JP2007023165A - Chipping-resistant coating and method for applying chipping-resistant coating - Google Patents
Chipping-resistant coating and method for applying chipping-resistant coating Download PDFInfo
- Publication number
- JP2007023165A JP2007023165A JP2005207787A JP2005207787A JP2007023165A JP 2007023165 A JP2007023165 A JP 2007023165A JP 2005207787 A JP2005207787 A JP 2005207787A JP 2005207787 A JP2005207787 A JP 2005207787A JP 2007023165 A JP2007023165 A JP 2007023165A
- Authority
- JP
- Japan
- Prior art keywords
- chipping
- paint
- coating
- resistant
- urethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 93
- 239000011248 coating agent Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000004070 electrodeposition Methods 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 125000002091 cationic group Chemical group 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 239000003973 paint Substances 0.000 claims description 87
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010422 painting Methods 0.000 claims 1
- -1 hydrazine compound Chemical class 0.000 abstract description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract 1
- 238000007665 sagging Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 8
- 235000015067 sauces Nutrition 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002981 blocking agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- UJTTUOLQLCQZEA-UHFFFAOYSA-N 9h-fluoren-9-ylmethyl n-(4-hydroxybutyl)carbamate Chemical compound C1=CC=C2C(COC(=O)NCCCCO)C3=CC=CC=C3C2=C1 UJTTUOLQLCQZEA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LJTFFORYSFGNCT-UHFFFAOYSA-N Thiocarbohydrazide Chemical compound NNC(=S)NN LJTFFORYSFGNCT-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- LEHOGBUBQSGCOK-UHFFFAOYSA-N aminothiourea;hydron;chloride Chemical compound Cl.NNC(N)=S LEHOGBUBQSGCOK-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- GRGBENNNGZARRZ-UHFFFAOYSA-N dodecanedihydrazide Chemical compound NNC(=O)CCCCCCCCCCC(=O)NN GRGBENNNGZARRZ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、例えば、自動車のロッカーパネル、ドア下部、フェンダー等に防錆、チッピング傷対策を目的に使用される耐チッピング塗料に関する。更に詳しくは、未硬化カチオン電着塗装上に焼き付け可能な耐チッピング塗料と、その塗装方法に関する。 The present invention relates to a chipping-resistant coating material used for the purpose of preventing rust and chipping scratches on, for example, an automobile rocker panel, a lower part of a door, and a fender. More specifically, the present invention relates to a chipping-resistant paint that can be baked on an uncured cationic electrodeposition coating and a coating method thereof.
従来、耐チッピング塗料として、ウレタン系、ポリエステル・メラミン系、ＰＶＣ系等の耐チッピング塗料が使用され、これら耐チッピング塗料の塗装に当たっては、先ず、カチオン電着塗料を塗装後、１６０〜１８０℃×２０分程度の焼き付けを行い、その後、耐チッピング塗料を塗装し、１００〜１４０℃×１０分程度の焼き付けを行い、その後、中塗り塗料を塗装し、１３０〜１５０℃×１０分程度の焼き付けを行っている。
近年、省エネルギーや、ＣＯ2排出減量等の環境対策への要求が強まり、また、自動車生産工程における効率向上を目的に、カチオン電着塗装、耐チッピング塗装、中塗り塗装までを、各工程で焼き付けをせず、３材料塗装後に、これらを１回の焼き付けで硬化を終了させる工程（３ＷＥＴ工程）が検討されている。尚、ここでいう３ＷＥＴ工程は、カチオン電着塗装後の水分を揮発させるためのプレヒート（一般的に８０〜１００℃×１０分程度）を含む。
このような現状に鑑みて、前記３ＷＥＴ工程に適した耐チッピング塗料の提案と、３ＷＥＴ工程の実現が望まれており、例えば、特許文献１には、中塗り塗料を塗装する段階を開始するときの耐チッピング塗料の溶解性パラメーターを９．５（ｃａｌ／ｃｍ3）1/2以上とすることが開示されている。
しかしながら、特許文献１に開示されるような耐チッピング塗料の溶解性パラメーターの場合には、未硬化電着塗装上での耐チッピング塗料のタレ及び耐チッピング塗料上の中塗り塗料のタレやスケが生じるという不都合があった。
Conventionally, urethane-based, polyester-melamine-based, PVC-based and other chipping-resistant paints are used as chipping-resistant paints. In applying these chipping-resistant paints, first, after applying a cationic electrodeposition paint, 160 to 180 ° C. × Bake for about 20 minutes, then apply a chipping-resistant paint, bake at 100 to 140 ° C for about 10 minutes, then apply an intermediate coat and bake at about 130 to 150 ° C for about 10 minutes. Is going.
In recent years, demand for environmental measures such as energy saving and CO 2 emission reduction has been strengthened, and cationic electrodeposition coating, chipping resistance coating, and intermediate coating are baked in each process for the purpose of improving efficiency in the automobile production process. A process (3WET process) in which curing is completed by baking once after three materials are coated is being studied. In addition, the 3WET process here includes preheating (generally about 80 to 100 ° C. × 10 minutes) for volatilizing water after cationic electrodeposition coating.
In view of such a current situation, proposal of a chipping resistant paint suitable for the 3WET process and realization of the 3WET process are desired. For example, Patent Document 1 discloses that a stage of applying an intermediate paint is started. It is disclosed that the solubility parameter of the anti-chipping paint of 9.5 is not less than 9.5 (cal / cm 3 ) 1/2 .
However, in the case of the solubility parameter of the chipping-resistant paint as disclosed in Patent Document 1, the sagging of the chipping-resistant paint on the uncured electrodeposition coating and the sagging or scale of the intermediate-coat paint on the chipping-resistant paint are There was an inconvenience that it occurred.
そこで、本発明は、３ＷＥＴ工程に適した耐チッピング塗料を提供することを目的とする。 Then, an object of this invention is to provide the chipping-resistant coating material suitable for a 3WET process.
本発明者ら前記要望に応えるべく鋭意検討の結果、ＳＰ値８．７以下の溶剤を使用してウレタン系耐チッピング塗料を構成することにより、前記３ＷＥＴ工程に適した耐チッピング塗料が得られることを知見した。
本発明の耐チッピング塗料は前記知見に基づきなされたもので、請求項１記載の通り、未硬化カチオン電着塗料上に塗布され、且つ、更に、その上に他の塗料が塗布されるようにして使用される耐チッピング塗料であって、樹脂成分としてウレタン系樹脂を用いると共に、ＳＰ値８．７以下の溶剤を使用するようにしたことを特徴とする。
また、請求項２記載の耐チッピング塗料は、請求項１に記載の耐チッピング塗料において、前記ウレタン系樹脂の硬化剤として、ヒドラジド化合物を使用することを特徴とする。
また、本発明の耐チッピング塗料の塗装方法は、請求項３記載の通り、未硬化カチオン電着塗料上に塗布され、且つ、更に、その上に他の塗料が塗布されるようにして使用される耐チッピング塗料を塗装する方法であって、未硬化カチオン電着塗装上に、その焼き付け前に、樹脂成分としてウレタン系樹脂を用いると共に、ＳＰ値８．７以下の溶剤を使用するようにした耐チッピング塗料を塗布し、これら塗料を同時に焼き付けることを特徴とする。
また、請求項４記載の耐チッピング塗料の塗装方法は、請求項３記載の耐チッピング塗料の塗装方法において、前記焼き付け前に、中塗り塗料を塗布し、該中塗り塗料も含め、これら塗料を同時に焼き付けることを特徴とする。
また、請求項５記載の耐チッピング塗料の塗装方法は、請求項４記載の耐チッピング塗料の塗装方法において、前記中塗り塗料として、水性塗料を用いることを特徴とする。
As a result of intensive studies to meet the above-mentioned demands, the chipping-resistant paint suitable for the 3WET process can be obtained by constructing the urethane-type chipping-resistant paint using a solvent having an SP value of 8.7 or less. I found out.
The chipping-resistant coating material of the present invention has been made based on the above knowledge, and as described in claim 1, it is applied on an uncured cationic electrodeposition coating material, and further, another coating material is applied thereon. The anti-chipping coating used in the present invention is characterized in that a urethane resin is used as a resin component and a solvent having an SP value of 8.7 or less is used.
The chipping resistant paint according to claim 2 is characterized in that, in the chipping resistant paint according to claim 1, a hydrazide compound is used as a curing agent for the urethane resin.
In addition, the chipping resistant coating method of the present invention is used in such a manner that it is applied on an uncured cationic electrodeposition coating and further coated with another coating. A method of applying a chipping-resistant paint, wherein a urethane resin is used as a resin component and a solvent having an SP value of 8.7 or less is used on the uncured cationic electrodeposition coating before baking. It is characterized by applying a chipping resistant paint and baking these paints simultaneously.
Further, the method for applying the chipping-resistant paint according to claim 4 is the method for applying the chipping-resistant paint according to claim 3, wherein the intermediate paint is applied before the baking, and the paint including the intermediate paint is applied. It is characterized by baking at the same time.
According to a fifth aspect of the present invention, there is provided a method for applying a chipping-resistant coating material, wherein the intermediate coating material is a water-based coating material.
本発明によれば、ＳＰ値８．７以下の溶剤を使用してウレタン系耐チッピング塗料を構成するようにしたため、３ＷＥＴ工程を実現可能なウレタン系耐チッピング塗料が得られ、未硬化カチオン電着塗料及び耐チッピング塗料のタレを発生させず、しかも、耐チッピング塗料上の中塗り塗料にスケを発生せることなく、これらを同時に焼き付けることができる。
また、更に、ウレタン系樹脂の硬化剤として、ヒドラジド化合物を使用することにより、耐チッピング塗料のワキ性を抑え、優れたものとすることができる。
また、本発明によれば、未硬化電着塗装上での耐チッピング塗料のタレ及び耐チッピング塗料上の中塗り塗料のタレやスケが生じることなく、効率的な３ＷＥＴ工程を実現することができる。
According to the present invention, the urethane-type chipping-resistant coating material is constituted by using a solvent having an SP value of 8.7 or less, so that a urethane-type chipping-resistant coating material capable of realizing the 3WET process is obtained, and uncured cationic electrodeposition is performed. These can be baked at the same time without causing sagging of the paint and chipping-resistant paint, and without causing any scum in the intermediate coating on the chipping-resistant paint.
Furthermore, by using a hydrazide compound as a curing agent for urethane-based resin, it is possible to suppress the cracking resistance of the chipping-resistant paint and make it excellent.
Further, according to the present invention, an efficient 3WET process can be realized without causing sagging of the anti-chipping paint on the uncured electrodeposition coating and no sagging or scaling of the intermediate coating on the anti-chipping paint. .
前記の通り、本発明の耐チッピング塗料は、樹脂成分としてウレタン系樹脂を用いると共に、ＳＰ値８．７以下の溶剤を使用するものである。前記ウレタン系樹脂としては、ＴＤＩ、ＭＤＩ、ＨＤＩ、ＨＭＤＩ、ＩＰＤＩ、ＨＭＤＩ、ＸＤＩ、ＨＸＤＩ又はこれらの変性体や誘導体のイソシアネート基を、アルコール系、フェノール系、オキシム系、アミンアミド系、ラクタム系、活性メチレン系などの活性水素を有するブロック剤であって、−ＮＣＯをマスクしたブロックイソシアネートを使用する。ウレタンの反応相手としては、水酸基、アミノ基、イミノ基、カルボン酸、ウレタン基、尿素基などの活性水素を有する化合物を使用することができる。 As described above, the chipping resistant paint of the present invention uses a urethane resin as a resin component and uses a solvent having an SP value of 8.7 or less. As the urethane resin, the isocyanate group of TDI, MDI, HDI, HMDI, IPDI, HMDI, XDI, HXDI or a modified product or derivative thereof may be alcohol, phenol, oxime, amine amide, lactam, or active. A blocking agent having an active hydrogen such as methylene and having blocked -NCO is used. As the reaction partner of urethane, compounds having active hydrogen such as hydroxyl group, amino group, imino group, carboxylic acid, urethane group, urea group can be used.
また、前記ＳＰ値８．７以下の厚塗型耐チッピング塗料用の溶剤としては、丸善石油社製スワゾール１０００、１８００、エクソル化学社製ソルベッツ１００、１５０、キシレン、ＭＩＢＫ（メチルイソブチルケトン）、シェルケミカル社製ＬＡＷＳ（ターペン）等が挙げられる。
ここで、溶剤のＳＰ値を８．７以下としたのは、ＳＰ値が８．７を超えると、耐チッピング塗料の被着体である未硬化カチオン電着塗料が溶解してしまい、未硬化カチオン電着塗料及び耐チッピング塗料のタレが発生するからである。また、３ＷＥＴ工程用の中塗り塗料との相溶性が悪いため、耐チッピング塗料上の中塗り塗料にスケやタレが発生してしまうからでもある。
このように、ＳＰ値８．７以下の溶剤を使用したウレタン系耐チッピング塗料を用いることにより、前記３ＷＥＴ工程においても、未硬化カチオン電着塗料及び耐チッピング塗料のタレが発生することなく、また、耐チッピング塗料上の中塗り塗料にスケが発生することなく、３ＷＥＴ工程を実現可能ならしめることができる。
Further, as a solvent for the thick-type chipping resistant paint having an SP value of 8.7 or less, Maruzen Petroleum's Swazol 1000, 1800, Exol Chemical's Solvets 100, 150, xylene, MIBK (methyl isobutyl ketone), shell Examples include LAWS (Turpen) manufactured by Chemical Corporation.
Here, the SP value of the solvent was set to 8.7 or less. When the SP value exceeded 8.7, the uncured cationic electrodeposition coating material, which is the adherend of the chipping-resistant coating material, was dissolved and uncured. This is because sagging of the cationic electrodeposition paint and the chipping resistant paint occurs. In addition, since the compatibility with the intermediate coating material for the 3WET process is poor, the intermediate coating material on the chipping-resistant coating material may be scaled or sagged.
Thus, by using a urethane-based chipping resistant paint using a solvent having an SP value of 8.7 or less, there is no sagging of uncured cationic electrodeposition paint and chipping resistant paint even in the 3WET process. In addition, it is possible to realize a 3WET process without causing any scale in the intermediate coating on the chipping-resistant coating.
尚、本発明における溶剤のＳＰ値（溶解性パラメーター）は、下記式、
ＳＰ値＝（分子凝集エネルギー／分子容）1/2
で求められた値である。また、前記溶剤は、１種又は２種以上の混合溶剤であってもよい。２種以上の混合溶剤のＳＰ値は、下記式、
ＳＰ値＝Ｓ1・ψ1＋Ｓ2・ψ2＋・・・
（式中、Ｓ1、Ｓ2・・・は混合溶剤に使用されたそれぞれの溶解性パラメーターを示し、ψ1、ψ2・・・は混合溶剤中のそれぞれの溶剤の容積分率を示す。）で求めることができる。
In addition, SP value (solubility parameter) of the solvent in this invention is a following formula,
SP value = (molecular cohesive energy / molecular volume) 1/2
This is the value obtained in. Moreover, the said solvent may be 1 type, or 2 or more types of mixed solvents. The SP value of two or more mixed solvents is expressed by the following formula:
SP value = S 1 · ψ 1 + S 2 · ψ 2 +
(In the formula, S 1 , S 2 ... Indicate respective solubility parameters used in the mixed solvent, and ψ 1 , ψ 2 ... Indicate the volume fraction of each solvent in the mixed solvent. ).
また、前記溶剤は、蒸留範囲１５０〜２２０℃のものを用いることが好ましい。これは、蒸留範囲が１５０℃未満の場合、焼き付け時に耐チッピング塗料のワキが発生しやすく、また、２２０℃を超えた場合、未硬化耐チッピング塗料上の中塗り塗料のスケが発生しやすいためである。尚、以下に説明するように、ウレタン系耐チッピング塗料の硬化剤として、ヒドラジド化合物を使用する場合には、蒸留範囲１１０〜２５０℃の溶剤であっても使用することができ、溶剤の選択範囲を広げることができる。
このような溶剤としては、特に制限はないが、例えば、エクソル化学製ソルベッツ１００、ソルベッツ１５０、丸善石油製スワゾール１０００、スワゾール１５００等を使用することができる。
Moreover, it is preferable to use the said solvent of the distillation range 150-220 degreeC. This is because when the distillation range is less than 150 ° C., the chipping-resistant paint is likely to crack during baking, and when it exceeds 220 ° C., the coating of the intermediate coating on the uncured anti-chipping paint is likely to occur. It is. As will be described below, when a hydrazide compound is used as a curing agent for a urethane-based chipping resistant coating, even a solvent having a distillation range of 110 to 250 ° C. can be used. Can be spread.
Although there is no restriction | limiting in particular as such a solvent, For example, Exol Chemical's Solvets 100, Solvets 150, Maruzen Petroleum Swazol 1000, Swazol 1500, etc. can be used.
また、前記ウレタン系耐チッピング塗料には、炭酸カルシウム、硫酸バリウム、タルク、クレー、二酸化チタン、カーボン等の充填剤、或いは、消泡剤、分散剤、酸化防止剤、レベリング剤等の各種添加剤を含ませることは任意であり、溶剤のＳＰ値を除けば、従来のウレタン系耐チッピング塗料と特にその組成を異にするものではない。 In addition, the urethane-based chipping-resistant coating material includes fillers such as calcium carbonate, barium sulfate, talc, clay, titanium dioxide, and carbon, or various additives such as an antifoaming agent, a dispersant, an antioxidant, and a leveling agent. Including the SP value of the solvent, the composition is not particularly different from that of the conventional urethane-based anti-chipping paint.
本発明の耐チッピング塗料の塗装方法では、未硬化カチオン電着塗装上に、その焼き付け前に、前記ＳＰ値８．７以下の溶剤を使用した耐チッピング塗料を塗布し、これら塗料を同時に焼き付けることにより、耐チッピング塗料の被着体である未硬化カチオン電着塗料を溶解させることなく、未硬化カチオン電着塗料及び耐チッピング塗料のタレを発生させることなく、これらを同時に焼き付けることができる。
この場合の焼き付け条件は、温度１２０〜１８０℃、時間１０分〜６０分である。
In the method of coating a chipping resistant coating of the present invention, a chipping resistant coating using a solvent having an SP value of 8.7 or less is applied on an uncured cationic electrodeposition coating before baking, and these coatings are baked simultaneously. Thus, the uncured cationic electrodeposition paint, which is the adherend of the chipping-resistant paint, can be simultaneously baked without dissolving the uncured cationic electrodeposition paint and the chipping-resistant paint.
The baking conditions in this case are a temperature of 120 to 180 ° C. and a time of 10 minutes to 60 minutes.
また、本発明の耐チッピング塗料の塗装方法では、前記未硬化カチオン電着塗料と未硬化耐チッピング塗料の焼き付け前に、更に他の塗料を塗布するものであるが、他の塗料として、中塗り塗料を塗布し、該中塗り塗料も含め、これら塗料を同時に焼き付けることにより、耐チッピング塗料の被着体である未硬化カチオン電着塗料を溶解させることなく、未硬化カチオン電着塗料及び耐チッピング塗料のタレを発生させず、しかも、耐チッピング塗料上の中塗り塗料にスケを発生せることなく、これらを同時に焼き付けることができる。 Further, in the coating method of the chipping resistant coating material of the present invention, another coating material is further applied before baking the uncured cationic electrodeposition coating material and the uncured chipping resistant coating material. By applying paint and baking these paints at the same time, including the intermediate paint, uncured cationic electrodeposition paint and chipping resistance without dissolving the uncured cationic electrodeposition paint which is the adherend of the chipping-resistant paint These can be baked at the same time without causing sagging of the paint and without causing any scum in the intermediate coating on the chipping-resistant paint.
前記中塗り塗料としては、一般的に自動車製造工程で使用される溶剤型中塗塗料や水性中塗塗料等が使用できるが、近年の環境問題の観点から、排出ＶＯＣ量の少ない中性中塗り塗料の使用が好ましい。
この場合の焼き付け条件は、温度１２０〜１８０℃、時間１０分〜６０分である。
As the intermediate coating material, a solvent-type intermediate coating material and a water-based intermediate coating material that are generally used in automobile manufacturing processes can be used. However, from the viewpoint of environmental problems in recent years, a neutral intermediate coating material with a small amount of discharged VOC is used. Use is preferred.
The baking conditions in this case are a temperature of 120 to 180 ° C. and a time of 10 minutes to 60 minutes.
上記耐チッピング塗料において、ウレタン系樹脂の硬化剤として、ヒドラジド化合物を使用することが好ましい。
ヒドラジド化合物は、粉体であるため、常温において、ブロックイソシアネートのブロック剤の乖離させる触媒機能を保有しておらず、また、本発明で使用される溶剤にも不溶であり、１液で保管しても粘度変化はなく、良好な安定性が得られるためである。
また、従来の耐チッピング塗料に比べて、膜厚を、例えば、２／３程度と薄くしても、同様のチッピング性能が得られる。また、従来の耐チッピング剤に比べて、低温で硬化させることができ、耐ワキ性が良好であるとともに、厚塗り部のクラック性を向上させることができる。
更に、従来品と比べて、硬化剤が粉体であるため、塗料への硬化剤の移行が少なく、塗膜が黄変を抑えることができる。
前記ヒドラジド化合物としては、例えば、ドデカンジオヒドラジド、イソフタル酸ジヒドラジド、カルボヒドラジド、セミカルバジド塩酸塩、アジピン酸ジヒドラジド、チオカルボヒドラジド、セバシン酸ジヒドラジド、チオセミカルバジド塩酸塩、カルボヒドラジド、コハク酸ジヒドラジド、Ｎ，Ｎ’−ヘキサメチレンビスセミカルバジド等を使用することができる。
In the chipping-resistant coating material, it is preferable to use a hydrazide compound as a curing agent for the urethane resin.
Since the hydrazide compound is a powder, it does not have a catalytic function to dissociate the blocking agent of the blocked isocyanate at room temperature, and is insoluble in the solvent used in the present invention. This is because there is no change in viscosity and good stability is obtained.
Further, the same chipping performance can be obtained even if the film thickness is reduced to, for example, about 2/3 as compared with the conventional chipping resistant paint. Moreover, compared with the conventional chipping-resistant agent, it can be cured at a low temperature, it has good resistance to cracking and can improve the cracking property of the thick-coated portion.
Furthermore, since the curing agent is a powder as compared with the conventional product, there is little migration of the curing agent to the paint, and the coating film can suppress yellowing.
Examples of the hydrazide compound include dodecanediohydrazide, isophthalic acid dihydrazide, carbohydrazide, semicarbazide hydrochloride, adipic acid dihydrazide, thiocarbohydrazide, sebacic acid dihydrazide, thiosemicarbazide hydrochloride, carbohydrazide, succinic acid dihydrazide, N, '-Hexamethylenebissemicarbazide or the like can be used.
次に、具体的実施例を比較例と共に説明する。
表１に示す配合で、ＳＰ値が８．７以下の溶剤を使用した実施例１乃至６のウレタン系耐チッピング塗料と、ＳＰ値が９．４以上の溶剤を使用した比較例１乃至３のウレタン系耐チッピング塗料とを、常法にしたがって作成した。
尚、前記ブロックドイソシアネートは、ＮＣＯ％が５．５％で、ブロック剤としてＭＥＫオキシムを用いた平均分子量３，０００のＭＤＩ系ブロックイソシアネートプレポリマーであり、ポリオールはＯＨ価８２０のポリエステルポリオールである。
溶剤Ａ〜Ｈは、以下の通りである。
Ａ：エクソンモービル社製ペガソール３０４０
Ｂ：エクソンモービル社製ベガソールＡＮ４５
Ｃ：ＭＩＢＫ（メチルイソブチルケトン）
Ｄ：シェルケミカルズ社製ＨＡＷＳ
Ｅ：丸善石油化学社製スワゾール１８００
Ｆ：丸善石油化学社製スワゾール１５００
Ｇ：エクソンモービル社製ソルベッツ１００
Ｈ：キシレン
Ｉ：ジオキシトールアセテート
Ｊ：シクロヘキサノン
Ｋ：ブチルジオキシトール
尚、実施例４及び１０では、ウレタン系樹脂の硬化剤として、ヒドラジド化合物として、大塚化学社製ドデカンジオヒドラジドを用いた。
Next, specific examples will be described together with comparative examples.
In the formulations shown in Table 1, the urethane-type chipping resistant paints of Examples 1 to 6 using a solvent having an SP value of 8.7 or less and those of Comparative Examples 1 to 3 using a solvent having an SP value of 9.4 or more. A urethane-based chipping resistant paint was prepared according to a conventional method.
The blocked isocyanate is an MDI block isocyanate prepolymer having an NCO% of 5.5% and an average molecular weight of 3,000 using MEK oxime as a blocking agent, and the polyol is a polyester polyol having an OH number of 820. .
Solvents A to H are as follows.
A: Pegasol 3040 manufactured by ExxonMobil
B: Vegasol AN45 manufactured by ExxonMobil
C: MIBK (methyl isobutyl ketone)
D: HAWS manufactured by Shell Chemicals
E: SWAZOL 1800 manufactured by Maruzen Petrochemical Co., Ltd.
F: SWAZOL 1500 manufactured by Maruzen Petrochemical Co., Ltd.
G: ExxonMobil Solvets 100
H: Xylene I: Dioxitol acetate J: Cyclohexanone K: Butyldioxitol In Examples 4 and 10, dodecandiohydrazide manufactured by Otsuka Chemical Co., Ltd. was used as a hydrazide compound as a curing agent for urethane resins.
次に、前記実施例及び比較例の耐チッピング塗料を用いて塗装を行い、未硬化電着塗料上のタレ、未硬化ウレタン系耐チッピング塗料上の中塗り塗料のタレ、未硬化ウレタン系耐チッピング塗料上の中塗り塗料のスケ、ウレタン系耐チッピング塗料のワキ性の各塗装特性について、観察、評価した。
尚、前記各塗装特性については、次のようにして観察、評価した。
Next, coating is performed using the chipping-resistant paints of the above-described Examples and Comparative Examples, and the sauce on the uncured electrodeposition paint, the sauce of the intermediate paint on the uncured urethane-based chipping paint, and the uncured urethane-based chipping-resistant We observed and evaluated the coating properties of the intermediate coating on the coating and the coating properties of the urethane-type chipping-resistant coating.
In addition, about each said coating characteristic, it observed and evaluated as follows.
ａ）未硬化電着塗料上のタレ
関西ペイント社製テストパネル上の１００℃でプレヒートされた未硬化電着塗料上にウレタン系耐チッピング塗料をＷＥＴ状態で４００μｍ塗布し、更に、水性中塗り塗料をＷＥＴ状態で２０μｍ塗布後、テストパネルを垂直に保持して６５℃×１０分、１７０℃×２０分の焼き付を行い、ウレタン系耐チッピング塗料のタレを目視観察し、次のように評価した。
○+：タレの発生がほとんどなく、スリップの発生なし
○：タレ長さ５ｍｍ以下でスリップの発生なし
×：タレ長さ５ｍｍ超えか、スリップの発生あり
a) Sauce on uncured electrodeposition paint Urethane-type chipping-resistant paint is applied in a wet state to 400 μm on an uncured electrodeposition paint preheated at 100 ° C. on a test panel manufactured by Kansai Paint Co. After applying 20μm in WET state, hold the test panel vertically and perform baking at 65 ° C x 10 minutes and 170 ° C x 20 minutes, visually observe the sagging of the urethane-based anti-chipping paint and evaluate as follows did.
○ + : Almost no sagging and no slipping ○: Sagging length of 5mm or less, no slipping ×: Sagging length exceeds 5mm or slipping
ｂ）未硬化ウレタン系耐チッピング塗料上の中塗り塗料のタレ
関西ペイント社製テストパネル上の１００℃でプレヒートされた未硬化電着塗料上にウレタン系耐チッピング塗料をＷＥＴ状態で３００μｍ塗布し、更に、水性中塗り塗料をＷＥＴ状態で２０μｍ塗布後、テストパネルを垂直に保持して６５℃×１０分、１７０℃×２０分の焼き付けを行い、ウレタン系耐チッピング塗料上の中塗り塗料のタレを目視観察し、次のように評価した。
○+：タレの発生がほとんどなし
○：中塗り塗料のタレ長さ５ｍｍ以下
×：中塗り塗料のタレ長さ５ｍｍ超え
b) Sauce of intermediate coating on uncured urethane-based chipping-resistant paint Apply urethane-type chipping-resistant paint 300 μm in wet state on uncured electrodeposition paint preheated at 100 ° C. on a test panel manufactured by Kansai Paint Co., Ltd. Further, after applying 20 μm of the water-based intermediate coating in the wet state, the test panel is held vertically and baked at 65 ° C. for 10 minutes and 170 ° C. for 20 minutes. Were visually observed and evaluated as follows.
○ + : Almost no occurrence of sagging ○: Sauce length of intermediate coating is 5 mm or less ×: Sauce length of intermediate coating exceeds 5 mm
ｃ）未硬化ウレタン系耐チッピング塗料上の中塗り塗料のスケ
関西ペイント社製テストパネル上の１００℃でプレヒートされた未硬化電着塗料上にウレタン系耐チッピング塗料をＷＥＴ状態で３００μｍ塗布し、更に、水性中塗り塗料をＷＥＴ状態で２０μｍ塗布後、テストパネルを垂直に保持して６５℃×１０分、１７０℃×２０分の焼き付けを行い、ウレタン系耐チッピング塗料上の中塗り塗料のスケを目視観察し、次のように評価した。
○：中塗り塗料のスケなし
○-：中塗り塗料のスケが若干見受けられる
×：中塗り塗料のスケあり
c) Scale of intermediate coating on uncured urethane-based anti-chipping coating Apply 300 μm of urethane-based anti-chipping coating on the uncured electrodeposition coating pre-heated at 100 ° C. on a test panel manufactured by Kansai Paint, Further, after applying 20 μm of the water-based intermediate coating in the wet state, the test panel is held vertically and baked at 65 ° C. for 10 minutes and 170 ° C. for 20 minutes. Were visually observed and evaluated as follows.
○: the intermediate coating without scale ○ -: × scale of the intermediate coating is seen slightly: Yes schedule of intermediate paint
ｄ）ウレタン系耐チッピング塗料のワキ性
関西ペイント社製テストパネル上の１００℃でプレヒートされた未硬化電着塗料上にウレタン系耐チッピング塗料をｄｒｙ状態で１００〜３００μｍとなるように塗布し、更に、水性中塗り塗料をＷＥＴ状態で２０μｍ塗布後、テストパネルを垂直に保持して６５℃×１０分、１７０℃×２０分の焼き付けを行い、ウレタン系耐チッピング塗料上のワキを目視観察し、次のように評価した。
○：ワキ限界２００μｍ以上
△：ワキ限界１５０μｍ以上２００μ未満
×：ワキ限界１５０未満
d) Extensibility of urethane-based chipping-resistant paint On the uncured electrodeposition paint preheated at 100 ° C. on a test panel manufactured by Kansai Paint Co., Ltd., a urethane-type chipping-resistant paint is applied in a dry state to be 100 to 300 μm. Furthermore, after applying 20 μm of water-based intermediate coating in the wet state, the test panel is held vertically and baked at 65 ° C. for 10 minutes and 170 ° C. for 20 minutes. The evaluation was as follows.
○: Waki limit 200 μm or more Δ: Waki limit 150 μm or more and less than 200 μ ×: Waki limit 150 or less
前記表１から明らかなように、ＳＰ値８．７以下の溶剤を用いた実施例１乃至１０の耐チッピング塗料は、未硬化電着塗料上のタレ、未硬化ウレタン系耐チッピング塗料上の中塗り塗料のタレ、未硬化ウレタン系耐チッピング塗料上の中塗り塗料のスケに優れ、特に、ウレタン系樹脂の硬化剤として、ヒドラジド化合物を使用した耐チッピング塗料である実施例３及び９では、ウレタン系耐チッピング塗料のワキ性に優れることが確認できた。 As is apparent from Table 1, the chipping resistant paints of Examples 1 to 10 using a solvent having an SP value of 8.7 or less are sagging on an uncured electrodeposition paint, Excellent in coating paint sagging and intermediate coating paint on uncured urethane-based chipping-resistant paints. In particular, in Examples 3 and 9, which are anti-chipping paints using a hydrazide compound as a curing agent for urethane-based resins, urethane is used. It was confirmed that the anti-chipping paint has excellent resistance to cracking.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005207787A JP5230060B2 (en) | 2005-07-15 | 2005-07-15 | Anti-chipping paint and method of applying anti-chipping paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005207787A JP5230060B2 (en) | 2005-07-15 | 2005-07-15 | Anti-chipping paint and method of applying anti-chipping paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007023165A true JP2007023165A (en) | 2007-02-01 |
| JP5230060B2 JP5230060B2 (en) | 2013-07-10 |
Family
ID=37784369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005207787A Expired - Fee Related JP5230060B2 (en) | 2005-07-15 | 2005-07-15 | Anti-chipping paint and method of applying anti-chipping paint |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5230060B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013087103A (en) * | 2011-10-20 | 2013-05-13 | Sekisui Chem Co Ltd | Hydrazide multimer, curable resin composition, sealing agent for one drop fill process, vertical conduction material, and liquid crystal display element |
Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04143295A (en) * | 1990-10-05 | 1992-05-18 | Kansai Paint Co Ltd | Formation of coated film |
| JPH04214783A (en) * | 1990-12-14 | 1992-08-05 | Dainippon Ink & Chem Inc | Chipping-resistant coating composition |
| JPH0610189A (en) * | 1992-06-26 | 1994-01-18 | Kansai Paint Co Ltd | Formation of coating film |
| JPH0617294A (en) * | 1992-07-02 | 1994-01-25 | Kansai Paint Co Ltd | Formation of coating film |
| JPH0641788A (en) * | 1992-07-23 | 1994-02-15 | Kansai Paint Co Ltd | Forming method of coating film |
| JPH0641787A (en) * | 1992-07-23 | 1994-02-15 | Kansai Paint Co Ltd | Forming method of coating film |
| JPH0688054A (en) * | 1992-09-09 | 1994-03-29 | Aisin Chem Co Ltd | Thick coating composition |
| JPH0693227A (en) * | 1992-09-11 | 1994-04-05 | Nippon Paint Co Ltd | Coating composition having chipping resistance and method for forming coating film having chipping resistance |
| JPH06254482A (en) * | 1993-03-04 | 1994-09-13 | Toyota Motor Corp | Printing method |
| JPH07228834A (en) * | 1994-02-17 | 1995-08-29 | Nippon Paint Co Ltd | Chipping-resistant coating composition and method for forming chipping-resistant composite coating film |
| JP2002126623A (en) * | 2000-10-20 | 2002-05-08 | Nissan Motor Co Ltd | Method for applying coating material for automobile by wet-on-wet coating |
| JP2002180000A (en) * | 2000-12-14 | 2002-06-26 | Nippon Paint Co Ltd | Chipping primer, method for forming double-layer coating film, and coated article |
| JP2002285388A (en) * | 2001-03-28 | 2002-10-03 | Nippon Paint Co Ltd | Method for forming multiply layered coating film |
| JP2002348532A (en) * | 2001-05-24 | 2002-12-04 | Kansai Paint Co Ltd | Aqueous coating material and method for forming multilayer coating film |
| WO2004050739A1 (en) * | 2002-12-02 | 2004-06-17 | Kyoeisha Chemical Co., Ltd. | Curable urethane resin composition |
| JP2004298837A (en) * | 2003-04-01 | 2004-10-28 | Nippon Paint Co Ltd | Formation method for multilayer coating film |
| JP2004322029A (en) * | 2003-04-28 | 2004-11-18 | Nissan Motor Co Ltd | Painting method |
| JP2005153232A (en) * | 2003-11-21 | 2005-06-16 | Toyoda Gosei Co Ltd | Manufacturing method for injection-molded product |
| JP2006026497A (en) * | 2004-07-14 | 2006-02-02 | Nippon Paint Co Ltd | Multi-layer coating film forming method |
-
2005
- 2005-07-15 JP JP2005207787A patent/JP5230060B2/en not_active Expired - Fee Related
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04143295A (en) * | 1990-10-05 | 1992-05-18 | Kansai Paint Co Ltd | Formation of coated film |
| JPH04214783A (en) * | 1990-12-14 | 1992-08-05 | Dainippon Ink & Chem Inc | Chipping-resistant coating composition |
| JPH0610189A (en) * | 1992-06-26 | 1994-01-18 | Kansai Paint Co Ltd | Formation of coating film |
| JPH0617294A (en) * | 1992-07-02 | 1994-01-25 | Kansai Paint Co Ltd | Formation of coating film |
| JPH0641788A (en) * | 1992-07-23 | 1994-02-15 | Kansai Paint Co Ltd | Forming method of coating film |
| JPH0641787A (en) * | 1992-07-23 | 1994-02-15 | Kansai Paint Co Ltd | Forming method of coating film |
| JPH0688054A (en) * | 1992-09-09 | 1994-03-29 | Aisin Chem Co Ltd | Thick coating composition |
| JPH0693227A (en) * | 1992-09-11 | 1994-04-05 | Nippon Paint Co Ltd | Coating composition having chipping resistance and method for forming coating film having chipping resistance |
| JPH06254482A (en) * | 1993-03-04 | 1994-09-13 | Toyota Motor Corp | Printing method |
| JPH07228834A (en) * | 1994-02-17 | 1995-08-29 | Nippon Paint Co Ltd | Chipping-resistant coating composition and method for forming chipping-resistant composite coating film |
| JP2002126623A (en) * | 2000-10-20 | 2002-05-08 | Nissan Motor Co Ltd | Method for applying coating material for automobile by wet-on-wet coating |
| JP2002180000A (en) * | 2000-12-14 | 2002-06-26 | Nippon Paint Co Ltd | Chipping primer, method for forming double-layer coating film, and coated article |
| JP2002285388A (en) * | 2001-03-28 | 2002-10-03 | Nippon Paint Co Ltd | Method for forming multiply layered coating film |
| JP2002348532A (en) * | 2001-05-24 | 2002-12-04 | Kansai Paint Co Ltd | Aqueous coating material and method for forming multilayer coating film |
| WO2004050739A1 (en) * | 2002-12-02 | 2004-06-17 | Kyoeisha Chemical Co., Ltd. | Curable urethane resin composition |
| JP2004298837A (en) * | 2003-04-01 | 2004-10-28 | Nippon Paint Co Ltd | Formation method for multilayer coating film |
| JP2004322029A (en) * | 2003-04-28 | 2004-11-18 | Nissan Motor Co Ltd | Painting method |
| JP2005153232A (en) * | 2003-11-21 | 2005-06-16 | Toyoda Gosei Co Ltd | Manufacturing method for injection-molded product |
| JP2006026497A (en) * | 2004-07-14 | 2006-02-02 | Nippon Paint Co Ltd | Multi-layer coating film forming method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013087103A (en) * | 2011-10-20 | 2013-05-13 | Sekisui Chem Co Ltd | Hydrazide multimer, curable resin composition, sealing agent for one drop fill process, vertical conduction material, and liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5230060B2 (en) | 2013-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wicks et al. | Blocked isocyanates III: Part B: Uses and applications of blocked isocyanates | |
| JP5870938B2 (en) | Aqueous polyurethane resin dispersion and use thereof | |
| KR101024131B1 (en) | Method for forming plural-layered coated film | |
| JPWO2005075587A1 (en) | Water-based intermediate coating composition and method for forming multilayer coating film | |
| JP6015747B2 (en) | Aqueous polyurethane resin dispersion | |
| JP7028018B2 (en) | Aqueous polyurethane resin dispersion and its use | |
| TW201708388A (en) | Aqueous urethane resin composition and articles | |
| JP2012116879A (en) | Aqueous intermediate coating composition and method for forming multilayer coating film | |
| JP5546121B2 (en) | Coating composition and coated article | |
| JP2002506113A5 (en) | ||
| JPWO2015033939A1 (en) | Aqueous polyurethane resin dispersion and use thereof | |
| JP5230060B2 (en) | Anti-chipping paint and method of applying anti-chipping paint | |
| JP2008229433A (en) | Method for forming multilayer coating film | |
| JP7064291B2 (en) | Cationic electrodeposition coating composition | |
| JP6546932B2 (en) | Thermosetting paint composition | |
| JP5607479B2 (en) | Aqueous primer composition | |
| JP6183124B2 (en) | Aqueous polyurethane resin dispersion | |
| US11566147B2 (en) | Polyurethane coating composition | |
| JP2005298694A (en) | Coating composition for pre-coated steel plate and pre-coated steel plate using the same | |
| JP2018159031A (en) | Cationic electrodeposition paint composition | |
| WO2012039217A1 (en) | Aqueous primer composition, method for forming multi layer coating and coated article | |
| JP2008202122A (en) | Method for forming cured electrodeposition coating film and method for forming multiple layer coating film | |
| JP2008231452A (en) | Method for depositing multilayer coating film | |
| JP2007039659A (en) | Adhesiveness imparting agent | |
| JP2004209791A (en) | Precoated steel plate excellent in environmental consistency and corrosion resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20071213 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110426 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110616 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120321 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130305 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130319 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160329 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5230060 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |