JP2008208339A - Cationic electrodeposition coating composition and coated article coated with electrodeposition coating material - Google Patents
Cationic electrodeposition coating composition and coated article coated with electrodeposition coating material Download PDFInfo
- Publication number
- JP2008208339A JP2008208339A JP2008003898A JP2008003898A JP2008208339A JP 2008208339 A JP2008208339 A JP 2008208339A JP 2008003898 A JP2008003898 A JP 2008003898A JP 2008003898 A JP2008003898 A JP 2008003898A JP 2008208339 A JP2008208339 A JP 2008208339A
- Authority
- JP
- Japan
- Prior art keywords
- electrodeposition coating
- resin
- amide
- coating composition
- compound
- 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
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- 238000004070 electrodeposition Methods 0.000 title claims abstract description 70
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 67
- 239000008199 coating composition Substances 0.000 title claims abstract description 35
- 238000000576 coating method Methods 0.000 title abstract description 54
- 239000011248 coating agent Substances 0.000 title abstract description 53
- 239000000463 material Substances 0.000 title description 3
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 80
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 80
- 150000001875 compounds Chemical class 0.000 claims abstract description 68
- 229920005989 resin Polymers 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims abstract description 58
- 150000001412 amines Chemical class 0.000 claims abstract description 47
- 150000001408 amides Chemical class 0.000 claims abstract description 44
- 239000002981 blocking agent Substances 0.000 claims abstract description 36
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920000647 polyepoxide Polymers 0.000 claims description 42
- 239000003822 epoxy resin Substances 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- 125000003277 amino group Chemical group 0.000 claims description 16
- OIAUFEASXQPCFE-UHFFFAOYSA-N formaldehyde;1,3-xylene Chemical compound O=C.CC1=CC=CC(C)=C1 OIAUFEASXQPCFE-UHFFFAOYSA-N 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000008096 xylene Substances 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
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- 239000008397 galvanized steel Substances 0.000 abstract description 8
- 229910001297 Zn alloy Inorganic materials 0.000 abstract 1
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- -1 propylene glycol monoalkyl ether Chemical class 0.000 description 33
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- 238000012360 testing method Methods 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
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- 229920000768 polyamine Polymers 0.000 description 13
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- 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 12
- 201000006747 infectious mononucleosis Diseases 0.000 description 12
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- 239000006185 dispersion Substances 0.000 description 10
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 9
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
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- 239000003054 catalyst Substances 0.000 description 5
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- 229910021641 deionized water Inorganic materials 0.000 description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 235000019256 formaldehyde Nutrition 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
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- 239000004848 polyfunctional curative Substances 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 4
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 241000282320 Panthera leo Species 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 229930003836 cresol Natural products 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-Butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 235000014692 zinc oxide Nutrition 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 150000008431 aliphatic amides Chemical class 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
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- 238000006482 condensation reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 3
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- 239000000758 substrate Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 2
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
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Images
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Abstract
Description
本発明は、つきまわり性、合金化溶融亜鉛メッキ鋼板上の電着塗装適性、仕上り性及び防食性に優れたカチオン電着塗料組成物に関する。 The present invention relates to a cationic electrodeposition coating composition excellent in throwing power, suitability for electrodeposition coating on an alloyed hot-dip galvanized steel sheet, finish and corrosion resistance.
従来のブロック化ポリイソシアネートを含むカチオン性塗料組成物としては、アミノ基、アンモニウム基、ホスホニウム基、スルホニウム基などのカチオン性基又は中和されたこれらのカチオン性基を有する基体樹脂と、架橋剤（硬化剤）であるブロック化ポリイソシアネートとを含むカチオン電着塗料組成物が挙げられる。 Conventional cationic coating compositions containing blocked polyisocyanates include base resins having cationic groups such as amino groups, ammonium groups, phosphonium groups, sulfonium groups, or neutralized cationic groups, and crosslinking agents. And a cationic electrodeposition coating composition containing a blocked polyisocyanate which is a (curing agent).
上記カチオン電着塗料組成物のブロック化ポリイソシアネート化合物としては、塗膜の防食性や塗料安定性の観点からブロック化剤として、アルコール系、エーテルアルコール系及びオキシム系等が用いられている。
従来、上記ブロック化ポリイソシアネートとしては、芳香族イソシアヌレート環と、ブロックされた３つ以上のイソシアネート基とを有し、かつ上記ブロック化イソシアネート基の少なくとも１つが、グリコールエーテルによりブロックされているものが開示されている（特許文献１）。
As the blocked polyisocyanate compound of the cationic electrodeposition coating composition, alcohol-based, ether-alcohol-based, oxime-based, and the like are used as blocking agents from the viewpoint of corrosion resistance of the coating film and coating stability.
Conventionally, the blocked polyisocyanate has an aromatic isocyanurate ring and three or more blocked isocyanate groups, and at least one of the blocked isocyanate groups is blocked with a glycol ether. Is disclosed (Patent Document 1).
また、カチオン性基を有するエポキシ変性基体樹脂およびブロックイソシアネート硬化剤を含むカチオン電着塗料組成物において、前記ブロックイソシアネート硬化剤のブロック剤として、プロピレングリコールモノアルキルエーテルを用いた発明が開示されている（特許文献２）。 Further, in a cationic electrodeposition coating composition containing an epoxy-modified base resin having a cationic group and a blocked isocyanate curing agent, an invention using propylene glycol monoalkyl ether as a blocking agent for the blocked isocyanate curing agent is disclosed. (Patent Document 2).
さらに、カチオン性樹脂（Ａ）と、互いに反応性の異なる２個の水酸基を有する分子量７６〜１５０のジオール成分を含有するブロック剤にてポリイソシアネート化合物がブロック化されてなるブロック化ポリイソシアネートとを含有するカチオン性塗料組成物が開示されている（特許文献３）。 Further, a cationic resin (A) and a blocked polyisocyanate obtained by blocking a polyisocyanate compound with a blocking agent containing a diol component having a molecular weight of 76 to 150 having two hydroxyl groups having different reactivity. A cationic coating composition is disclosed (Patent Document 3).
さらに、乾きムラ性や水滴跡性等の塗装作業性を向上させることを目的として、天然脂肪酸アミンまたはアミド誘導体を、カチオン電着塗料組成物中の樹脂固形分１００重量部に対して０．１〜３．０重量部含有するカチオン電着塗料組成物が開示されている（特許文献４）。 Furthermore, for the purpose of improving the coating workability such as drying unevenness and water drop property, the natural fatty acid amine or amide derivative is added in an amount of 0.1 to 100 parts by weight of the resin solid content in the cationic electrodeposition coating composition. A cationic electrodeposition coating composition containing ˜3.0 parts by weight is disclosed (Patent Document 4).
しかし、特許文献１〜４に挙げられたブロック化ポリイソシアネートを含むカチオン性塗料組成物は、高いつきまわり性を得るために高電圧を印加すると合金化溶融亜鉛メッキ鋼板上へのピンホール発生の抑制、仕上り性又は防食性のいずれかが不十分となることがあった。
However, the cationic coating composition containing the blocked polyisocyanate listed in
本発明の目的は、つきまわり性、合金化溶融亜鉛メッキ鋼板上の電着塗装適性、仕上り性及び防食性に優れたカチオン電着塗料組成物を提供することである。 An object of the present invention is to provide a cationic electrodeposition coating composition that is excellent in throwing power, suitability for electrodeposition coating on an alloyed hot-dip galvanized steel sheet, finish and corrosion resistance.
本発明者らは、上記の課題を解決するために鋭意検討した結果、カチオン性樹脂（Ａ）及びイソシアネート基を２個以上有するポリイソシアネート化合物（ｂ１）と、アミドまたはアミン誘導体（ｂ２）と、ブロック剤（ｂ３）とを反応させて得られたブロック化ポリイソシアネート（Ｂ）を含有するカチオン電着塗料組成物を見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that the cationic resin (A) and a polyisocyanate compound (b1) having two or more isocyanate groups, an amide or amine derivative (b2), A cationic electrodeposition coating composition containing the blocked polyisocyanate (B) obtained by reacting with the blocking agent (b3) was found, and the present invention was completed.
カチオン電着塗料に使用するブロック化ポリイソシアネート（Ｂ）中の特定のアミドまたはアミン誘導体（ｂ２）によって、電着塗膜の析出開始が早くなり、さらに塗膜の融着性及び被塗物への密着性が良好となる。 The specific amide or amine derivative (b2) in the blocked polyisocyanate (B) used for the cationic electrodeposition paint accelerates the deposition start of the electrodeposition coating film, and further improves the fusing property of the coating film and the object to be coated. The adhesiveness of is improved.
具体的には、電着塗膜の析出開始が早く、かつ塗膜の融着性が良好なため高電圧を印加することが可能となるので「つきまわり性」が向上する。さらに塗膜の融着性及び被塗物への密着性が良好となるので、合金化溶融亜鉛メッキ鋼板の電着塗装時に発生するスパークにも耐え得る丈夫な析出膜を形成することができ「合金化溶融亜鉛メッキ鋼板の電着塗装適性」に優れ、かつ仕上り性や防食性が良好な塗装物品を得ることができる。 Specifically, since the deposition start of the electrodeposition coating film is early and the adhesion property of the coating film is good, it is possible to apply a high voltage, thereby improving the “throwing power”. Furthermore, since the adhesion of the coating film and the adhesion to the object are improved, it is possible to form a strong deposited film that can withstand the sparks generated during electrodeposition coating of galvannealed steel sheets. It is possible to obtain a coated article that is excellent in “electrodeposition coating properties of galvannealed steel sheet” and has good finish and corrosion resistance.
本発明のカチオン電着塗料組成物は、カチオン性樹脂（Ａ）、及びイソシアネート基を２個以上有するポリイソシアネート化合物（ｂ１）に、特定のアミドまたはアミン誘導体（ｂ２）と、ブロック剤（ｂ３）とを反応させて得られるブロック化ポリイソシアネート（Ｂ）を含有する。以下、各成分について、詳しく説明する。 The cationic electrodeposition coating composition of the present invention comprises a cationic resin (A), a polyisocyanate compound (b1) having two or more isocyanate groups, a specific amide or amine derivative (b2), and a blocking agent (b3). The blocked polyisocyanate (B) obtained by reacting with. Hereinafter, each component will be described in detail.
［カチオン性樹脂（Ａ）］
カチオン性樹脂（Ａ）は、分子中にアミノ基、アンモニウム塩基、スルホニウム塩基、ホスホニウム塩基などのカチオン化可能な基を有する樹脂であり、樹脂種としては、通常使用されているもの、例えば、エポキシ樹脂、アクリル樹脂、ポリブタジエン樹脂、アルキド樹脂、ポリエステル樹脂などが挙げられる。特に、エポキシ樹脂にアミノ基含有化合物を付加反応させて得られるアミン付加エポキシ樹脂が防食性、合金化溶融メッキ鋼板上の電着塗装適性の両立から好適である。
[Cationic resin (A)]
The cationic resin (A) is a resin having a cationizable group such as an amino group, an ammonium base, a sulfonium base, or a phosphonium base in the molecule. Examples thereof include resins, acrylic resins, polybutadiene resins, alkyd resins, and polyester resins. In particular, an amine-added epoxy resin obtained by addition reaction of an amino group-containing compound with an epoxy resin is suitable from the viewpoint of both corrosion resistance and suitability for electrodeposition coating on an alloyed hot-dip steel sheet.
上記のアミン付加エポキシ樹脂としては、例えば、（１）エポキシ樹脂と第１級モノ−及びポリアミン、第２級モノ−及びポリアミン又は第１、２級混合ポリアミンとの付加物（例えば、米国特許第３，９８４，２９９号明細書参照）；（２）エポキシ樹脂とケチミン化された第１級アミノ基を有する第２級モノ−及びポリアミンとの付加物（例えば、米国特許第４，０１７，４３８号 明細書参照）；（３）エポキシ樹脂とケチミン化された第１級アミノ基を有するヒドロキシ化合物とのエーテル化により得られる反応物（例えば、特開昭５９−４３０１３号公報参照）等を挙げることができる。 Examples of the above amine-added epoxy resins include (1) adducts of epoxy resins with primary mono- and polyamines, secondary mono- and polyamines, or primary and secondary mixed polyamines (for example, US Pat. No. 3,984,299); (2) Adducts of epoxy resins with secondary mono- and polyamines having ketiminated primary amino groups (eg, US Pat. No. 4,017,438). (3) Reactants obtained by etherification of an epoxy resin and a ketiminated hydroxy compound having a primary amino group (for example, see JP-A-59-43013) be able to.
上記のアミン付加エポキシ樹脂の製造に使用されるエポキシ樹脂は、１分子中にエポキシ基を少なくとも１個、好ましくは２個以上有する化合物であり、その分子量は一般に少なくとも３００、好ましくは４００〜４，０００、さらに好ましくは８００〜２，５００の範囲内の［数平均分子量］及び少なくとも１６０、好ましくは１８０〜２，５００、さらに好ましくは４００〜１，５００の範囲内のエポキシ当量を有するものが適しており、特に、ポリフェノール化合物とエピハロヒドリンとの反応によって得られるものが好ましい。 The epoxy resin used in the production of the amine-added epoxy resin is a compound having at least one, preferably two or more epoxy groups in one molecule, and its molecular weight is generally at least 300, preferably 400 to 4, preferably. Having a [number average molecular weight] in the range of 000, more preferably in the range of 800 to 2,500 and an epoxy equivalent weight in the range of at least 160, preferably 180 to 2,500, more preferably 400 to 1,500 In particular, those obtained by reaction of a polyphenol compound and epihalohydrin are preferred.
ここで、「数平均分子量」は、ＪＩＳ Ｋ ０１２４−８３に記載の方法に準じ、分離カラムとして「ＴＳＫ ＧＥＬ４０００ＨＸＬ」、「ＴＳＫ Ｇ３０００ＨＸＬ」、「ＴＳＫ Ｇ２５００ＨＸＬ」、「ＴＳＫ Ｇ２０００ＨＸＬ」（東ソー株式会社製）の４本を用いて、溶離液としてＧＰＣ用テトラヒドロフランを用いて４０℃及び流速１．０ｍｌ／分において、ＲＩ屈折計で得られたクロマトグラムと標準ポリスチレンの検量線から求めた。 Here, the “number average molecular weight” is “TSK GEL4000HXL”, “TSK G3000HXL”, “TSK G2500HXL”, “TSK G2000HXL” (manufactured by Tosoh Corporation) according to the method described in JIS K 0124-83. Were obtained from a chromatogram obtained with an RI refractometer and a standard polystyrene calibration curve at 40 ° C. and a flow rate of 1.0 ml / min using tetrahydrofuran for GPC as an eluent.
該エポキシ樹脂の形成のために用いられるポリフェノール化合物としては、例えば、ビス（４−ヒドロキシフェニル）−２，２−プロパン［ビスフェノールＡ］、ビス（４−ヒドロキシフェニル）メタン［ビスフェノールＦ］、ビス（４−ヒドロキシシクロヘキシル）メタン［水添ビスフェノールＦ］、２，２−ビス（４−ヒドロキシシクロヘキシル）プロパン［水添ビスフェノールＡ］、４，４’−ジヒドロキシベンゾフェノン、ビス（４−ヒドロキシフェニル）−１，１−エタン、ビス（４−ヒドロキシフェニル）−１，１−イソブタン、ビス（４−ヒドロキシ−３−ｔｅｒｔ−ブチル−フェニル）−２，２−プロパン、ビス（２−ヒドロキシナフチル）メタン、テトラ（４−ヒドロキシフェニル）−１，１，２，２−エタン、４，４’−ジヒドロキシジフェニルスルホン、フェノールノボラック、クレゾールノボラックなどを挙げることができる。 Examples of the polyphenol compound used for forming the epoxy resin include bis (4-hydroxyphenyl) -2,2-propane [bisphenol A], bis (4-hydroxyphenyl) methane [bisphenol F], bis ( 4-hydroxycyclohexyl) methane [hydrogenated bisphenol F], 2,2-bis (4-hydroxycyclohexyl) propane [hydrogenated bisphenol A], 4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) -1, 1-ethane, bis (4-hydroxyphenyl) -1,1-isobutane, bis (4-hydroxy-3-tert-butyl-phenyl) -2,2-propane, bis (2-hydroxynaphthyl) methane, tetra ( 4-hydroxyphenyl) -1,1,2,2-ethane, 4,4 ′ Dihydroxydiphenyl sulfone, phenol novolak, and the like cresol novolak.
また、ポリフェノール化合物とエピクロルヒドリンとの反応によって得られるエポキシ樹脂としては、中でも、ビスフェノールＡから誘導される下記式の樹脂が好適である。 Moreover, as an epoxy resin obtained by reaction of a polyphenol compound and epichlorohydrin, the resin of the following formula induced | guided | derived from bisphenol A is suitable especially.
ここで、ｎ＝０〜８で示されるものが好適である。
かかるエポキシ樹脂の市販品としては、例えば、ジャパンエポキシレジン（株）からｊＥＲ８２８ＥＬ、ｊＥＲ１００２、ｊＥＲ１００４、ｊＥＲ１００７なる商品名で販売されているものが挙げられる。
Here, what is shown by n = 0-8 is suitable.
Examples of commercially available epoxy resins include those sold by Japan Epoxy Resins Co., Ltd. under the trade names jER828EL, jER1002, jER1004, and jER1007.
該エポキシ樹脂は、ポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリアミドアミン、ポリカルボン酸、ポリイソシアネート化合物などと部分的に反応させたものであってもよく、さらにまた、ε−カプロラクトンなどのラクトン類、アクリルモノマーなどをグラフト重合させたものであってもよい。 The epoxy resin may be partially reacted with a polyol, a polyether polyol, a polyester polyol, a polyamidoamine, a polycarboxylic acid, a polyisocyanate compound or the like, and a lactone such as ε-caprolactone, An acrylic monomer or the like may be graft-polymerized.
上記（１）のアミン付加エポキシ樹脂の製造に使用される第１級モノ−及びポリアミン、第２級モノ−及びポリアミン又は第１、２級混合ポリアミンとしては、例えば、モノメチルアミン、ジメチルアミン、モノエチルアミン、ジエチルアミン、モノイソプロピルアミン、ジイソプロピルアミン、モノブチルアミン、ジブチルアミンなどのモノ−もしくはジ−アルキルアミン；モノエタノールアミン、ジエタノールアミン、モノ（２−ヒドロキシプロピル）アミン、モノメチルアミノエタノールなどのアルカノールアミン；エチレンジアミン、プロピレンジアミン、ブチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミンなどのアルキレンポリアミンなどを挙げることができる。 Examples of the primary mono- and polyamines, secondary mono- and polyamines, and primary and secondary mixed polyamines used in the production of the amine-added epoxy resin of (1) above include monomethylamine, dimethylamine, and monoamine. Mono- or di-alkylamines such as ethylamine, diethylamine, monoisopropylamine, diisopropylamine, monobutylamine, dibutylamine; alkanolamines such as monoethanolamine, diethanolamine, mono (2-hydroxypropyl) amine, monomethylaminoethanol; ethylenediamine And alkylene polyamines such as propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.
上記（２）のアミン付加エポキシ樹脂の製造に使用されるケチミン化された第１級アミノ基を有する第２級モノ−及びポリアミンとしては、例えば、上記（１）のアミン付加エポキシ樹脂の製造に使用される第１、２級混合ポリアミンのうち、例えば、ジエチレントリアミンなどにケトン化合物を反応させて生成させたケチミン化物を挙げることができる。 Examples of the secondary mono- and polyamines having a ketimized primary amino group used in the production of the amine-added epoxy resin (2) include, for example, the production of the amine-added epoxy resin (1). Among the primary and secondary mixed polyamines used, for example, ketimine compounds produced by reacting a ketone compound with diethylenetriamine or the like can be mentioned.
上記（３）のアミン付加エポキシ樹脂の製造に使用されるケチミン化された第１級アミノ基を有するヒドロキシ化合物としては、例えば、上記（１）のアミン付加エポキシ樹脂の製造に使用される第１級モノ−及びポリアミン、第２級モノ−及びポリアミン又は第１、２級混合ポリアミンのうち、第１級アミノ基とヒドロキシル基を有する化合物、例えば、モノエタノールアミン、モノ（２−ヒドロキシプロピル）アミンなどにケトン化合物を反応させてなるヒドロキシル基含有ケチミン化物を挙げることができる。 Examples of the hydroxy compound having a ketiminated primary amino group used in the production of the amine-added epoxy resin (3) include, for example, a first compound used in the production of the amine-added epoxy resin (1). Of primary mono- and polyamines, secondary mono- and polyamines or primary and secondary mixed polyamines, compounds having a primary amino group and a hydroxyl group, such as monoethanolamine, mono (2-hydroxypropyl) amine Examples thereof include a hydroxyl group-containing ketimine compound obtained by reacting a ketone compound with the above.
特に、カチオン性樹脂（Ａ）として、エポキシ当量が１８０〜２，５００、好ましくは２５０〜２，０００のエポキシ樹脂に、フェノール性水酸基を有するキシレンホルムアルデヒド樹脂及びアミノ基含有化合物を反応させて得られるキシレン樹脂変性アミン付加エポキシ樹脂であって、アミノ基含有化合物の使用割合が、エポキシ樹脂、キシレンホルムアルデヒド樹脂及びアミノ基含有化合物の合計固形分質量を基準にして５〜２５質量％であるキシレン樹脂変性アミン付加エポキシ樹脂を用いることが、本発明の効果を得るにはよい。 In particular, the cationic resin (A) is obtained by reacting an epoxy resin having an epoxy equivalent of 180 to 2,500, preferably 250 to 2,000, with a xylene formaldehyde resin having a phenolic hydroxyl group and an amino group-containing compound. Xylene resin-modified amine-added epoxy resin, wherein the proportion of amino group-containing compound used is 5 to 25% by mass based on the total solid mass of the epoxy resin, xylene formaldehyde resin and amino group-containing compound Use of an amine-added epoxy resin is good for obtaining the effects of the present invention.
上記アミノ基含有エポキシ樹脂の製造のための出発材料として用いられるエポキシ樹脂としては、前記のカチオン性樹脂について述べたものと同様のエポキシ樹脂を用いることができる。 As the epoxy resin used as a starting material for the production of the amino group-containing epoxy resin, the same epoxy resin as described for the cationic resin can be used.
キシレンホルムアルデヒド樹脂は、エポキシ樹脂の内部可塑化（変性）に役立つものであり、例えばキシレン及びホルムアルデヒド類ならびにフェノール類を酸性触媒の存在下で縮合反応させることにより製造することができる。 The xylene formaldehyde resin is useful for internal plasticization (modification) of the epoxy resin, and can be produced, for example, by subjecting xylene, formaldehyde and phenols to a condensation reaction in the presence of an acidic catalyst.
上記のホルムアルデヒド類としては、工業的に入手容易なホルマリン、パラホルムアルデヒドを例示することができる。さらに、ホルムアルデヒド類を直接添加するだけでなく、トリオキサン等のホルムアルデヒド類を発生する化合物等を上記樹脂の合成に用いることができる。 Examples of the formaldehydes include formalin and paraformaldehyde which are industrially easily available. Furthermore, not only formaldehydes are directly added, but also compounds such as trioxane that generate formaldehyde can be used for the synthesis of the resin.
さらに、上記のフェノール類には、２又は３個の反応部位を持つ１もしくは２価のフェノール性化合物が包含され、具体的には、例えば、フェノール、クレゾール、パラ−オクチルフェノール、ノニルフェノール、ビスフェノールプロパン、ビスフェノールメタン、レゾルシン、ピロカテコール、ハイドロキノン、パラ−ｔｅｒｔ−ブチルフェノール、ビスフェノールスルホン、ビスフェノールエーテル、パラ−フェニルフェノール等が挙げられ、これらはそれぞれ単独で又は２種以上組み合わせて用いることができる。この中で特に、フェノール、クレゾールが好適である。 Further, the above phenols include mono- or divalent phenolic compounds having 2 or 3 reaction sites, specifically, for example, phenol, cresol, para-octylphenol, nonylphenol, bisphenolpropane, Bisphenol methane, resorcin, pyrocatechol, hydroquinone, para-tert-butylphenol, bisphenol sulfone, bisphenol ether, para-phenylphenol and the like can be mentioned, and these can be used alone or in combination of two or more. Of these, phenol and cresol are particularly preferred.
上記キシレン及びホルムアルデヒド類ならびにフェノール類の縮合反応に使用される酸性触媒としては、例えば、硫酸、塩酸、パラトルエンスルホン酸及びシュウ酸等が挙げられるが、一般的には、特に硫酸が特に好適である。 Examples of the acidic catalyst used in the condensation reaction of xylene, formaldehydes, and phenols include sulfuric acid, hydrochloric acid, paratoluenesulfonic acid, and oxalic acid. In general, sulfuric acid is particularly preferable. is there.
縮合反応は、例えば、反応系に存在するキシレン、フェノール類、水、ホルマリン等が還流する温度、通常、約８０〜約１００℃の温度に加熱することにより行うことができ、通常、２〜６時間程度で終了させることができる。 The condensation reaction can be performed, for example, by heating to a temperature at which xylene, phenols, water, formalin and the like existing in the reaction system are refluxed, usually about 80 to about 100 ° C. It can be completed in about hours.
上記条件下で、キシレン及びホルムアルデヒド類及びさらに場合によりフェノール類を酸性触媒の存在下で加熱反応させることによって、キシレンホルムアルデヒド樹脂を得ることができる。 Under the above conditions, xylene-formaldehyde resin can be obtained by heat-reacting xylene and formaldehyde, and optionally phenols in the presence of an acidic catalyst.
かくして得られるキシレンホルムアルデヒド樹脂は、一般に、２０〜５０，０００ｍＰａ・ｓ（２５℃）、好ましくは２５〜３０，０００、さらに好ましくは３０〜１５，０００ｍＰａ・ｓ（２５℃）の範囲内の粘度を有することができ、そして一般に１００〜５０，０００、特に１５０〜３０，０００、さらに特に２００〜１０，０００の範囲内の水酸基当量を有していることが好ましい。 The xylene formaldehyde resin thus obtained generally has a viscosity in the range of 20 to 50,000 mPa · s (25 ° C.), preferably 25 to 30,000, more preferably 30 to 15,000 mPa · s (25 ° C.). And preferably have a hydroxyl equivalent weight in the range of from 100 to 50,000, in particular from 150 to 30,000, more particularly from 200 to 10,000.
アミノ基含有化合物は、エポキシ樹脂にアミノ基を導入して、該エポキシ樹脂をカチオン性化するためのカチオン性基付与化合物であり、前記カチオン性樹脂の製造の際に用いたものと同様のものを用いることができる。 The amino group-containing compound is a cationic group-imparting compound for introducing an amino group into an epoxy resin to make the epoxy resin cationic, and is the same as that used in the production of the cationic resin. Can be used.
前記エポキシ樹脂に対する上記のキシレンホルムアルデヒド樹脂及びアミノ基含有化合物の反応は任意の順序で行うことができるが、一般には、エポキシ樹脂に対して、キシレンホルムアルデヒド樹脂及びアミノ基含有化合物を同時に付加反応させるのが好適である。 Although the reaction of the xylene formaldehyde resin and the amino group-containing compound with the epoxy resin can be performed in any order, generally, the xylene formaldehyde resin and the amino group-containing compound are simultaneously added to the epoxy resin. Is preferred.
上記の付加反応は、通常、適当な溶媒中で、約８０〜約１７０℃、好ましくは約９０〜約１５０℃の温度で１〜６時間程度、好ましくは１〜５時間程度行うことができる。上記の溶媒としては、例えば、トルエン、キシレン、シクロヘキサン、ｎ−ヘキサンなどの炭化水素系溶媒；酢酸メチル、酢酸エチル、酢酸ブチルなどのエステル系溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルアミルケトンなどのケトン系溶媒；ジメチルホルムアミド、ジメチルアセトアミドなどのアミド系溶媒；メタノール、エタノール、ｎ−プロパノール、ｉｓｏ−プロパノールなどのアルコール系溶媒；あるいはこれらの混合物などが挙げられる。 The above addition reaction can be usually performed in a suitable solvent at a temperature of about 80 to about 170 ° C., preferably about 90 to about 150 ° C. for about 1 to 6 hours, preferably about 1 to 5 hours. Examples of the solvent include hydrocarbon solvents such as toluene, xylene, cyclohexane, and n-hexane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone. Ketone solvents; amide solvents such as dimethylformamide and dimethylacetamide; alcohol solvents such as methanol, ethanol, n-propanol, and iso-propanol; or a mixture thereof.
上記の付加反応における各反応成分の使用割合は、厳密に制限されるものではなく適宜変えることができるが、エポキシ樹脂、キシレンホルムアルデヒド樹脂及びアミノ基含有化合物の３成分の合計固形分質量を基準にして以下の範囲内が適当である。
すなわち、エポキシ樹脂は、一般に５０〜９０質量％、好ましくは５０〜８５質量％；キシレンホルムアルデヒド樹脂は、一般に５〜４５質量％、好ましくは６〜４３質量％；アミノ基含有化合物は、一般に５〜２５質量％、好ましくは６〜２０質量％の範囲内で用いることが好ましい。
The use ratio of each reaction component in the above addition reaction is not strictly limited and can be appropriately changed. However, based on the total solid mass of the three components of epoxy resin, xylene formaldehyde resin and amino group-containing compound. The following range is appropriate.
That is, the epoxy resin is generally 50 to 90% by mass, preferably 50 to 85% by mass; the xylene formaldehyde resin is generally 5 to 45% by mass, preferably 6 to 43% by mass; It is preferably used within a range of 25% by mass, preferably 6 to 20% by mass.
上記のカチオン性樹脂がアミノ基を有する場合には、ギ酸、酢酸、プロピオン酸、乳酸等の有機カルボン酸；塩酸、硫酸などの無機酸などの酸を用いて中和して、水溶化又は水分散化することができる。 When the cationic resin has an amino group, it is neutralized with an organic carboxylic acid such as formic acid, acetic acid, propionic acid, or lactic acid; an acid such as hydrochloric acid, sulfuric acid, or the like; Can be decentralized.
［ブロック化ポリイソシアネート（Ｂ）］
本発明のカチオン電着塗料組成物は、架橋剤として、イソシアネート基を２個以上有するポリイソシアネート化合物（ｂ１）に、特定のアミドまたはアミン誘導体（ｂ２）とブロック剤（ｂ３）を反応させてなるブロック化ポリイソシアネート（Ｂ）を含有することが、つきまわり性、合金化溶融メッキ鋼板上の電着塗装適性、仕上り性及び防食性の面から好ましい。
[Blocked polyisocyanate (B)]
The cationic electrodeposition coating composition of the present invention is obtained by reacting a specific amide or amine derivative (b2) and a blocking agent (b3) with a polyisocyanate compound (b1) having two or more isocyanate groups as a crosslinking agent. It is preferable to contain the blocked polyisocyanate (B) from the viewpoints of throwing power, suitability for electrodeposition coating on an alloyed hot dip plated steel sheet, finish and corrosion resistance.
［ポリイソシアネート化合物（ｂ１）］
ブロック化ポリイソシアネート（Ｂ）で使用されるポリイソシアネート化合物（ｂ１）としては、公知のものを使用することができ、例えば、トリレンジイソシアネート、キシリレンジイソシアネート、フェニレンジイソシアネート、ジフェニルメタン−２，２’−ジイソシアネート、ジフェニルメタン−２，４’−ジイソシアネート、ジフェニルメタン−４，４’−ジイソシアネート、クルードＭＤＩ（「ポリメチレンポリフェニルイソシアネート」）、ビス（イソシアネートメチル）シクロヘキサン、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、メチレンジイソシアネート、イソホロンジイソシアネートなどの芳香族、脂肪族又は脂環族ポリイソシアネート化合物；これらのポリイソシアネート化合物の環化重合体又はビゥレット体；又はこれらの組合せを挙げることができる。
[Polyisocyanate compound (b1)]
As the polyisocyanate compound (b1) used in the blocked polyisocyanate (B), known compounds can be used. For example, tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, diphenylmethane-2,2'- Diisocyanate, diphenylmethane-2,4′-diisocyanate, diphenylmethane-4,4′-diisocyanate, crude MDI (“polymethylene polyphenyl isocyanate”), bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, Aromatic, aliphatic or alicyclic polyisocyanate compounds such as isophorone diisocyanate; cyclized polymers of these polyisocyanate compounds The biuret thereof; may be mentioned, or a combination thereof.
特に、トリレンジイソシアネート、キシリレンジイソシアネート、フェニレンジイソシアネート、ジフェニルメタン−２，４’−ジイソシアネート、ジフェニルメタン−４，４’−ジイソシアネート、クルードＭＤＩ等の芳香族ポリイソシアネート化合物が、防食性の観点から特に好適である。 In particular, aromatic polyisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, diphenylmethane-2,4′-diisocyanate, diphenylmethane-4,4′-diisocyanate, and crude MDI are particularly suitable from the viewpoint of corrosion resistance. is there.
［特定のアミドまたはアミン誘導体（ｂ２）］
ブロック化ポリイソシアネート（Ｂ）で使用される特定のアミンまたはアミド誘導体（ｂ２）としては、下記式（１）又は下記式（２）
[Specific amide or amine derivative (b2)]
As the specific amine or amide derivative (b2) used in the blocked polyisocyanate (B), the following formula (1) or the following formula (2)
式（１） Formula (1)
式（２）
（式（１）及び式（２）において、Ｒは炭素数６〜２０の飽和又は不飽和の脂肪族炭化水素基を示し、ｍ及びｎは同一又は異なって１〜２０の整数を示す。）で表わされるアミドまたはアミン誘導体（ｂ２）である。
Formula (2)
(In Formula (1) and Formula (2), R represents a saturated or unsaturated aliphatic hydrocarbon group having 6 to 20 carbon atoms, and m and n are the same or different and represent an integer of 1 to 20). An amide or amine derivative (b2) represented by
上記式（１）又は式（２）で表わされるアミドまたはアミン誘導体（ｂ２）（以下、式（１）又は式（２）で表わされるアミドまたはアミン誘導体（ｂ２）を「アミドまたはアミン誘導体（ｂ２）」と略することがある）は、脂肪族アミンＲ−ＮＨ２または脂肪族アミドＲ−ＣＯ−ＮＨ２に、酸化エチレンを反応させて得られるものである。
脂肪族アミンＲ−ＮＨ２または脂肪族アミドＲ−ＣＯ−ＮＨ２のＲは、炭素数６〜２０、好ましくは炭素数８〜１８の飽和又は不飽和の脂肪族炭化水素基を示す。
Amide or amine derivative (b2) represented by the above formula (1) or formula (2) (hereinafter, the amide or amine derivative (b2) represented by formula (1) or formula (2) is referred to as “amide or amine derivative (b2) ) ”(Sometimes abbreviated as“) ”is obtained by reacting an aliphatic amine R—NH 2 or an aliphatic amide R—CO—NH 2 with ethylene oxide.
R of the aliphatic amine R—NH 2 or the aliphatic amide R—CO—NH 2 represents a saturated or unsaturated aliphatic hydrocarbon group having 6 to 20 carbon atoms, preferably 8 to 18 carbon atoms.
上記Ｒ−ＮＨ２で示される脂肪族アミン及びＲ−ＣＯ−ＮＨ２で示される脂肪族アミドは、いずれも脂肪酸をはじめとする脂肪族カルボン酸Ｒ−ＣＯＯＨから誘導される。このような脂肪酸としては、トール油脂肪酸、ひまわり油脂肪酸、パーム核油脂肪酸、落花生油脂肪酸、大豆油脂肪酸、ヤシ油脂肪酸、綿花油脂肪酸、アマニ油脂肪酸、ゴマ油脂肪酸、サフラワー油脂肪酸、オリーブ油脂肪酸、脱水ヒマシ油脂肪酸、ラウリン酸、ミリスチン酸、パルミチン酸、リノール酸、リノレン酸、オレイン酸などが挙げられる。 Aliphatic amides represented by aliphatic amines and R-CO-NH 2 represented by the R-NH 2 are both derived from an aliphatic carboxylic acid R-COOH, including fatty acid. Such fatty acids include tall oil fatty acid, sunflower oil fatty acid, palm kernel oil fatty acid, peanut oil fatty acid, soybean oil fatty acid, coconut oil fatty acid, cotton oil fatty acid, linseed oil fatty acid, sesame oil fatty acid, safflower oil fatty acid, olive oil fatty acid , Dehydrated castor oil fatty acid, lauric acid, myristic acid, palmitic acid, linoleic acid, linolenic acid, oleic acid and the like.
式（１）で表されるアミド誘導体の市販品として、エソマイド（ライオン株式会社製、商品名）、アミノーンＬ−０２（花王株式会社製、商品名）、プロファンエキストラ２４、プロファンエキストラ１２８、プロファンエキストラＡＡ−６２ＥＸ（三洋化成社製）等が挙げられる。 As commercial products of the amide derivative represented by the formula (1), esomide (trade name, manufactured by Lion Corporation), aminone L-02 (trade name, manufactured by Kao Corporation), Prophan Extra 24, Profan Extra 128, Examples include Profan Extra AA-62EX (manufactured by Sanyo Chemical Co., Ltd.).
式（２）で表されるアミン誘導体の市販品としては、エソミンＣ／１２、エソミンＣ／１５、エソミンＣ／２５（ライオン株式会社製、商品名）等が挙げられる。
このような特定のアミドまたはアミン誘導体（ｂ２）を使用したブロック化ポリイソシアネート（Ｂ）をカチオン電着塗料組成物中に配合することによって、具体的には、電着塗膜の析出開始が早く、かつ塗膜の融着性が良好なため高電圧を印加することが可能となるので「つきまわり性」が向上する。
Examples of commercially available amine derivatives represented by the formula (2) include esomine C / 12, esomine C / 15, esomine C / 25 (trade name, manufactured by Lion Corporation), and the like.
By blending the blocked polyisocyanate (B) using such a specific amide or amine derivative (b2) into the cationic electrodeposition coating composition, specifically, the deposition start of the electrodeposition coating film is accelerated. In addition, since the coating film has good fusing property, it is possible to apply a high voltage, so that “throwing power” is improved.
さらに塗膜の融着性及び被塗物への密着性が良好となるので、合金化溶融亜鉛メッキ鋼板の電着塗装時に発生するスパークにも耐え得る丈夫な析出膜を形成することができ「合金化溶融亜鉛メッキ鋼板の電着塗装適性」に優れ、かつ仕上り性や防食性が良好な塗装物品を得ることができる。 Furthermore, since the adhesion of the coating film and the adhesion to the object are improved, it is possible to form a strong deposited film that can withstand the sparks generated during electrodeposition coating of galvannealed steel sheets. It is possible to obtain a coated article that is excellent in “electrodeposition coating properties of galvannealed steel sheet” and has good finish and corrosion resistance.
ブロック化ポリイソシアネート（Ｂ）で使用されるブロック剤（ｂ３）は、ポリイソシアネート化合物のイソシアネート基に付加してブロックするものであり、そして付加によって生成するブロックポリイソシアネート化合物は常温においては安定であるが、塗膜の焼付け温度（通常約１００〜約２００℃）に加熱した際、ブロック剤が解離して遊離のイソシアネート基を再生しうるものであることが望ましい。 The blocking agent (b3) used in the blocked polyisocyanate (B) is a block added to the isocyanate group of the polyisocyanate compound, and the blocked polyisocyanate compound produced by the addition is stable at room temperature. However, it is desirable that the blocking agent can be dissociated to regenerate free isocyanate groups when heated to the baking temperature of the coating film (usually about 100 to about 200 ° C.).
ブロック化ポリイソシアネート（Ｂ）で使用されるブロック剤（ｂ３）としては、例えば、メチルエチルケトオキシム、シクロヘキサノンオキシムなどのオキシム系化合物；フェノール、パラ−ｔ−ブチルフェノール、クレゾールなどのフェノール系化合物；ｎ−ブタノール、２−エチルヘキサノールなどの脂肪族アルコール類；フェニルカルビノール、メチルフェニルカルビノールなどの芳香族アルキルアルコール類；エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテルなどのエーテルアルコール系化合物；ε−カプロラクタム、γ−ブチロラクタムなどのラクタム系化合物；等が挙げられる。これらの中で水酸基を有するブロック剤が好ましく、さらに下記式（３）で表されるエーテルアルコール系化合物が特に好ましい。 Examples of the blocking agent (b3) used in the blocked polyisocyanate (B) include oxime compounds such as methyl ethyl ketoxime and cyclohexanone oxime; phenol compounds such as phenol, para-t-butylphenol and cresol; n-butanol Aliphatic alcohols such as 2-ethylhexanol; aromatic alkyl alcohols such as phenyl carbinol and methyl phenyl carbinol; ether alcohol compounds such as ethylene glycol monobutyl ether and diethylene glycol monoethyl ether; ε-caprolactam, γ- And lactam compounds such as butyrolactam; and the like. Among these, a blocking agent having a hydroxyl group is preferable, and an ether alcohol compound represented by the following formula (3) is particularly preferable.
ＨＯ-（Ｒ１Ｏ）ｎＲ２・・・式（３）
（式中、ｎ個の繰り返し単位中のＲ１は、それぞれ、同一又は相異なってもよく、炭素数２〜４の直鎖又は分枝鎖状のアルキレン基であり、Ｒ２は炭素数１〜１５、好ましくは１〜８のアルキル基であり、そしてｎは１〜４の整数を表す）
なお、ブロック化ポリイソシアネート（Ｂ）を製造する場合には、最初に、ポリイソシアネート化合物（ｂ１）をアミドまたはアミン誘導体（ｂ２）と反応させ、次にブロック剤（ｂ３）を反応させることが、カチオン電着塗料のつきまわり性向上の観点から好ましい。
HO— (R 1 O) n R 2 Formula (3)
(In the formula, R 1 in n repeating units may be the same or different, and each is a linear or branched alkylene group having 2 to 4 carbon atoms, and R 2 has 1 carbon atom. -15, preferably an alkyl group of 1-8, and n represents an integer of 1-4)
When producing the blocked polyisocyanate (B), first, the polyisocyanate compound (b1) is reacted with an amide or amine derivative (b2), and then the blocking agent (b3) is reacted. It is preferable from the viewpoint of improving throwing power of the cationic electrodeposition paint.
ここで、ポリイソシアネート化合物（ｂ１）に対する特定のアミドまたはアミン誘導体（ｂ２）及びブロック剤（ｂ３）の配合割合は、アミドまたはアミン誘導体（ｂ２）の活性水素基（水酸基）／ポリイソシアネート化合物（ｂ１）のイソシアネート基の当量比が、０．０２〜０．５、好ましくは０．０５〜０．４であり、ブロック剤（ｂ３）の活性水素基／ポリイソシアネート化合物（ｂ１）のイソシアネート基の当量比は、０．５〜１．２、好ましくは０．６〜１．１であり、そして
［前記アミドまたはアミン誘導体（ｂ２）の活性水素基＋前記ブロック剤（ｂ３）の活性水素基］／［前記ポリイソシアネート化合物（ｂ１）のイソシアネート基］の当量比が１．０〜１．５、好ましくは１．０〜１．３であることが、特に、得られるカチオン電着塗料のつきまわり性及び防食性の観点から好ましい。
Here, the mixing ratio of the specific amide or amine derivative (b2) and the blocking agent (b3) to the polyisocyanate compound (b1) is the active hydrogen group (hydroxyl group) / polyisocyanate compound (b1) of the amide or amine derivative (b2). ) Is an equivalent ratio of isocyanate groups of 0.02 to 0.5, preferably 0.05 to 0.4, and the equivalent of the active hydrogen groups of the blocking agent (b3) / isocyanate groups of the polyisocyanate compound (b1). The ratio is 0.5 to 1.2, preferably 0.6 to 1.1, and [active hydrogen group of the amide or amine derivative (b2) + active hydrogen group of the blocking agent (b3)] / It is particularly obtained that the equivalent ratio of [isocyanate group of the polyisocyanate compound (b1)] is 1.0 to 1.5, preferably 1.0 to 1.3. From the viewpoint of throwing power and corrosion resistance of the cationic electrodeposition paint, it is preferable.
なお、上記反応には、副生成物として、ポリイソシアネート化合物（ｂ１）のイソシアネート基に、アミドまたはアミン誘導体（ｂ２）が付加せず、２個以上のブロック剤（ｂ３）のみが付加したブロック化ポリイソシアネート（Ｂ）も生成する。この副生成物もブロック化ポリイソシアネート（Ｂ）に包含されるものとする。ブロック化ポリイソシアネート（Ｂ）を用いたカチオン電着塗料は、つきまわり性、合金化溶融メッキ鋼板上の電着塗装適性、仕上り性及び防食性が良好である。 In the above reaction, as a by-product, the isocyanate group of the polyisocyanate compound (b1) is not added with the amide or amine derivative (b2), but only with two or more blocking agents (b3). Polyisocyanate (B) is also produced. This by-product is also included in the blocked polyisocyanate (B). The cationic electrodeposition coating using the blocked polyisocyanate (B) has good throwing power, suitability for electrodeposition coating on an alloyed hot dip galvanized steel sheet, finish and corrosion resistance.
また、上記アミドまたはアミン誘導体（ｂ２）の含有量としては、ブロック化ポリイソシアネート（Ｂ）の製造に使用するイソシアネート基を２個以上有するポリイソシアネート化合物（ｂ１）とアミドまたはアミン誘導体（ｂ２）及びブロック剤（ｂ３）の合計質量を基準にして、２〜５０質量％、好ましくは３〜４５質量％、さらに４〜４０質量％が、つきまわり性、仕上り性と防食性の観点から好ましい。 The content of the amide or amine derivative (b2) is as follows. The polyisocyanate compound (b1) having two or more isocyanate groups used for the production of the blocked polyisocyanate (B), the amide or amine derivative (b2), and Based on the total mass of the blocking agent (b3), 2 to 50% by mass, preferably 3 to 45% by mass, and further 4 to 40% by mass are preferable from the viewpoint of throwing power, finish, and corrosion resistance.
本発明のカチオン電着塗料組成物における、カチオン性樹脂（Ａ）及びブロック化ポリイソシアネート（Ｂ）の配合割合は、一般に、両者の合計固形分を基準にして、カチオン性樹脂（Ａ）は５０〜９５質量％、特に６０〜９０質量％の範囲内、そしてブロック化ポリイソシアネート（Ｂ）は５〜５０質量％、特に１０〜４０質量％の範囲内にあることが好適である。 The blending ratio of the cationic resin (A) and the blocked polyisocyanate (B) in the cationic electrodeposition coating composition of the present invention is generally 50 for the cationic resin (A) based on the total solid content of both. It is preferred that the content is in the range of -95% by weight, especially 60-90% by weight, and the blocked polyisocyanate (B) is in the range of 5-50% by weight, in particular 10-40% by weight.
さらに本発明のカチオン電着塗料組成物は、目的とする塗膜性能に応じて、
ブロック化ポリイソシアネート（Ｂ）に加えて、その他のブロック化ポリイソシアネート化合物を併用することも可能である。
その他のブロック化ポリイソシアネート化合物に用いるポリイソシアネート化合物及びブロック剤としては、上記したポリイソシアネート化合物（ｂ１）、ブロック剤（ｂ３）を用いることができる。
Furthermore, the cationic electrodeposition coating composition of the present invention, depending on the intended coating film performance,
In addition to the blocked polyisocyanate (B), other blocked polyisocyanate compounds can be used in combination.
As the polyisocyanate compound and blocking agent used for other blocked polyisocyanate compounds, the above-described polyisocyanate compound (b1) and blocking agent (b3) can be used.
本発明組成物において、ブロック化ポリイソシアネート（Ｂ）とその他のブロック化ポリイソシアネート化合物の固形分合計に対して、アミド又はアミン誘導体（ｂ２）に基づく含有率は、１〜５０質量％、好ましくは２〜４５質量％、さらに３〜４０質量％であることが、つきまわり性、仕上り性及び防食性の面から好ましい。 In the composition of the present invention, the content based on the amide or amine derivative (b2) is 1 to 50% by mass, preferably based on the total solid content of the blocked polyisocyanate (B) and other blocked polyisocyanate compounds. It is preferably 2 to 45% by mass, and more preferably 3 to 40% by mass, from the viewpoint of throwing power, finish, and corrosion resistance.
本発明の組成物において、他に、硬化触媒、界面活性剤、表面調整剤等の各種添加剤及び有機溶剤などを適宜配合することができ、このうち硬化触媒は、カチオン性樹脂（Ａ）とブロック化ポリイソシアネート（Ｂ）との架橋反応を促進するために有効である。
本発明のカチオン電着塗料において、下記式（４）で示される芳香族カルボン酸のアルキル錫エステル化合物の少なくとも１種を、カチオン性樹脂（Ａ）及びブロック化ポリイソシアネート（Ｂ）の固形分合計に対して、０〜１０質量％、好ましくは０．０１〜５質量％含有することが、仕上り性及び防食性を両立させる為に好ましい。
In the composition of the present invention, in addition, various additives such as a curing catalyst, a surfactant and a surface conditioner, and an organic solvent can be appropriately blended, and among these, the curing catalyst includes a cationic resin (A) and This is effective for promoting the crosslinking reaction with the blocked polyisocyanate (B).
In the cationic electrodeposition coating composition of the present invention, at least one of the alkyl tin ester compounds of aromatic carboxylic acids represented by the following formula (4) is added to the total solid content of the cationic resin (A) and the blocked polyisocyanate (B). The content of 0 to 10% by mass, preferably 0.01 to 5% by mass, is preferable in order to achieve both finish and corrosion resistance.
式（４）
（式中、Ｒ３は１〜１２個の炭素原子を有するアルキル基を表わし、Ｒ４は水素原子又は１〜４個の炭素原子を有するアルキル基、ｍは１〜３の整数を表す）。
Formula (4)
(Wherein R 3 represents an alkyl group having 1 to 12 carbon atoms, R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 1 to 3).
式（４）で表される芳香族カルボン酸のアルキル錫エステル化合物としては、例えば、ジオクチル錫ジベンゾエート、ジブチル錫ジベンゾエートが挙げられる。カチオン電着塗料組成物の製造は、カチオン性樹脂（Ａ）及びブロック化ポリイソシアネート（Ｂ）に加え、並びに必要に応じて、界面活性剤、表面調整剤、芳香族カルボン酸のアルキル錫エステル化合物等の各種添加剤や有機溶剤等を十分に混合して調合樹脂を生成させ、次いで、一般的には、水性媒体中において、上記調合樹脂を水溶性有機カルボン酸で中和して、調合樹脂を水溶化又は水分散化して、エマルションを得る。なお調合樹脂の中和には、一般的には、公知の酸を用いることができるが、中でも酢酸、ギ酸、乳酸又はこれらの混合物が好適である。 Examples of the alkyl tin ester compound of the aromatic carboxylic acid represented by the formula (4) include dioctyl tin dibenzoate and dibutyl tin dibenzoate. In addition to the cationic resin (A) and the blocked polyisocyanate (B), the production of the cationic electrodeposition coating composition includes a surfactant, a surface conditioner, and an alkyl tin ester compound of an aromatic carboxylic acid. In the aqueous medium, the compounded resin is generally neutralized with a water-soluble organic carboxylic acid, and the compounded resin is prepared by thoroughly mixing various additives such as organic solvents and the like. Is water-soluble or water-dispersed to obtain an emulsion. In general, a known acid can be used for neutralization of the prepared resin, and among them, acetic acid, formic acid, lactic acid, or a mixture thereof is preferable.
また、上記界面活性剤としては、例えば、ＨＬＢが３〜１８、好ましくは５〜１５の範囲内にあるアセチレングリコール系、ポリエチレングリコール系、多価アルコール系などのノニオン系界面活性剤が挙げられる。ＨＬＢが、上記範囲内であると水分散性と塗料安定性の為に好ましい。 Moreover, as said surfactant, nonionic surfactants, such as acetylene glycol type | system | group, polyethyleneglycol type | system | group, a polyhydric alcohol type, etc. which have HLB in the range of 3-18, preferably 5-15 are mentioned, for example. HLB within the above range is preferred for water dispersibility and paint stability.
また、上記有機溶剤としては、例えば、アルコール系として、例えば、メチルアルコール、エチルアルコール、ｎ−ブチルアルコール、イソプロピルアルコール、２−エチルヘキサノール、ベンジルアルコール、エチレングリコール、プロピレングリコール；エーテル系、例えば、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコールモノ−２−エチルヘキシルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノフェニルエーテル、３−メチル−３−メトキシブタノール、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル；ケトン系、例えば、アセトン、メチルイソブチルケトン、シクロヘキサノン、イソホロン、アセチルアセトン；エステル系、例えば、エチレングルコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテートやこれらの混合物が挙げられる。 Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, n-butyl alcohol, isopropyl alcohol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, propylene glycol; ethers such as ethylene. Glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monophenyl ether, 3-methyl-3-methoxybutanol, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether; ketone series For example, acetone, methyl isobutyl ketone, cyclohexanone, isophorone, acetyl acetone; esters, for example, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate and mixtures thereof.
カチオン電着塗料組成物は、カチオン性樹脂（Ａ）及びブロック化ポリイソシアネート（Ｂ）などを分散したエマルションと、あらかじめ製造しておいた顔料分散ペーストを混合して製造することが好ましい。 The cationic electrodeposition coating composition is preferably produced by mixing an emulsion in which the cationic resin (A) and the blocked polyisocyanate (B) are dispersed with a pigment dispersion paste that has been produced in advance.
上記顔料分散ペーストは、着色顔料、防錆顔料及び体質顔料などをあらかじめ微細粒子に分散したものであって、例えば、顔料分散用樹脂、中和剤及び顔料類、さらに必要に応じてビスマス化合物を配合し、ボールミル、サンドミル、ペブルミル等の分散混合機中で分散処理して調製することができる。 The pigment dispersion paste is prepared by dispersing colored pigments, rust preventive pigments, extender pigments and the like in advance in fine particles. For example, a pigment dispersing resin, a neutralizing agent and pigments, and a bismuth compound as necessary. It can mix | blend and can prepare by carrying out the dispersion process in dispersion | distribution mixers, such as a ball mill, a sand mill, and a pebble mill.
上記顔料分散用樹脂としては、公知のものが使用でき、例えば水酸基及びカチオン性基を有する基体樹脂や界面活性剤等を使用することができる。例えば、上記分散用樹脂として、水酸基及びカチオン性基を有する基体樹脂、界面活性剤等、又は３級アミン型、４級アンモニウム塩型、３級スルホニウム塩型などの樹脂を使用できる。上記顔料分散剤の使用量は、顔料１００質量部あたり、１〜１５０質量部、特に１０〜１００質量部の範囲内が好適である。 As the pigment dispersion resin, known resins can be used. For example, a base resin having a hydroxyl group and a cationic group, a surfactant, and the like can be used. For example, as the resin for dispersion, a base resin having a hydroxyl group and a cationic group, a surfactant, or the like, or a resin such as a tertiary amine type, a quaternary ammonium salt type, or a tertiary sulfonium salt type can be used. The amount of the pigment dispersant used is preferably in the range of 1 to 150 parts by weight, particularly 10 to 100 parts by weight, per 100 parts by weight of the pigment.
上記顔料には、特に制限なく使用でき、例えば、酸化チタン、カーボンブラック、ベンガラ等の着色顔料；クレー、マイカ、バリタ、炭酸カルシウム、シリカなどの体質顔料；リンモリブデン酸アルミニウム、トリポリリン酸アルミニウム、酸化亜鉛（亜鉛華）等の防錆顔料；を添加することができる。 The above pigments can be used without particular limitation, for example, colored pigments such as titanium oxide, carbon black, bengara, etc .; extender pigments such as clay, mica, barita, calcium carbonate, silica, etc .; Anticorrosive pigments such as zinc (zinc white) can be added.
さらに、腐食抑制又は防錆を目的として、ビスマス化合物を含有させることができる。上記ビスマス化合物としては、例えば、酸化ビスマス、水酸化ビスマス、塩基性炭酸ビスマス、硝酸ビスマス、ケイ酸ビスマス及び有機酸ビスマス等を用いることができる。
また、硬化性向上を目的として、ジオクチル錫オキサイド、ジブチル錫オキサイド等の有機錫化合物を用いることができるが、前記酸化亜鉛（亜鉛華）等の防錆顔料及び／又はビスマス化合物を、必要に応じて、増量、微細化（ナノ化）等をすることによって、これらの有機錫化合物を含有せずに硬化性の向上を図ることもできる。
Furthermore, a bismuth compound can be contained for the purpose of inhibiting corrosion or preventing rust. Examples of the bismuth compound include bismuth oxide, bismuth hydroxide, basic bismuth carbonate, bismuth nitrate, bismuth silicate, and organic acid bismuth.
In addition, for the purpose of improving curability, organic tin compounds such as dioctyltin oxide and dibutyltin oxide can be used. However, the anticorrosive pigment and / or bismuth compound such as zinc oxide (zinc white) may be used as necessary. Thus, by increasing the amount, miniaturization (nanoization), etc., it is possible to improve the curability without containing these organotin compounds.
これらの顔料成分とビスマス化合物及び／又は有機錫化合物の合計配合量は、基体樹脂及び硬化剤との合計固形分１００質量部あたり、１〜１００質量部、特に１０〜５０質量部の範囲内が好ましい。
本発明のカチオン電着塗料組成物の被塗物としては、自動車ボディ、２輪車部品、家庭用機器、その他の機器等が挙げられ、金属であれば特に制限はない。
The total amount of these pigment components and the bismuth compound and / or organotin compound is 1 to 100 parts by weight, particularly 10 to 50 parts by weight, per 100 parts by weight of the total solid content of the base resin and the curing agent. preferable.
Examples of the object to be coated with the cationic electrodeposition coating composition of the present invention include automobile bodies, motorcycle parts, household equipment, other equipment, and the like.
被塗物としての金属鋼板としては、冷延鋼板、合金化溶融亜鉛めっき鋼板、電気亜鉛めっき鋼板、電気亜鉛−鉄二層めっき鋼板、有機複合めっき鋼板、Ａｌ素材、Ｍｇ素材など、並びにこれらの金属板を必要に応じてアルカリ脱脂等の表面を洗浄化した後、リン酸塩化成処理、クロメート処理等の表面処理を行ったものが挙げられる。 Examples of metal steel plates to be coated include cold-rolled steel plates, galvannealed steel plates, electrogalvanized steel plates, electrogalvanized steel double-layer plated steel plates, organic composite plated steel plates, Al materials, Mg materials, and these metals. The surface of the plate may be subjected to surface treatment such as phosphate chemical treatment or chromate treatment after washing the surface such as alkali degreasing as required.
本発明のカチオン電着塗料組成物を、電着塗装によって所望の基材表面に塗装することができる。電着塗装は、一般的には、脱イオン水等で希釈して固形分濃度が約５〜４０質量％とし、さらにｐＨを５．５〜９．０の範囲内に調整した電着塗料組成物からなる電着浴を、通常、浴温１５〜３５℃に調整し、負荷電圧１００〜４００Ｖの条件で被塗物を陰極として通電することによって行うことができる。電着塗装後、通常、余分に付着したカチオン電着塗料を落とすために、限外濾過液（ＵＦ濾液）、逆浸透透過水（ＲＯ水）、工業用水、純水等で十分に水洗する。 The cationic electrodeposition coating composition of the present invention can be applied to a desired substrate surface by electrodeposition coating. Electrodeposition coating is generally an electrodeposition coating composition that is diluted with deionized water or the like to have a solid content concentration of about 5 to 40% by mass and further adjusted to a pH in the range of 5.5 to 9.0. An electrodeposition bath made of a product can be usually performed by adjusting the bath temperature to 15 to 35 ° C. and energizing the article to be coated as a cathode under a load voltage of 100 to 400V. In general, after electrodeposition coating, in order to remove the excessively deposited cationic electrodeposition paint, it is sufficiently washed with ultrafiltrate (UF filtrate), reverse osmosis permeated water (RO water), industrial water, pure water or the like.
電着塗膜の膜厚は、特に制限されるものではないが、一般的には、乾燥塗膜に基づいて５〜４０μｍ、好ましくは１２〜３０μｍの範囲内とすることができる。 Although the film thickness of an electrodeposition coating film is not specifically limited, In general, it can be in the range of 5 to 40 μm, preferably 12 to 30 μm based on the dry coating film.
また、塗膜の焼き付け乾燥は、電着塗膜を電気熱風乾燥機、ガス熱風乾燥機などの乾燥設備を用いて、塗装物表面の温度で１１０℃〜２００℃、好ましくは１４０〜１８０℃にて、時間としては１０分間〜１８０分間、好ましくは２０分間〜５０分間、電着塗膜を加熱して行う。上記焼付け乾燥により塗膜を硬化させることができる。 The coating film is baked and dried by using a drying facility such as an electric hot air dryer or a gas hot air dryer, and the coating surface temperature is 110 ° C. to 200 ° C., preferably 140 to 180 ° C. Then, the electrodeposition coating film is heated for 10 minutes to 180 minutes, preferably 20 minutes to 50 minutes. The coating film can be cured by baking and drying.
なお、本発明のカチオン電着塗料組成物は、つきまわり性、合金化溶融亜鉛メッキ鋼板上の電着塗装適性、仕上り性及び防食性に優れた硬化塗膜を形成するものであり、例えば、自動車車体、自動車部品、家電製品、建設機材及び鋼構造物などにおける塗料として有用である。 The cationic electrodeposition coating composition of the present invention forms a cured coating film having excellent throwing power, suitability for electrodeposition coating on an alloyed hot-dip galvanized steel sheet, finish, and anticorrosion. It is useful as a paint for automobile bodies, automobile parts, home appliances, construction equipment, steel structures, and the like.
以下、実施例を挙げて本発明をさらに詳細に説明する。本発明はこれによって限定されるものではない。尚、「部」及び「％」は「質量部」及び「質量％」を示す。 Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited thereby. “Parts” and “%” indicate “parts by mass” and “% by mass”.
製造例１ 硬化剤Ｎｏ．１溶液の製造例
反応容器中に、コスモネートＭ−２００（注１）２７０部及びメチルイソブチルケトン１２０部を加え７０℃に昇温した。この中にアミノーンＬ−０２（注１）を３０部添加し、イソシアネート価が２５０ｍｇＮＣＯ／ｇになるまで反応させた。
次いで、エチレングリコールモノブチルエーテル２２０部を１時間かけて滴下し、その後、１００℃に昇温した。この温度を保ちながら、経時でサンプリングし、赤外線吸収スペクトル測定にて２２７０ｃｍ−１に未反応のイソシアナネート基の吸収が判別できなくなったことを確認してから温度を下げ、樹脂固形分が８０％の硬化剤Ｎｏ．１溶液を得た。
硬化剤Ｎｏ．１において、アミドまたはアミン誘導体（ｂ２）の活性水素基／ポリイソシアネート化合物（ｂ１）のイソシアネート基の当量比は、０．１であり、ブロック剤（ｂ３）の活性水素基／ポリイソシアネート化合物（ｂ１）のイソシアネート基の当量比は０．９３であり、
そして［アミドまたはアミン誘導体（ｂ２）の活性水素基＋ブロック剤（ｂ３）の活性水素基］／［ポリイソシアネート化合物（ｂ１）のイソシアネート基］の当量比は、１．０３であった。また、アミドまたはアミン誘導体（ｂ２）の割合は、ポリイソシアネート化合物（ｂ１）とアミドまたはアミン誘導体（ｂ２）とブロック剤（ｂ３）との合計質量を基準にして、６質量％であった。
Production Example 1 Hardener No. Production Example of 1 Solution In a reaction vessel, 270 parts of Cosmonate M-200 (Note 1) and 120 parts of methyl isobutyl ketone were added and heated to 70 ° C. 30 parts of Aminone L-02 (Note 1) was added thereto, and the reaction was continued until the isocyanate value reached 250 mg NCO / g.
Subsequently, 220 parts of ethylene glycol monobutyl ether was added dropwise over 1 hour, and then the temperature was raised to 100 ° C. While maintaining this temperature, sampling was performed over time, and after confirming that absorption of unreacted isocyanate group could not be discriminated at 2270 cm −1 by infrared absorption spectrum measurement, the temperature was lowered and the resin solid content was 80 % Curing agent No. One solution was obtained.
Hardener No. 1, the equivalent ratio of active hydrogen group of amide or amine derivative (b2) / isocyanate group of polyisocyanate compound (b1) is 0.1, and active hydrogen group / polyisocyanate compound (b1) of blocking agent (b3). ) Is an isocyanate group equivalent ratio of 0.93,
The equivalent ratio of [active hydrogen group of amide or amine derivative (b2) + active hydrogen group of blocking agent (b3)] / [isocyanate group of polyisocyanate compound (b1)] was 1.03. The ratio of the amide or amine derivative (b2) was 6% by mass based on the total mass of the polyisocyanate compound (b1), the amide or amine derivative (b2), and the blocking agent (b3).
（注１）コスモネートＭ−２００：三井化学社製、商品名、クルードＭＤＩ、イソシアネート価３１１ｍｇＮＣＯ／ｇ
（注２）アミノーンＬ−０２：花王社製、商品名、式（１）においてｎ＝１、ｍ＝１）。
(Note 1) Cosmonate M-200: manufactured by Mitsui Chemicals, trade name, crude MDI, isocyanate value 311 mg NCO / g
(Note 2) Aminone L-02: Kao Corporation, trade name, n = 1 in formula (1), m = 1).
製造例２ 硬化剤Ｎｏ．２溶液の製造例
反応容器中に、コスモネートＭ−２００（注１） ２７０部及びメチルイソブチルケトン１２２部を加え７０℃に昇温した。この中にエソミンＣ／１２（注３）を２８部添加し、イソシアネート価が２６５ｍｇＮＣＯ／ｇになるまで反応させた。
次いで、エチレングリコールモノブチルエーテル２２０部を１時間かけて滴下し、その後、１００℃に昇温した。この温度を保ちながら、経時でサンプリングし、赤外線吸収スペクトル測定にて２２７０ｃｍ−１に未反応のイソシアナネート基の吸収が判別できなくなったことを確認してから温度を下げ、樹脂固形分が８０％の硬化剤Ｎｏ．２溶液を得た。
硬化剤Ｎｏ．２において、アミドまたはアミン誘導体（ｂ２）の活性水素基／ポリイソシアネート化合物（ｂ１）のイソシアネート基の当量比は、０．１であり、ブロック剤（ｂ３）の活性水素基／ポリイソシアネート化合物（ｂ１）のイソシアネート基の当量比は０．９３であり、
そして［アミドまたはアミン誘導体（ｂ２）の活性水素基＋ブロック剤（ｂ３）の活性水素基］／［ポリイソシアネート化合物（ｂ１）のイソシアネート基］の当量比は、１．０３であった。また、アミドまたはアミン誘導体（ｂ２）の割合は、ポリイソシアネート化合物（ｂ１）とアミドまたはアミン誘導体（ｂ２）とブロック剤（ｂ３）との合計質量を基準にして５質量％であった。
Production Example 2 Curing Agent No. 2 Solution Production Example In a reaction vessel, 270 parts of Cosmonate M-200 (Note 1) and 122 parts of methyl isobutyl ketone were added and heated to 70 ° C. In this, 28 parts of Esomine C / 12 (Note 3) was added and reacted until the isocyanate value reached 265 mg NCO / g.
Subsequently, 220 parts of ethylene glycol monobutyl ether was added dropwise over 1 hour, and then the temperature was raised to 100 ° C. While maintaining this temperature, sampling was performed over time, and after confirming that absorption of unreacted isocyanate group could not be discriminated at 2270 cm −1 by infrared absorption spectrum measurement, the temperature was lowered and the resin solid content was 80 % Curing agent No. Two solutions were obtained.
Hardener No. 2, the equivalent ratio of active hydrogen group of amide or amine derivative (b2) / isocyanate group of polyisocyanate compound (b1) is 0.1, and active hydrogen group / polyisocyanate compound (b1) of blocking agent (b3). ) Is an isocyanate group equivalent ratio of 0.93,
The equivalent ratio of [active hydrogen group of amide or amine derivative (b2) + active hydrogen group of blocking agent (b3)] / [isocyanate group of polyisocyanate compound (b1)] was 1.03. The ratio of the amide or amine derivative (b2) was 5% by mass based on the total mass of the polyisocyanate compound (b1), the amide or amine derivative (b2), and the blocking agent (b3).
（注３）エソミンＣ／１２：ライオン社製、商品名、式（２）においてｎ＋ｍ＝２。 (Note 3) Esomine C / 12: product of Lion, trade name, n + m = 2 in formula (2).
製造例３ 硬化剤Ｎｏ．３溶液の製造例
反応容器中に、コスモネートＭ−２００（注１）２７０部及びメチルイソブチルケトン １６５部を加え７０℃に昇温した。この中にエソマイドＨＴ／１５（注４）を２２０部添加し、イソシアネート価が１４０ｍｇＮＣＯ／ｇになるまで反応させた。
次いで、エチレングリコールモノブチルエーテル１９５部を１時間かけて滴下し、その後、１００℃に昇温した。この温度を保ちながら、経時でサンプリングし、赤外線吸収スペクトル測定にて２２７０ｃｍ−１に未反応のイソシアナネート基の吸収が判別できなくなったことを確認してから温度を下げ、樹脂固形分が８０％の硬化剤Ｎｏ．３溶液を得た。
硬化剤Ｎｏ．３において、アミドまたはアミン誘導体（ｂ２）の活性水素基／ポリイソシアネート化合物（ｂ１）のイソシアネート基の当量比は、０．２であり、ブロック剤（ｂ３）の活性水素基／ポリイソシアネート化合物（ｂ１）のイソシアネート基の当量比は０．８３であり、
そして［アミドまたはアミン誘導体（ｂ２）の活性水素基＋ブロック剤（ｂ３）の活性水素基］／［ポリイソシアネート化合物（ｂ１）のイソシアネート基］の当量比は、１．０３であった。また、アミドまたはアミン誘導体（ｂ２）の割合は、ポリイソシアネート化合物（ｂ１）とアミドまたはアミン誘導体（ｂ２）とブロック剤（ｂ３）との合計質量を基準にして３２．０質量％であった。
Production Example 3 Hardener No. Production Example of 3 Solution In a reaction vessel, 270 parts of Cosmonate M-200 (Note 1) and 165 parts of methyl isobutyl ketone were added and heated to 70 ° C. 220 parts of esomide HT / 15 (Note 4) was added thereto, and the reaction was continued until the isocyanate value reached 140 mg NCO / g.
Subsequently, 195 parts of ethylene glycol monobutyl ether was added dropwise over 1 hour, and then the temperature was raised to 100 ° C. While maintaining this temperature, sampling was performed over time, and after confirming that absorption of unreacted isocyanate group could not be discriminated at 2270 cm −1 by infrared absorption spectrum measurement, the temperature was lowered and the resin solid content was 80 % Curing agent No. Three solutions were obtained.
Hardener No. 3, the equivalent ratio of the active hydrogen group of the amide or amine derivative (b2) / the isocyanate group of the polyisocyanate compound (b1) is 0.2, and the active hydrogen group / polyisocyanate compound (b1) of the blocking agent (b3) is ) Is an isocyanate group equivalent ratio of 0.83,
The equivalent ratio of [active hydrogen group of amide or amine derivative (b2) + active hydrogen group of blocking agent (b3)] / [isocyanate group of polyisocyanate compound (b1)] was 1.03. The ratio of the amide or amine derivative (b2) was 32.0% by mass based on the total mass of the polyisocyanate compound (b1), the amide or amine derivative (b2), and the blocking agent (b3).
（注４）エソマイドＨＴ／１５：ライオン社製、商品名、式（１）においてｎ＋ｍ＝５。 (Note 4) Esomide HT / 15: manufactured by Lion Corporation, trade name, n + m = 5 in formula (1).
製造例４ 硬化剤Ｎｏ．４溶液の製造例
反応容器中に、コスモネートＭ−２００（注１）２７０部及びメチルイソブチルケトン１３０部を加え、７０℃に昇温した。
この中にエチレングリコールモノブチルエーテル２４０部を１時間かけて滴下して加え、その後１００℃に昇温した。この温度を保ちながら、経時でサンプリングし、赤外線吸収スペクトル測定にて未反応のイソシアネート基の吸収が判別できなかったことを確認してから温度を下げ、樹脂固形分が８０％の硬化剤Ｎｏ．４を得た。
Production Example 4 Curing Agent No. 4 Solution Production Example In a reaction vessel, 270 parts of Cosmonate M-200 (Note 1) and 130 parts of methyl isobutyl ketone were added and heated to 70 ° C.
240 parts of ethylene glycol monobutyl ether was added dropwise thereto over 1 hour, and then the temperature was raised to 100 ° C. While maintaining this temperature, sampling was carried out over time, and after confirming that the absorption of unreacted isocyanate groups could not be determined by infrared absorption spectrum measurement, the temperature was lowered, and the curing agent no. 4 was obtained.
製造例５ 硬化剤Ｎｏ．５溶液の製造例
反応容器中に、イソホロンジイソシアネート２２２部及びメチルイソブチル
ケトン１００部を加え、５０℃に昇温した。この中にメチルエチルケトオキシム１７４部をゆっくり加えた後、６０℃に昇温した。この温度を保ちながら、経時でサンプリングし、赤外線吸収スペクトル測定にて未反応のイソシアネート基の吸収が判別できなくなったことを確認してから温度を下げ、樹脂固形分８０％の硬化剤Ｎｏ．５溶液を得た。
Production Example 5 Curing Agent No. 5 Solution Production Example Into a reaction vessel, 222 parts of isophorone diisocyanate and 100 parts of methyl isobutyl ketone were added and heated to 50 ° C. To this was slowly added 174 parts of methyl ethyl ketoxime, and then the temperature was raised to 60 ° C. While maintaining this temperature, sampling was carried out over time, and after confirming that absorption of unreacted isocyanate groups could not be determined by infrared absorption spectrum measurement, the temperature was lowered and curing agent No. 80 having a resin solid content of 80% was obtained. Five solutions were obtained.
製造例６ 基体樹脂Ｎｏ．１溶液の製造例
温度計、還流冷却器、及び攪拌機を備えた内容積２リットルのセパラブルフラスコに、ｊＥＲ８２８ＥＬ（ジャパンエポキシレジン（株）製、商品名、エポキシ樹脂）１０１０部に、ビスフェノールＡ ３９０部とジメチルベンジルアミン０．２部とを加え、１３０ でエポキシ当量８００になるまで反応させた。
次に、ジエタノールアミン１６０部及びジエチレントリアミンのケチミン化物６５部を加え、１２０℃で４時間反応させた後、エチレングリコールモノブチルエーテル３５５部を加え、樹脂固形分８０質量％の基体樹脂Ｎｏ．１溶液を得た。基体樹脂Ｎｏ．１は、アミン価６７ｍｇＫＯＨ／ｇ、数平均分子量２，０００であった。
Production Example 6 Base resin No. Production example of one solution
A separable flask having an internal volume of 2 liters equipped with a thermometer, a reflux condenser, and a stirrer, jER828EL (trade name, epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd.), 1010 parts, 390 parts of bisphenol A and dimethylbenzylamine 0.2 part was added and reacted at 130 until an epoxy equivalent of 800 was reached.
Next, 160 parts of diethanolamine and 65 parts of diethylenetriamine ketiminate were added and reacted at 120 ° C. for 4 hours, and then 355 parts of ethylene glycol monobutyl ether was added. One solution was obtained. Base resin No. 1 had an amine value of 67 mgKOH / g and a number average molecular weight of 2,000.
製造例７ 基体樹脂Ｎｏ．２溶液の製造例
製造例６と同様のセパラブルフラスコに、５０％ホルマリン４８０部、フェノール１１０部、９８％工業用硫酸２０２部及びメタキシレン４２４部を仕込み、８４〜８８℃で４時間反応させた。
反応終了後、静置して樹脂相を溶解しているキシレン溶液と硫酸水相とを分離した後、樹脂相を３回水洗し、２０〜３０ｍｍＨｇ／１２０〜１３０℃の条件で２０分間処理し、未反応メタキシレンを留去して、粘度１０５０センチポイズ（２５℃）のフェノール変性のキシレンホルムアルデヒド樹脂４８０部を得た。
別のフラスコに、ｊＥＲ８２８ＥＬ（ジャパンエポキシレジン社製、商品名、エポキシ樹脂 、エポキシ当量１９０、分子量３５０）１０００部、ビスフェノールＡ４００部と、ジメチルベンジルアミン０．２部を加え、１３０℃でエポキシ当量７５０になるまで反応させた。
次に、上記キシレンホルムアルデヒド樹脂を３００部、ジエタノールアミンを１３７部及びジエチレントリアミンのケチミン化物を９５部加え１２０℃で４時間反応させた後、メチルイソブチルケトンを４０３部加え、キシレンホルムアルデヒド樹脂変性のアミノ基含有エポキシ樹脂溶液である樹脂固形分８０質量％の基体樹脂Ｎｏ．２溶液を得た。基体樹脂Ｎｏ．２は、アミン価５７ｍｇＫＯＨ／ｇ、数平均分子量２，０００であった。
Production Example 7 Base resin no. Example of manufacturing two solutions
In a separable flask similar to Production Example 6, 480 parts of 50% formalin, 110 parts of phenol, 202 parts of 98% industrial sulfuric acid and 424 parts of metaxylene were prepared and reacted at 84 to 88 ° C. for 4 hours.
After completion of the reaction, the xylene solution in which the resin phase is dissolved and the aqueous sulfuric acid phase are separated, and then the resin phase is washed with water three times and treated for 20 minutes at 20-30 mmHg / 120-130 ° C. Then, unreacted meta-xylene was distilled off to obtain 480 parts of a phenol-modified xylene formaldehyde resin having a viscosity of 1050 centipoise (25 ° C.).
To another flask, 1000 parts of jER828EL (manufactured by Japan Epoxy Resin, trade name, epoxy resin, epoxy equivalent 190, molecular weight 350), 400 parts of bisphenol A and 0.2 part of dimethylbenzylamine were added, and epoxy equivalent of 750 at 130 ° C. The reaction was continued until
Next, after adding 300 parts of the above xylene formaldehyde resin, 137 parts of diethanolamine and 95 parts of ketimine compound of diethylenetriamine, the mixture was reacted at 120 ° C. for 4 hours, and then added with 403 parts of methyl isobutyl ketone to contain xylene formaldehyde resin-modified amino groups. An epoxy resin solution having a resin solid content of 80% by mass, a base resin No. Two solutions were obtained. Base resin No. 2 had an amine value of 57 mgKOH / g and a number average molecular weight of 2,000.
［エマルションの製造］
製造例８ エマルションＮｏ．１の製造例
製造例６で得られた樹脂固形分８０％の基体樹脂Ｎｏ．１溶液を８７．５部（固形分７０部）と、製造例１で得られた硬化剤Ｎｏ．１を３７．５部（固形分３０部）を混合し、さらに１０％蟻酸１１部を配合して均一に攪拌した後、強く攪拌しながら約１５分間を要して脱イオン水１５８部を滴下して、固形分３４％のエマルションＮｏ．１を得た。
[Emulsion production]
Production Example 8 Emulsion No. Production Example 1 Substrate resin No. 80 having a resin solid content of 80% obtained in Production Example 6 One solution was 87.5 parts (solid content 70 parts) and the curing agent No. obtained in Production Example 1 was obtained. 17.5 was mixed with 37.5 parts (solid content 30 parts), and further mixed with 11 parts of 10% formic acid and stirred uniformly. Then, 158 parts of deionized water was added dropwise over about 15 minutes while stirring vigorously. Emulsion No. 34 with a solid content of 34%. 1 was obtained.
製造例９〜２０ エマルションＮｏ．２〜Ｎｏ．１３の製造例
表１の配合内容とする以外は、製造例８と同様にしてエマルションＮｏ．２〜Ｎｏ．１３を得た。
Production Examples 9 to 20 Emulsion No. 2-No. Production Example No. 13 Emulsion No. 13 was prepared in the same manner as in Production Example 8 except that the contents shown in Table 1 were used. 2-No. 13 was obtained.
製造例２１ 顔料分散用樹脂の製造例
ｊＥＲ８２８ＥＬ（ジャパンエポキシレジン株式会社製、商品名、エポキシ樹脂）１０１０部に、ビスフェノールＡを３９０部、プラクセル２１２（ポリカプロラクトンジオール、ダイセル化学工業株式会社、商品名、重量平均分子量約１，２５０）２４０部及びジメチルベンジルアミン０．２部を加え、１３０℃でエポキシ当量が約１０９０になるまで反応させた。
次に、ジメチルエタノールアミン１３４部及び濃度９０％の乳酸水溶液１５０部を加え、１２０℃で４時間反応させた。次いで、メチルイソブチルケトンを加えて固形分を調整し、固形分６０％のアンモニウム塩型樹脂系の顔料分散用樹脂を得た。上記分散用樹脂のアンモニウム塩濃度は、０．７８ｍｍｏｌ／ｇであった。
Production Example 21 Production Example of Resin for Dispersing Pigment jER828EL (trade name, epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd.) 1010 parts, 390 parts of bisphenol A, Plaxel 212 (polycaprolactone diol, Daicel Chemical Industries, Ltd., trade name) , 240 parts by weight, and 0.2 parts by weight of dimethylbenzylamine were added and reacted at 130 ° C. until the epoxy equivalent was about 1090.
Next, 134 parts of dimethylethanolamine and 150 parts of a 90% strength lactic acid aqueous solution were added and reacted at 120 ° C. for 4 hours. Next, methyl isobutyl ketone was added to adjust the solid content, and an ammonium salt resin-based pigment dispersion resin having a solid content of 60% was obtained. The ammonium salt concentration of the dispersing resin was 0.78 mmol / g.
製造例２２ 顔料分散ペーストＮｏ．１の製造例
製造例２１で得た固形分６０％の顔料分散用樹脂８．３部（固形分５部）、酸化チタン１４．５部、精製クレー７．０部、カーボンブラック０．３部、ジオクチル錫オキサイド１部、水酸化ビスマス１部及び脱イオン水２０．３部を加え、ボールミルにて２０時間分散し、固形分５５％の顔料分散ペーストＮｏ．１を得た。
Production Example 22 Pigment Dispersion Paste No. Production Example 1 1 Pigment-dispersing resin with a solid content of 60% obtained in Production Example 21 (solid content 5 parts), titanium oxide 14.5 parts, refined clay 7.0 parts, carbon black 0.3 parts In addition, 1 part of dioctyl tin oxide, 1 part of bismuth hydroxide and 20.3 parts of deionized water were added and dispersed in a ball mill for 20 hours. 1 was obtained.
製造例２３ 顔料分散ペーストＮｏ．２の製造例
製造例２１で得た固形分６０％の顔料分散用樹脂８．３部（固形分５部）、酸化チタン１４．５部、精製クレー６．０部、カーボンブラック０．３部、酸化亜鉛３．０部及び脱イオン水２０．３部を加え、ボールミルにて２０時間分散し、固形分５５％の顔料分散ペーストＮｏ．２を得た。
Production Example 23 Pigment dispersion paste No. Production Example 2 2 8.3 parts of a pigment-dispersing resin 60% solids obtained in Production Example 21 (5 parts solids), 14.5 parts titanium oxide, 6.0 parts purified clay, 0.3 parts carbon black Then, 3.0 parts of zinc oxide and 20.3 parts of deionized water were added and dispersed in a ball mill for 20 hours. 2 was obtained.
［カチオン電着塗料の製造］
実施例1
カチオン電着用のエマルションＮｏ．１を２９４部（固形分１００部）、５５％の顔料分散ペーストＮｏ．１を５２．４部（固形分２８．８部）、脱イオン水２９７．６部を加え、固形分２０％のカチオン電着塗料Ｎｏ．１を製造した。
[Manufacture of cationic electrodeposition coatings]
Example 1
Emulsion no. No. 1 294 parts (solid content 100 parts), 55% pigment dispersion paste No. 1 No. 1 was added 52.4 parts (solid content 28.8 parts) and deionized water 297.6 parts. 1 was produced.
実施例２〜７
実施例１と同様にして、表２で示されるような配合内容にてカチオン電着塗料Ｎｏ．２〜Ｎｏ．７を製造した。
Examples 2-7
In the same manner as in Example 1, a cationic electrodeposition paint No. 1 having the blending contents shown in Table 2 was used. 2-No. 7 was produced.
比較例１〜７
実施例１と同様にして、表２で示されるような配合内容にてカチオン電着塗料Ｎｏ．８〜Ｎｏ．１４を製造した。
Comparative Examples 1-7
In the same manner as in Example 1, a cationic electrodeposition paint No. 1 having the blending contents shown in Table 2 was used. 8-No. 14 was produced.
［試験板の作成］
実施例及び比較例で得た各カチオン電着塗料を用い、パルボンド＃３０２０（日本パーカライジング社製、商品名、リン酸亜鉛化成処理剤）を施した冷延鋼板（０．８ｍｍ×１５０ｍｍ×７０ｍｍ）、又は同様の化成処理を施した合金化溶融亜鉛メッキ鋼板（０．８ｍｍ×１５０ｍｍ×７０ｍｍ）を被塗物として電着塗装し、試験板を作成した。
得られた試験板を用いて実施した試験結果を、表３及び表４に示す。
[Create test plate]
Cold-rolled steel sheet (0.8 mm x 150 mm x 70 mm) to which Palbond # 3020 (manufactured by Nippon Parkerizing Co., Ltd., trade name, zinc phosphate chemical conversion treatment agent) was applied using each cationic electrodeposition paint obtained in Examples and Comparative Examples. Alternatively, an alloyed hot-dip galvanized steel sheet (0.8 mm × 150 mm × 70 mm) subjected to the same chemical conversion treatment was electrodeposited as a coating object to prepare a test plate.
Tables 3 and 4 show the results of tests performed using the obtained test plates.
（注５）つきまわり性：直径８ｍｍの穴を空け、４枚の鋼板を２ｃｍ間隔で設置した「４枚ボックス法つきまわり性試験の治具」（図１参照）を、図２のように配線した。図２の４枚の鋼板のうち、最も左側の鋼板に向かって左側の面を「Ａ面」、向かって右側の面を「Ｂ面」とする。同様に、左から２番目の鋼板の左右の面を、それぞれ、「Ｃ面」及び「Ｄ面」、左から３番目の鋼板の左右の面を、それぞれ、「Ｅ面」及び「Ｆ面」、そして最も右側の鋼板の左右の面が、それぞれ、「Ｇ面」と「Ｈ面」となる。この中で、Ａ面が「外板」であり、Ｇ面が「内板」となる。
図２の装置において、塗装浴温３０℃、Ａ面と電極との極間距離１０ｃｍ、通電時間３分間にて、外板硬化膜厚１５μｍとなる電圧にて電着塗装した。つきまわり性は、外板硬化膜厚、内板硬化膜厚及びつきまわり性（％）（＝内板硬化膜厚／外板硬化膜厚×１００）で評価した。
(Note 5) Throwing power: A “four-box box throwing power test jig” (see FIG. 1) in which holes of 8 mm in diameter are drilled and four steel plates are installed at intervals of 2 cm is as shown in FIG. Wired. Of the four steel plates in FIG. 2, the left-hand surface toward the leftmost steel plate is referred to as “A surface”, and the right-hand surface is referred to as “B surface”. Similarly, the left and right surfaces of the second steel plate from the left are “C surface” and “D surface”, respectively, and the left and right surfaces of the third steel plate from the left are “E surface” and “F surface”, respectively. The right and left surfaces of the rightmost steel sheet are the “G plane” and the “H plane”, respectively. Among these, the A surface is an “outer plate”, and the G surface is an “inner plate”.
In the apparatus of FIG. 2, electrodeposition coating was performed at a coating bath temperature of 30 ° C., a distance between the A surface and the electrode of 10 cm, a current-carrying time of 3 minutes, and a voltage of 15 μm on the outer plate cured film thickness. The throwing power was evaluated by the outer plate cured film thickness, the inner plate cured film thickness, and the throwing power (%) (= inner plate cured film thickness / outer plate cured film thickness × 100).
（注６）合金化溶融亜鉛メッキ鋼板の電着塗装適性：パルボンド＃３０２０（日本パーカライジング社製、商品名、リン酸亜鉛処理剤）で化成処理した０．８×１５０×７０ｍｍの合金化溶融亜鉛メッキ鋼板を、電着塗料浴の陰極として浸漬し、つきまわり性試験と同様の通電電圧にて電着塗装した。得られた塗膜を１７０℃で２０分間焼付け硬化させて塗膜面のピンホール数（試験面：１５０ｍｍ×７０ｍｍ中）を数えた。
各評価については、
◎：ピンホールなし、
○：小さいピンホール（ガスヘコ）が１個（中塗り塗膜にて隠蔽可能なレベル）、
△：ピンホールが２〜９個、
×：ピンホールが１０個以上、
を表している。
(Note 6) Suitability for electrodeposition coating of alloyed hot-dip galvanized steel sheet: 0.8 × 150 × 70 mm alloyed hot-dip zinc subjected to chemical conversion treatment with Palbond # 3020 (trade name, zinc phosphate treatment agent manufactured by Nihon Parkerizing Co., Ltd.) The plated steel sheet was dipped as the cathode of the electrodeposition paint bath and electrodeposited at the same energizing voltage as the throwing power test. The obtained coating film was baked and cured at 170 ° C. for 20 minutes, and the number of pinholes on the coating surface (test surface: 150 mm × 70 mm) was counted.
For each evaluation,
A: No pinhole,
○: One small pinhole (gas hem) (a level that can be concealed with an intermediate coating film),
Δ: 2 to 9 pinholes,
×: 10 or more pinholes,
Represents.
（注７）仕上り性：上記電着塗装適性と同様の条件で塗装して硬化膜厚１５μｍの塗板を得た。上記塗板の表面粗度を、ＪＩＳ Ｂ ０６５１に準じて、サーフテスト３０１（株式会社ミツトヨ社製、商品名、表面粗さ測定機）を用いて、中心線平均粗さ（Ｒａ）値として評価した。
各評価については、
◎：Ｒａ値が、０．２３μｍ未満、
○：Ｒａ値が、０．２３以上、０．３０μｍ未満、
△：Ｒａ値が、０．３０以上で、かつ０．４０μｍ未満
×：Ｒａ値が、０．４０μｍ超、を表している。
(Note 7) Finishing property: A coated plate having a cured film thickness of 15 μm was obtained by coating under the same conditions as the above electrodeposition coating suitability. The surface roughness of the coated plate was evaluated as a center line average roughness (Ra) value using Surf Test 301 (trade name, surface roughness measuring machine manufactured by Mitutoyo Corporation) according to JIS B 0651. .
For each evaluation,
A: Ra value is less than 0.23 μm,
○: Ra value is 0.23 or more and less than 0.30 μm,
Δ: Ra value is 0.30 or more and less than 0.40 μm x: Ra value is more than 0.40 μm.
（注８）防食性：上記電着塗装適性と同様の条件で塗装して、硬化膜厚２０μｍの試験板を得た。
次に、上記試験板上の塗膜に、試験板の素地に達するようにカッターナイフでクロスカットキズを入れ、ＪＩＳ Ｚ−２３７１に準じて、３５℃ソルトスプレー試験を８４０時間行い、カット部からの錆又はフクレの幅を評価した。
各評価については、錆又はフクレの最大幅が、
◎：カット部から片側２．０ｍｍ以下
○：カット部から片側２．０ｍｍ超、３．０ｍｍ以下、
△：カット部から片側３．０ｍｍ超、３．５ｍｍ以下、
×：カット部から片側３．５ｍｍ超、
を表している。
(Note 8) Anticorrosion: A test plate having a cured film thickness of 20 μm was obtained by coating under the same conditions as the electrodeposition coating suitability.
Next, in the coating film on the test plate, a cross cut scratch is put with a cutter knife so as to reach the base of the test plate, and a 35 ° C. salt spray test is performed for 840 hours in accordance with JIS Z-2371. The width of rust or blisters was evaluated.
For each evaluation, the maximum width of rust or swelling is
◎: 2.0 mm or less on one side from cut part ○: More than 2.0 mm on one side from cut part, 3.0 mm or less,
Δ: More than 3.0 mm on one side from the cut part, 3.5 mm or less,
X: More than 3.5 mm on one side from the cut part,
Represents.
（注９）耐暴露性：
上記防食性と同様の条件で作成した試験板に、ＷＰ−３００（関西ペイント株式会社製、水性中塗り塗料）を、硬化膜厚が２５μｍとなるようにスプレー塗装した後、電気熱風乾燥器で１４０℃で３０分焼き付けを行なった。
さらに、上記中塗塗膜上に、ネオアミラック６０００スプレー塗装により、ネオアミラック６０００（関西ペイント株式会社製、熱硬化性上塗り塗料）を、硬化膜厚が３５μｍとなるようにスプレー塗装した後、電気熱風乾燥器で１４０℃で３０分間焼き付け、暴露試験板を作製した。
得られた暴露試験板上の塗膜に、素地に達するようにナイフでクロスカットキズを入れ、千葉県 千倉町で水平にて１年間暴露した後、ナイフ傷からの錆、フクレ幅によって以下の基準で評価した。
各評価については、錆又はフクレの最大幅が、
◎：カット部から片側２ｍｍ未満、
○：カット部から片側２ｍｍ以上、３ｍｍ未満、
△：カット部から片側３ｍｍ以上、４ｍｍ未満、
×：カット部から片側４ｍｍ以上、
を表している。
(Note 9) Exposure resistance:
After spray-coating WP-300 (manufactured by Kansai Paint Co., Ltd., water-based intermediate coating) on a test plate prepared under the same conditions as the above-mentioned anticorrosion properties, an electric hot air dryer is used. Baking was performed at 140 ° C. for 30 minutes.
Furthermore, after spray-coating Neoamylak 6000 (manufactured by Kansai Paint Co., Ltd., thermosetting topcoat) on the intermediate coating film by spray coating with Neoamilac 6000 so that the cured film thickness becomes 35 μm, an electric hot air dryer is used. Was baked at 140 ° C. for 30 minutes to prepare an exposure test plate.
After putting a cross-cut wound on the coating film on the obtained exposure test board with a knife so as to reach the substrate and exposing it horizontally in Chikura-cho, Chiba for one year, the following rust and blister width from the knife scratch Evaluated by criteria.
For each evaluation, the maximum width of rust or swelling is
A: Less than 2 mm on one side from the cut part,
○: 2 mm or more and less than 3 mm on one side from the cut part,
Δ: 3 mm or more and less than 4 mm on one side from the cut part,
X: 4 mm or more on one side from the cut part,
Represents.
本発明は、つきまわり性、合金化溶融亜鉛メッキ鋼板上の電着塗装適性、仕上り性及び防食性に優れた塗装物品を提供できるので産業上有用である。 INDUSTRIAL APPLICABILITY The present invention is industrially useful because it can provide a coated article having excellent throwing power, suitability for electrodeposition coating on an alloyed hot-dip galvanized steel sheet, finish, and corrosion resistance.
１．直径８ｍｍの穴
２．４枚ボックス法のつきまわり性試験用治具における外板（Ａ面）
３．４枚ボックス法のつきまわり性試験用治具における内板（Ｇ面）
４．電着塗料浴
1. Outer plate in jig for testing throwing power of 2.4-hole box method with 8mm diameter hole
3. Inner plate (G surface) in the throwing power test jig of the 4-sheet box method
4). Electrodeposition paint bath
Claims (8)
（式（１）及び式（２）において、Ｒは炭素数６〜２０の飽和又は不飽和の脂肪族炭化水素基を示し、ｍ及びｎは同一又は異なって１〜２０の整数を示す。）で表わされるアミドまたはアミン誘導体（ｂ２）と、ブロック剤（ｂ３）とを反応してなるブロック化ポリイソシアネート（Ｂ）を含有するカチオン電着塗料組成物。 Cationic resin (A), polyisocyanate compound (b1) having two or more isocyanate groups, and the following formula (1) or the following formula (2)
(In Formula (1) and Formula (2), R represents a saturated or unsaturated aliphatic hydrocarbon group having 6 to 20 carbon atoms, and m and n are the same or different and represent an integer of 1 to 20). A cationic electrodeposition coating composition containing a blocked polyisocyanate (B) obtained by reacting an amide or amine derivative (b2) represented by formula (b2) with a blocking agent (b3).
ブロック剤（ｂ３）の活性水素基／前記ポリイソシアネート化合物（ｂ１）のイソシアネート基の当量比が０．５〜１．２であり、かつ
［前記アミドまたはアミン誘導体（ｂ２）の活性水素基＋前記ブロック剤（ｂ３）の活性水素基］／［前記ポリイソシアネート化合物（ｂ１）のイソシアネート基］の当量比が１．０〜１．５の割合で、ポリイソシアネート化合物（ｂ１）、アミドまたはアミン誘導体（ｂ２）及びブロック剤（ｂ３）を反応させて得られた、請求項１に記載のカチオン電着塗料組成物。 The blocked polyisocyanate (B) has an equivalent ratio of active hydrogen groups of the amide or amine derivative (b2) / isocyanate groups of the polyisocyanate compound (b1) of 0.02 to 0.5,
The equivalent ratio of active hydrogen group of blocking agent (b3) / isocyanate group of polyisocyanate compound (b1) is 0.5 to 1.2, and [active hydrogen group of amide or amine derivative (b2) + The equivalent ratio of the active hydrogen group of the blocking agent (b3) / [isocyanate group of the polyisocyanate compound (b1)] is 1.0 to 1.5, and the polyisocyanate compound (b1), amide or amine derivative ( The cationic electrodeposition coating composition according to claim 1, obtained by reacting b2) and a blocking agent (b3).
ＨＯ-（Ｒ１Ｏ）ｎＲ２・・・式（３）
（式中、ｎ個の繰り返し単位中のＲ１は、同一又は相異なってもよい炭素数２〜４の直鎖又は分枝鎖状のアルキレン基であり、Ｒ２は炭素数１〜１５のアルキル基であり、そしてｎは１〜４の整数を表す） The cationic electrodeposition coating composition according to any one of claims 1 to 4, wherein the blocking agent (b3) is a compound represented by the following formula (3).
HO— (R 1 O) n R 2 Formula (3)
(In the formula, R 1 in the n repeating units is a linear or branched alkylene group having 2 to 4 carbon atoms which may be the same or different, and R 2 has 1 to 15 carbon atoms. An alkyl group, and n represents an integer of 1 to 4)
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