必要に応じて酢酸ビニル、マレイン酸、(メ
タ)アクリル酸、アクリルエステル類、水酸基含有モノ
マー、カルボキシル基含有モノマー、スチレン、アクリ
ロニトリル等を(共)重合してなる樹脂である。The vinyl chloride resin contains vinyl chloride as a main component, and further contains vinyl acetate, maleic acid, (meth) acrylic acid, acrylic esters, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, styrene, acrylonitrile, etc., if necessary. (Co) polymerized resin.
【0015】充填剤としては、例えばチタン白、硫酸バ
リウム、炭酸バリウム、炭酸カルシウム、クレー、シリ
カ、ホワイトカーボン、タルク、炭酸マグネシウム、カ
ーボンブラック、マイカ、亜鉛華、カドミウムレッド等
の着色顔料、体質顔料等があげられる。Examples of the filler include coloring pigments such as titanium white, barium sulfate, barium carbonate, calcium carbonate, clay, silica, white carbon, talc, magnesium carbonate, carbon black, mica, zinc white, and cadmium red; And the like.
【0016】可塑剤としては、例えばフタル酸ジブチ
ル、フタル酸ジイソブチル、フタル酸ジオクチル、リン
酸トリクレジル、リン酸トリフェニル、セバシン酸ジブ
チル等があげられる。Examples of the plasticizer include dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, tricresyl phosphate, triphenyl phosphate, dibutyl sebacate and the like.
【0017】有機溶剤としては炭化水素系溶剤、エステ
ル系溶剤、エーテル系溶剤、アルコール系溶剤、ケトン
系溶剤等があげられる。Examples of the organic solvent include hydrocarbon solvents, ester solvents, ether solvents, alcohol solvents, ketone solvents and the like.
【0018】塩化ビニル樹脂系塗料におけるこれらの成
分の構成比率は目的に応じて任意に選べるが、例えば、
塩化ビニル樹脂100重量部あたり、充填剤は5〜15
0重量部、可塑剤は5〜100重量部が好ましい。The composition ratio of these components in the vinyl chloride resin paint can be arbitrarily selected according to the purpose.
5 to 15 fillers per 100 parts by weight of vinyl chloride resin
0 parts by weight and the plasticizer are preferably 5 to 100 parts by weight.
【0019】塩化ビニル樹脂系塗料は、電着塗装し加熱
硬化させてなる自動車の外板部の砂利や小石等が当たり
やすい部分の電着塗面に、硬化塗膜に基いて約200〜
400μmの膜厚で、エアレススプレー、エアスプレー
等の塗装法により塗装することが好ましい。The vinyl chloride resin-based paint is applied to the electrodeposited surface of the outer plate portion of the automobile, which is electrodeposited and heat-cured, where the gravel, pebbles, etc. are likely to hit, and the cured coating film is applied in an amount of about 200 to
It is preferable to apply a coating having a thickness of 400 μm by a coating method such as airless spraying or air spraying.
【0020】本発明塗装法は、未硬化の塩化ビニル樹脂
系塗料の塗膜面にポリウレタン樹脂系塗料を塗装する。In the coating method of the present invention, a polyurethane resin-based paint is applied to the coating surface of an uncured vinyl chloride-based paint.
【0021】このポリウレタン樹脂系塗料は、ウレタン
変性ポリエステル樹脂、ブロックポリイソシアネート化
合物、メラミン樹脂、エポキシ樹脂及び充填剤を含有す
る液状熱硬化性塗料である。The polyurethane resin paint is a liquid thermosetting paint containing a urethane-modified polyester resin, a block polyisocyanate compound, a melamine resin, an epoxy resin and a filler.
【0022】ウレタン変性ポリエステル樹脂は、ポリエ
ステルポリオールとポリイソシアネート化合物とを水酸
基過剰のモル比でウレタン化反応させることにより得ら
れる樹脂で、1分子中に2個以上の水酸基を有してい
る。The urethane-modified polyester resin is a resin obtained by subjecting a polyester polyol and a polyisocyanate compound to a urethanization reaction in an excess molar ratio of hydroxyl groups, and has two or more hydroxyl groups in one molecule.
【0023】ブロックポリイソシアネート化合物は、ポ
リイソシアネート化合物が有する遊離のイソシアネート
基のすべて又は殆どをブロック剤で封鎖してなる化合物
であって、解離温度以上に加熱すると遊離イソシアネー
ト基が再生して架橋剤として機能する。The blocked polyisocyanate compound is a compound obtained by blocking all or most of the free isocyanate groups of the polyisocyanate compound with a blocking agent. When heated to a temperature higher than the dissociation temperature, the free isocyanate groups are regenerated to form a crosslinking agent. Function as
【0024】ポリイソシアネート化合物は、1分子中に
2個以上のイソシアネート基を有する化合物であり、芳
香族ジイソシアネート、脂肪族ジイソシアネート、脂環
族ジイソシアネート、ビユーレットタイプ付加物、イソ
シアヌル環タイプ付加物等があげられる。また、ブロッ
ク剤としては、フェノール類、オキシム類、ラクタム
類、活性メチレン系化合物、アルコール類、酸アミド系
化合物、イミド系化合物、アミン系化合物、イミダゾー
ル系化合物、尿素系化合物、カルバミン酸系化合物、イ
ミン系化合物、メルカプタン類等を使用することができ
る。The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule, and includes aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, violet type adduct, isocyanuric ring type adduct and the like. can give. Examples of the blocking agent include phenols, oximes, lactams, active methylene compounds, alcohols, acid amide compounds, imide compounds, amine compounds, imidazole compounds, urea compounds, carbamic acid compounds, Imine compounds, mercaptans and the like can be used.
【0025】ポリエステルオールとポリイソシアネート
化合物とのウレタン化反応は通常の方法で行うことがで
き、かくして得られるウレタン変性ポリエステル樹脂の
数平均分子量は1,500〜350,000、水酸基価
は50〜200mgKOH/gの範囲内が適している。The urethane-forming reaction between the polyesterol and the polyisocyanate compound can be carried out by a usual method. The urethane-modified polyester resin thus obtained has a number average molecular weight of 1,500 to 350,000 and a hydroxyl value of 50 to 200 mg KOH. / G is suitable.
【0026】メラミン樹脂としては、メチロール化メラ
ミン、及びこのメチロール化メラミンに炭素数1〜6の
1価アルコールを反応させてなるエーテル化メラミン樹
脂が使用できる。As the melamine resin, a methylolated melamine and an etherified melamine resin obtained by reacting the methylolated melamine with a monohydric alcohol having 1 to 6 carbon atoms can be used.
【0027】エポキシ樹脂としては、1分子中に2個以
上のエポキシ基を有する樹脂であり、例えば、ポリフェ
ノールをエピクロリヒドリンと反応させることにより得
られるポリフェノールのグリシジルエーテルが好適であ
る。ここで使用できるポリフェノールとして、例えば、
ビス(4−ヒドロキシフェニル)−2,2−プロパン、
ビス(4−ヒドロキシフェニル)−1,1−エタン、ビ
ス(4−ヒドロキシフェニル)−1,1−イソブタン、
ビス(2−ヒドロキシナフチル)−メタン、ビス(2,
4−ジヒドロキシフェニル)−メタン、テトラ(4−ヒ
ドロキシフェニル)−1,1,2,2−エタン等があげ
られる。このうち、ビスフェノールタイプが好ましい。The epoxy resin is a resin having two or more epoxy groups in one molecule. For example, glycidyl ether of polyphenol obtained by reacting polyphenol with epichlorohydrin is preferable. As polyphenols that can be used here, for example,
Bis (4-hydroxyphenyl) -2,2-propane,
Bis (4-hydroxyphenyl) -1,1-ethane, bis (4-hydroxyphenyl) -1,1-isobutane,
Bis (2-hydroxynaphthyl) -methane, bis (2
4-dihydroxyphenyl) -methane, tetra (4-hydroxyphenyl) -1,1,2,2-ethane and the like. Of these, the bisphenol type is preferred.
【0028】充填剤としては、前記塩化ビニル樹脂系塗
料で充填剤として例示したものから選ばれる1種又は2
種以上が使用できる。As the filler, one or two selected from those exemplified as the filler in the above-mentioned vinyl chloride resin-based paint are used.
More than species can be used.
【0029】本発明塗装法で使用するポリウレタン樹脂
系塗料において、ウレタン変性ポリエステル樹脂は耐チ
ッピング性を向上せしめ、又ブロックポリイソシアネー
ト化合物及びメラミン樹脂は硬化剤として作用し、この
両成分を併用することにより塗膜の可撓性と硬化性との
バランスがすぐれ、140℃以下の温度でも十分に架橋
硬化し、耐チッピング性も良好である。また、エポキシ
樹脂は被塗面との付着性を向上させ、耐チッピング性も
向上させる。In the polyurethane resin paint used in the coating method of the present invention, a urethane-modified polyester resin improves chipping resistance, and a block polyisocyanate compound and a melamine resin act as a curing agent. As a result, the balance between the flexibility and the curability of the coating film is excellent, and the film is sufficiently cross-linked and cured even at a temperature of 140 ° C. or less, and has good chipping resistance. Further, the epoxy resin improves the adhesion to the surface to be coated and also improves the chipping resistance.
【0030】ポリウレタン樹脂系塗料におけるこれらの
成分の構成比率は、これらの合計固形分重量を100重
量%として、ウレタン変性ポリエステル樹脂は50〜7
0重量%、ブロックポリイソシアネート化合物は5〜2
0重量%、メラミン樹脂は10〜30重量%、エポキシ
樹脂は1〜10重量%の範囲内が特に好ましい。充填剤
は、ウレタン変性ポリエステル樹脂、ブロックポリイソ
シアネート化合物、メラミン樹脂及びエポキシ樹脂の合
計固形分100重量部あたり、200〜300重量部の
範囲内であることが適しており、この範囲であると、耐
チッピング性、塗膜の耐タレ性、ワキ発生防止性等が向
上するので好ましい。The composition ratio of these components in the polyurethane resin-based coating is such that the total solid content of these components is 100% by weight, and the urethane-modified polyester resin is 50 to 7%.
0 wt%, blocked polyisocyanate compound is 5-2
It is particularly preferable that the content is 0% by weight, the melamine resin content is 10 to 30% by weight, and the epoxy resin content is 1 to 10% by weight. The filler is preferably in the range of 200 to 300 parts by weight per 100 parts by weight of the total solid content of the urethane-modified polyester resin, the block polyisocyanate compound, the melamine resin and the epoxy resin, and within this range, It is preferable because the chipping resistance, the sagging resistance of the coating film, and the prevention of the occurrence of wrinkles are improved.
【0031】本発明塗装法で使用するポリウレタン樹脂
系塗料は上記の成分を有機溶剤に混合分散せしめて得ら
れる。有機溶剤としては、前記塩化ビニル樹脂系塗料で
有機溶剤として例示したものから選ばれる1種又は2種
以上が使用できる。The polyurethane resin paint used in the coating method of the present invention can be obtained by mixing and dispersing the above components in an organic solvent. As the organic solvent, one or more kinds selected from those exemplified as the organic solvent in the vinyl chloride resin-based paint can be used.
【0032】ポリウレタン樹脂系塗料は、前記の塩化ビ
ニル樹脂系塗料の未硬化塗膜面に、硬化塗膜に基いて5
0〜100μmの膜厚で、静電塗装、エアレススプレ
ー、エアスプレー等の塗装法により塗装することが好ま
しい。The polyurethane resin-based paint is coated on the uncured coating surface of the above-mentioned vinyl chloride resin-based paint by 5% based on the cured coating film.
It is preferable to apply a coating having a thickness of 0 to 100 μm by a coating method such as electrostatic coating, airless spray, or air spray.
【0033】本発明塗装法は、耐チッピング性の塩化ビ
ニル樹脂系塗料及びポリウレタン樹脂系塗料をウエット
オンウエットで所定部分に塗装したのち、ついで外板部
の全面に中塗塗料を塗装する。In the coating method of the present invention, a predetermined portion of a chipping-resistant vinyl chloride resin coating and a polyurethane resin coating is applied by wet-on-wet, and then an intermediate coating is applied to the entire outer plate.
【0034】中塗塗料は、基体樹脂、架橋剤及び顔料を
配合してなる液状熱硬化性塗料であり、基体樹脂として
は、例えば水酸基含有ポリエステル樹脂、水酸基含有ア
ルキド樹脂等が好ましく、架橋剤としては、例えばメラ
ミン樹脂、尿素樹脂等のようなアミノ樹脂等が好まし
い。顔料としては、通常の塗料用顔料が使用でき、前記
塩化ビニル樹脂系塗料で充填剤として例示したものから
選ばれる1種又は2種以上が使用できる。The intermediate coating is a liquid thermosetting coating comprising a base resin, a cross-linking agent and a pigment. As the base resin, for example, a hydroxyl group-containing polyester resin, a hydroxyl group-containing alkyd resin and the like are preferable. For example, amino resins such as melamine resins and urea resins are preferred. As the pigment, an ordinary pigment for paints can be used, and one or more kinds selected from those exemplified as the filler in the vinyl chloride resin-based paint can be used.
【0035】中塗塗料は、基体樹脂、架橋剤、顔料等を
有機溶剤に混合し分散せしめることによって得られる。
有機溶剤としては、前記塩化ビニル樹脂系塗料で有機溶
剤として例示したものから選ばれる1種又は2種以上が
使用できる。The intermediate coating is obtained by mixing and dispersing a base resin, a crosslinking agent, a pigment and the like in an organic solvent.
As the organic solvent, one or more kinds selected from those exemplified as the organic solvent in the vinyl chloride resin-based paint can be used.
【0036】中塗塗料は、ポリウレタン樹脂系塗料の未
硬化塗膜面を含む外板部の全面に、硬化塗膜に基いて1
0〜20μmの膜厚で、静電塗装、エアレススプレー、
エアスプレー等の塗装法により塗装することが好まし
い。The intermediate coating is applied on the entire surface of the outer plate including the uncured coating surface of the polyurethane resin coating based on the cured coating film.
With a film thickness of 0 to 20 μm, electrostatic coating, airless spray,
It is preferable to apply the coating by a coating method such as air spray.
【0037】本発明塗装法は、このように塩化ビニル樹
脂系塗料、ポリウレタン樹脂系塗料、中塗塗料を塗装
し、硬化させずに、未硬化の中塗塗面の一部に第一の着
色塗料を塗装する。According to the coating method of the present invention, a vinyl chloride resin paint, a polyurethane resin paint, and an intermediate paint are applied as described above, and the first colored paint is applied to a part of the uncured intermediate coat without curing. Paint.
【0038】第一の着色塗料の塗装部位は、耐チッピン
グ性の塩化ビニル樹脂系塗料やポリウレタン樹脂系塗料
を塗装する部位と一致させる必要はなく、目的とする2
トーン仕上げの意匠性を考慮して決定されるが、通常、
車体外板部の下部に塗装することが好ましく、耐チッピ
ング性塗料の塗装部位と重複することが多い。The application site of the first colored coating does not need to coincide with the site where the chipping-resistant vinyl chloride resin-based coating or polyurethane resin-based coating is applied.
It is determined in consideration of the design of the tone finish, but usually,
It is preferable to apply the paint to the lower part of the vehicle body outer panel portion, and often overlaps the application portion of the chipping-resistant paint.
【0039】第一の着色塗料は、第二の着色塗料と異な
る色調を有しており、基体樹脂、架橋剤、着色顔料等を
含有し、これらを有機溶剤に混合せしめることにより得
られる熱硬化性塗料である。有機溶剤としては、前記塩
化ビニル樹脂系塗料で有機溶剤として例示したものから
選ばれる1種又は2種以上が使用できる。The first colored paint has a color tone different from that of the second colored paint, and contains a base resin, a cross-linking agent, a color pigment, and the like, and is obtained by mixing these with an organic solvent to obtain a thermosetting resin. Paint. As the organic solvent, one or more kinds selected from those exemplified as the organic solvent in the vinyl chloride resin-based paint can be used.
【0040】基体樹脂としては、例えば、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、ウレタン樹脂等が挙げられ、架橋剤としては、例え
ばメラミン樹脂、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等が挙げられ
る。また、着色顔料としてはフレーク状のアルミニウ
ム、ステンレス、雲母粉等等のメタリック顔料が好適に
使用できる。Examples of the base resin include an acrylic resin having a crosslinkable functional group, a polyester resin, an alkyd resin, and a urethane resin. Examples of the crosslinker include a melamine resin, a urea resin, a polyisocyanate compound, and a block polyisocyanate. Examples include isocyanate compounds. Further, as the coloring pigment, flake-like metallic pigments such as aluminum, stainless steel, and mica powder can be suitably used.
【0041】第一着色塗料は、上記の基体樹脂、架橋
剤、着色顔料を、必要に応じて塗料用添加剤等と共に、
有機溶剤に混合せしめることにより得られ、これを、車
体外板部の下部に、硬化塗膜に基いて一般に10〜50
μmの膜厚に、静電塗装、エアレススプレー、エアスプ
レー等の塗装法により塗装することが好ましい。The first colored paint comprises the above-mentioned base resin, cross-linking agent, and color pigment, together with paint additives, if necessary.
It is obtained by mixing with an organic solvent, and this is generally applied to the lower part of the outer body of the vehicle body by 10 to 50 based on the cured coating film.
It is preferable to apply a coating having a thickness of μm by a coating method such as electrostatic coating, airless spray, or air spray.
【0042】本発明塗装法では、第一着色塗料を塗装し
てから、約100〜170℃の温度で約10〜40分間
加熱して、上記の塩化ビニル樹脂系塗料、ポリウレタン
樹脂系塗料、中塗塗料及び第一着色塗料からなる4層塗
膜を同時に架橋硬化させる。In the coating method of the present invention, after the first colored coating is applied, the coating is heated at a temperature of about 100 to 170 ° C. for about 10 to 40 minutes to obtain the above-mentioned vinyl chloride resin coating, polyurethane resin coating, intermediate coating. The four-layer coating film composed of the paint and the first colored paint is simultaneously cross-linked and cured.
【0043】本発明塗装法では、第一着色塗料を塗装
し、加熱硬化させた後、車体外板部の上部のみに第二着
色塗料を塗装する。In the coating method of the present invention, the first colored paint is applied, cured by heating, and then the second colored paint is applied only to the upper portion of the vehicle body outer panel.
【0044】第二着色塗料は、第一着色塗料と異なる色
調で、基体樹脂、架橋剤、着色顔料等を含有し、これら
を有機溶剤に混合せしめることにより得られる熱硬化性
塗料である。有機溶剤としては、前記塩化ビニル樹脂系
塗料で有機溶剤として例示したものから選ばれる1種又
は2種以上が使用できる。The second color paint is a thermosetting paint obtained by mixing a base resin, a cross-linking agent, a color pigment and the like with an organic solvent in a color tone different from that of the first color paint. As the organic solvent, one or more kinds selected from those exemplified as the organic solvent in the vinyl chloride resin-based paint can be used.
【0045】基体樹脂としては、例えば、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、ウレタン樹脂等が挙げられ、架橋剤としては、例え
ば、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等があげられ
る。着色顔料としては、フレーク状のアルミニウム、ス
テンレス、雲母粉等のメタリック顔料が好適に使用でき
る。Examples of the base resin include acrylic resins, polyester resins, alkyd resins, and urethane resins having a crosslinkable functional group. Examples of the crosslinkers include melamine resins, urea resins, polyisocyanate compounds, and blocks. And polyisocyanate compounds. As the color pigment, flake-like metallic pigments such as aluminum, stainless steel, and mica powder can be suitably used.
【0046】第二着色塗料は、上記の基体樹脂、架橋
剤、着色顔料を、必要に応じて塗料用添加剤等と共に、
有機溶剤に混合せしめることにより得られる。The second colored paint is prepared by adding the above-mentioned base resin, cross-linking agent, and color pigment together with paint additives, if necessary.
It is obtained by mixing with an organic solvent.
【0047】本発明塗装法では、第一着色塗料を塗装し
加熱硬化してなる車体下部の該塗面をマスキングテープ
等でマスキングしてから、露出している車体上部のみに
第二着色塗料を硬化塗膜に基いて15〜25μmの膜厚
に、静電塗装、エアレススプレー、エアスプレー等の塗
装法により塗装し、硬化させることなく、さらにこの第
二着色塗料の塗面にクリヤ塗料を硬化塗膜に基いて10
〜100μmの膜厚に、静電塗装、エアレススプレー、
エアスプレー等の塗装法により塗装した後、加熱してこ
の両塗膜を硬化することにより、本発明塗装法による2
トーン仕上げが達成される。In the coating method of the present invention, the first colored paint is applied, and the coated surface of the lower part of the body formed by heating and curing is masked with a masking tape or the like, and then the second colored paint is applied only to the exposed upper part of the body. Apply a coating method such as electrostatic coating, airless spraying, or air spraying to a thickness of 15 to 25 μm based on the cured coating film, and then cure the clear paint on the surface of the second colored paint without curing. 10 based on coating
Electrostatic coating, airless spray,
After coating by a coating method such as air spraying, the two coating films are cured by heating, whereby the coating method of the present invention is applied.
A tone finish is achieved.
【0048】その結果、車体外板部は色調が異なる通常
メタリック調の第一着色塗料と第二着色塗料によって2
色に塗り分けられており、しかも両塗料の塗膜は接触隣
接しているか、又はモール等を介在させて隣接している
ことが好ましい。As a result, the outer body of the vehicle body is made up of the first metallic paint and the second metallic paint having different metallic tones.
It is preferable that the coatings are applied in different colors and that the coating films of the two paints are in contact with and adjacent to each other, or are adjacent to each other via a molding or the like.
【0049】車体上部の第二着色塗面に塗装するクリヤ
塗料は、基体樹脂、架橋剤及び有機溶剤を主成分とし、
さらに必要に応じて該塗膜の透明感を損なわない程度で
着色顔料及びその他の塗料用添加剤等を配合してなる無
色又は有色の透明塗膜を形成する液状熱硬化性塗料であ
る。クリヤ塗料の基体樹脂としては、例えば架橋性官能
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、ウレタン樹脂等が挙げられ、架橋剤としては、例
えばメラミン樹脂、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等があげられ
る。有機溶剤としては、前記塩化ビニル樹脂系塗料で有
機溶剤として例示したものから選ばれる1種又は2種以
上が使用できる。The clear paint to be applied to the second colored painted surface on the upper part of the vehicle body contains a base resin, a crosslinking agent and an organic solvent as main components,
Further, it is a liquid thermosetting paint which forms a colorless or colored transparent coating film containing a coloring pigment and other additives for coating materials to the extent that the transparency of the coating film is not impaired as required. Examples of the base resin of the clear paint include an acrylic resin having a crosslinkable functional group, a polyester resin, an alkyd resin, and a urethane resin. Examples of the crosslinker include a melamine resin, a urea resin, a polyisocyanate compound, and a block polyisocyanate. And the like. As the organic solvent, one or more kinds selected from those exemplified as the organic solvent in the vinyl chloride resin-based paint can be used.
【0050】クリヤ塗料を塗装したのち、約100〜1
70℃の温度で10〜40分間加熱して、第二着色塗料
及びクリヤ塗料の両塗膜を同時に架橋硬化させる。After applying the clear paint, about 100 to 1
By heating at a temperature of 70 ° C. for 10 to 40 minutes, both coating films of the second colored paint and the clear paint are simultaneously cross-linked and cured.
【0051】[0051]
【実施例】以下に、製造例、実施例及び比較例を挙げ
て、本発明を更に具体的に説明する。各例における部及
び%はいずれも重量に基く。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Production Examples, Examples, and Comparative Examples. All parts and percentages in each case are by weight.
【0052】製造例1 被塗物の調製 自動車車体用鋼板に、「エレクロン9600」(関西ペ
イント社製、商品名、エポキシ樹脂系カチオン電着塗
料)を硬化塗膜で15μmになるように電着塗装し、1
60℃で30分加熱して硬化せしめたものを被塗物とし
た。Production Example 1 Preparation of Coating Material "Electron 9600" (trade name, epoxy resin-based cationic electrodeposition paint, manufactured by Kansai Paint Co., Ltd.) was electrodeposited on a steel plate for an automobile body so as to have a cured film thickness of 15 μm. Painted, 1
What was cured by heating at 60 ° C. for 30 minutes was used as an object to be coated.
【0053】製造例2 塩化ビニル樹脂系塗料(a−
1)の調製 塩化ビニル樹脂100部、充填剤(チタン白、硫酸バリ
ウム、炭酸カルシウム)100部、可塑剤(フタル酸ジ
ブチル)50部、及び炭化水素系溶剤を配合して、塩化
ビニル樹脂系塗料(a−1)を調製した。Production Example 2 Vinyl chloride resin paint (a-
Preparation of 1) 100 parts of a vinyl chloride resin, 100 parts of a filler (titanium white, barium sulfate, calcium carbonate), 50 parts of a plasticizer (dibutyl phthalate), and a hydrocarbon solvent are blended, and a vinyl chloride resin paint (A-1) was prepared.
【0054】製造例3 ポリウレタン樹脂系塗料(b−
1)の調製 ヘキサメチレンジイソシアネート変性ポリエステル樹脂
(水酸基価90mgKOH/g、数平均分子量約2,7
00)60部、ε−カプロラクタムブロックヘキサメチ
レンジイソシアネート12部、「サイメル703」(三
井サイアナミド社製、商品名、メラミン樹脂)22部、
エポキシ樹脂(「エポン828」、シェル化学社製、商
品名、ビスフェノール型エポキシ樹脂)6部、顔料(チ
タン白、硫酸バリウム)260部、及び炭化水素系溶剤
を配合して、ポリウレタン樹脂系塗料(b−1)を調製
した。Production Example 3 Polyurethane resin paint (b-
Preparation of 1) Hexamethylene diisocyanate-modified polyester resin (hydroxyl value 90 mgKOH / g, number average molecular weight about 2,7
00) 60 parts, ε-caprolactam block hexamethylene diisocyanate 12 parts, “CYMEL 703” (trade name, melamine resin, manufactured by Mitsui Cyanamid Co.), 22 parts,
6 parts of an epoxy resin (“Epon 828”, manufactured by Shell Chemical Company, trade name, bisphenol type epoxy resin), 260 parts of a pigment (titanium white, barium sulfate), and a hydrocarbon solvent are blended, and a polyurethane resin paint ( b-1) was prepared.
【0055】実施例1 製造例1で得た被塗物の下部に製造例2で得た塩化ビニ
ル樹脂系塗料(a−1)をエアレススプレー塗装し(塗
装膜厚は硬化塗膜で250μm)、硬化させずに、該未
硬化塗面に製造例3で得たポリウレタン樹脂系塗料(b
−1)をエアレススプレーで塗り重ね(塗装膜厚は硬化
塗膜で75μm)、硬化させずに、「WSTPー65プ
ライマ」(関西ペイント社製、商品名、水酸基含有ポリ
エステル樹脂・メラミン樹脂系中塗塗料)を被塗物全面
にエアスプレー塗装したのち(塗装膜厚は硬化塗膜で1
5μm)、硬化させずに、上記のポリウレタン樹脂系塗
料(b−1)を塗装した部分に、第一着色塗料として
「WSTP−069シルバー」(関西ペイント社製、商
品名、水酸基含有ポリエステル樹脂・メラミン樹脂系シ
ルバーメタリック塗料)をエアスプレーで塗り重ねた
(塗装膜厚は硬化塗膜で20μm)後、140℃で30
分加熱して、これらの4層塗膜を同時に硬化させた。次
いで、この第一着色塗料の塗面をマスキングしたのち、
第二着色塗料として「NAD5500 B38M」(関
西ペイント社製、商品名、水酸基含有アクリル樹脂・メ
ラミン樹脂系ブルーメタリック塗料)を第一着色塗料の
塗膜に隣接するように被塗物上部にエアスプレー塗装し
(塗装膜厚は硬化塗膜で20μm)、硬化させずに、更
にクリヤ塗料として「DNC−K2クリヤ」(関西ペイ
ント社製、商品名、水酸基含有アクリル樹脂・メラミン
樹脂系クリヤ塗料)を第二着色塗料部分の全面にエアス
プレー塗装した(塗装膜厚は硬化塗膜で40μm)の
ち、140℃で30分加熱して、上部の2層塗膜を同時
に硬化させて、本発明塗装方法を実施した。Example 1 The vinyl chloride resin-based coating material (a-1) obtained in Production Example 2 was applied by airless spray coating to the lower part of the object to be coated obtained in Production Example 1 (coating thickness: 250 μm as a cured coating film). The polyurethane resin paint (b) obtained in Production Example 3 was applied to the uncured coated surface without curing.
-1) is applied by airless spray (the coating film thickness is 75 μm in a cured coating film), and without curing, “WSTP-65 Primer” (manufactured by Kansai Paint Co., Ltd., trade name, hydroxyl group-containing polyester resin / melamine resin middle coating) After coating the entire surface of the object with air spray coating (the coating thickness is 1
5 .mu.m), a portion of the above-mentioned polyurethane resin-based paint (b-1) coated without curing, as a first colored paint, "WSTP-069 silver" (manufactured by Kansai Paint Co., Ltd., trade name, hydroxyl group-containing polyester resin. Melamine resin-based silver metallic paint) was applied by air spray (the thickness of the coated film was 20 μm for the cured coating film), and then 30 ° C at 140 ° C.
By heating for a minute, these four-layer coatings were simultaneously cured. Next, after masking the coated surface of the first colored paint,
"NAD5500 B38M" (manufactured by Kansai Paint Co., Ltd., trade name, hydroxyl group-containing acrylic resin / melamine resin-based blue metallic paint) as a second colored paint is air-sprayed on the top of the object to be coated so as to be adjacent to the first colored paint film. After coating (the coating thickness is 20 μm with a cured coating film), without curing, further, as a clear paint, “DNC-K2 Clear” (trade name, manufactured by Kansai Paint Co., Ltd., hydroxyl group-containing acrylic resin / melamine resin clear paint) After applying air spray coating to the entire surface of the second colored paint portion (the coating film thickness is 40 μm as a cured coating film), the coating is heated at 140 ° C. for 30 minutes to simultaneously cure the upper two-layer coating film. Was carried out.
【0056】比較例1 実施例1においてポリウレタン樹脂系塗料(b−1)を
使用しない以外は、実施例1と同様にして、比較の塗装
方法を行った。Comparative Example 1 A comparative coating method was performed in the same manner as in Example 1 except that the polyurethane resin-based coating material (b-1) was not used.
【0057】上記実施例1及び比較例1で得られた塗膜
の性能を、下記試験方法により、調べた。The performance of the coating films obtained in Example 1 and Comparative Example 1 was examined by the following test methods.
【0058】層間付着性:カッターで、素地に達するよ
うに複層塗膜に1mm間隔で切り込み、大きさ1mm×
1mmのゴバン目を100個作り、その表面に粘着テー
プを貼着し、20℃でそれを急激に剥離した後の、残存
ゴバン目数により、各塗膜間の層間付着性を調べた。○
は100個残存、△は99〜90個残存、×は89個以
下残存を、それぞれ示す。Adhesion between layers: A multi-layer coating film was cut at intervals of 1 mm with a cutter so as to reach a substrate, and the size was 1 mm ×
100 pieces of 1 mm squares were formed, an adhesive tape was stuck on the surface, and the adhesive tape was rapidly peeled off at 20 ° C., and the interlayer adhesion between the coating films was examined based on the number of remaining squares. ○
Represents 100 remaining, Δ represents 99 to 90 remaining, and X represents 89 or less remaining.
【0059】耐チッピング性:グラベロメータ(Qパネ
ル社製)を用い、7号砕石500gを塗面に対して45
°の角度で、20℃においてエアー圧0.3MPaで塗
面に吹き付けて、衝撃を与えた。ついで、その塗面に粘
着テープを貼着し剥離した後の、衝撃によるキズの周囲
の状態を調べた。○はキズ周辺部に塗膜剥離が殆ど認め
られない、△はキズ周辺部に塗膜剥離が明確に認められ
る、×はキズ周辺部に塗膜剥離が著しく認められるを、
それぞれ示す。Chipping resistance: 500 g of No. 7 crushed stone was applied to a coated surface by using a gravelometer (manufactured by Q Panel Co., Ltd.).
It was sprayed onto the coated surface at an angle of ° and an air pressure of 0.3 MPa at 20 ° C to give an impact. Then, the state around the scratches due to impact after the adhesive tape was stuck to the coated surface and peeled off was examined. ○ indicates that the coating film peeling is hardly recognized around the scratch, Δ indicates that the coating peeling is clearly recognized around the scratch, and x indicates that the coating peeling is significantly recognized around the scratch.
Shown respectively.
【0060】ツヤ:60°鏡面反射率(%)で評価し
た。Gloss: Evaluated by 60 ° specular reflectance (%).
【0061】平滑性:塗面を目視で評価した。5は平滑
性良好、4は平滑性やや良好、3は平滑性やや劣るが実
用上問題なし、2は平滑性劣り実用的ではない、1は平
滑性非常に劣る、をそれぞれ示す。Smoothness: The coated surface was visually evaluated. 5 indicates good smoothness, 4 indicates somewhat good smoothness, 3 indicates slightly poor smoothness but no problem in practical use, 2 indicates poor smoothness and is not practical, and 1 indicates very poor smoothness.
【0062】色差:ミノルタ社製、色差計「CR−20
0型」を使用して、色標準板との色の差異(ΔE)を求
めた。数値が小さい方が色差が少なく、0.8以下であ
れば良好である。Color difference: Color difference meter “CR-20” manufactured by Minolta Co.
Using the “type 0”, the color difference (ΔE) from the color standard plate was determined. The smaller the numerical value is, the smaller the color difference is, and the better the value is 0.8 or less.
【0063】塗膜性能の試験結果を、表1に示した。Table 1 shows the test results of the coating film performance.
【0064】[0064]
【表1】 [Table 1]
【0065】表1における上部の性能の相違は、下部と
隣接する上部に、下部の4層塗膜やスプレーダストが存
在し、それによって上部の塗膜性能が変動するためであ
る。The difference in the performance of the upper part in Table 1 is that the lower four-layer coating film and the spray dust exist in the lower part and the adjacent upper part, and the performance of the upper part film fluctuates due to the presence of the lower four-layer coating film and spray dust.
【0066】[0066]
【発明の効果】自動車車体外板部を2トーンに仕上げ塗
装するにあたり、外板部の下部に塩化ビニル樹脂系耐チ
ッピング性塗料を塗装してから、さらに該塗面にポリウ
レタン樹脂系耐チッピング性塗料を塗装することによ
り、第一の着色塗料塗膜の光沢の低下、メタリック顔料
を含む場合におけるその配向性の乱れ、塩化ビニル系樹
脂塗料による平滑性の低下等を、いずれも効果的に防止
でき、自動車車体外板部に仕上り外観や耐チッピング性
等のすぐれた塗膜を形成できた。According to the present invention, a vinyl chloride resin-based chipping resistant paint is applied to the lower portion of the outer body of the automobile body when the exterior body of the automobile body is painted in two tones. By applying the paint, it effectively prevents the decrease of the gloss of the first colored paint film, the disorder of the orientation when metallic pigment is contained, the decrease of the smoothness by the vinyl chloride resin paint, etc. As a result, a coating film having excellent finish appearance, chipping resistance and the like was formed on the outer panel of the automobile body.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 中村 公紀 大阪府池田市ダイハツ町1番1号 ダイハ ツ工業株式会社内 (72)発明者 山口 政雄 大阪府池田市桃園2丁目1番1号 ダイハ ツ工業株式会社内 (72)発明者 井根 弘充 大阪府池田市桃園2丁目1番1号 ダイハ ツ工業株式会社内 (72)発明者 森本 等 大阪府池田市桃園2丁目1番1号 ダイハ ツ工業株式会社内 (72)発明者 久保田 直民 大阪府大阪市北区西天満3丁目13番7号 株式会社扇商会内 (72)発明者 大井 健 大阪府大阪市北区西天満3丁目13番7号 株式会社扇商会内 (72)発明者 藤原 英昭 兵庫県尼崎市神崎町33番1号 関西ペイン ト株式会社内 (72)発明者 峯本 勝 兵庫県尼崎市神崎町33番1号 関西ペイン ト株式会社内 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Kiminori Nakamura 1-1-1, Daihatsu-cho, Ikeda-shi, Osaka Inside Daihatsu Industry Co., Ltd. (72) Inventor Masao Yamaguchi 2-1-1 Taoyuan, Ikeda-shi, Osaka Daihatsu Inside Industrial Co., Ltd. (72) Inventor Hiromitsu Ine 2-1-1 Taoyuan, Ikeda-shi, Osaka Daihatsu Kogyo Co., Ltd. (72) Inventor, etc. 2-1-1 Taoyuan, Ikeda-shi, Osaka Daihatsu Kogyo Inside (72) Inventor Naoto Kubota 3-13-7 Nishitenma, Kita-ku, Osaka-shi, Osaka Inside Fan Trading Co., Ltd. (72) Inventor Ken Oi 3- 13-7, Nishitenma, Kita-ku, Osaka, Osaka Shares (72) Inventor Hideaki Fujiwara 33-1, Kanzakicho, Amagasaki City, Hyogo Kansai Paint Co., Ltd. (72) Inventor Masaru Minato 33, Kanzakicho, Amagasaki City, Hyogo Prefecture No. Kansai Paint Co., Ltd. in
Claims (1)
ーンに仕上げる自動車車体外板部の塗装方法であって、
該外板部の全面に電着塗料を塗装し、加熱硬化した後、
砂利や小石があたり易い部分に、塩化ビニル樹脂系耐チ
ッピング性塗料及びポリウレタン樹脂系耐チッピング性
塗料を塗装し、ついで該外板部の全面に中塗塗料を塗装
してから、該外板部の下部に第一の着色塗料を塗装し、
加熱してこれらの4層塗膜を同時に硬化させた後、該外
板部の上部のみに第二の着色塗料及びクリヤ塗料を塗装
し、加熱して上部のこれら2層塗膜を同時に硬化させる
ことを特徴とする2トーン仕上げ塗装方法。1. A method for coating an outer panel of an automobile body, which is finished to two tones using two kinds of colored paints having different color tones,
After coating the entire surface of the outer plate with an electrodeposition paint and curing by heating,
Apply a vinyl chloride resin-based chipping-resistant paint and polyurethane resin-based chipping-resistant paint to areas where gravel and pebbles are likely to hit, then apply an intermediate coating over the entire outer panel, and then apply Paint the first colored paint on the bottom,
After heating to cure these four-layer coatings at the same time, apply a second coloring paint and clear coating only to the upper part of the outer plate part, and heat to simultaneously cure these two-layer coatings on the upper part. A two-tone finish coating method characterized by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19541297A JPH1133485A (en) | 1997-07-22 | 1997-07-22 | Two-tone finish coating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19541297A JPH1133485A (en) | 1997-07-22 | 1997-07-22 | Two-tone finish coating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1133485A true JPH1133485A (en) | 1999-02-09 |
Family
ID=16340671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19541297A Pending JPH1133485A (en) | 1997-07-22 | 1997-07-22 | Two-tone finish coating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1133485A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005037442A3 (en) * | 2003-10-17 | 2005-06-02 | Du Pont | Improved method for achieving a two-tone finish on a vehicle |
-
1997
- 1997-07-22 JP JP19541297A patent/JPH1133485A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005037442A3 (en) * | 2003-10-17 | 2005-06-02 | Du Pont | Improved method for achieving a two-tone finish on a vehicle |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5976343A (en) | Multi-coat painting process | |
| JP4227192B2 (en) | Multi-layer coating method | |
| GB2167685A (en) | Process for coating automotive bodies | |
| JP5489976B2 (en) | Multi-layer coating formation method | |
| JP2858541B2 (en) | Coating method | |
| EP0714959A2 (en) | Paints for repairing lustrous agent-containing films and repairing process | |
| JPH1133485A (en) | Two-tone finish coating method | |
| US7943197B2 (en) | Process for producing two-tone coated substrates | |
| KR100435941B1 (en) | Method of forming multiple-layered coating film | |
| JPH06254482A (en) | Painting method | |
| KR100526730B1 (en) | Process for Forming Mutilayer Coating Films | |
| JP3710843B2 (en) | Coating method | |
| JP3262320B2 (en) | How to paint a car body | |
| JPH09131567A (en) | Coating method of aluminum foil | |
| JP4393752B2 (en) | Multi-layer coating formation method | |
| JP4976962B2 (en) | Coating method | |
| JPS62243660A (en) | Coating compound and method for forming composite coating film | |
| KR100679444B1 (en) | Multi-layer coating film formation method | |
| JP2000317394A (en) | Method for forming coating film | |
| JP2001104879A (en) | Coating method for automobile car body | |
| JP2001046952A (en) | Formation of coating film | |
| JPH09316373A (en) | Automotive coating composition and coating method | |
| JPH10244221A (en) | Car topcoating method | |
| JP2002079172A (en) | Method for forming coating film | |
| JPS6249973A (en) | Formation of coated film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Effective date: 20040513 Free format text: JAPANESE INTERMEDIATE CODE: A621 |
|
| A977 | Report on retrieval |
Effective date: 20060908 Free format text: JAPANESE INTERMEDIATE CODE: A971007 |
|
| A131 | Notification of reasons for refusal |
Effective date: 20061025 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A02 | Decision of refusal |
Effective date: 20070307 Free format text: JAPANESE INTERMEDIATE CODE: A02 |