JP6406848B2 - Electrodeposition coating composition - Google Patents
Electrodeposition coating composition Download PDFInfo
- Publication number
- JP6406848B2 JP6406848B2 JP2014064396A JP2014064396A JP6406848B2 JP 6406848 B2 JP6406848 B2 JP 6406848B2 JP 2014064396 A JP2014064396 A JP 2014064396A JP 2014064396 A JP2014064396 A JP 2014064396A JP 6406848 B2 JP6406848 B2 JP 6406848B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- electrodeposition coating
- pigment dispersion
- coating composition
- resin
- 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.)
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- 238000004070 electrodeposition Methods 0.000 title claims description 127
- 239000008199 coating composition Substances 0.000 title claims description 85
- 239000000049 pigment Substances 0.000 claims description 138
- 229920005989 resin Polymers 0.000 claims description 134
- 239000011347 resin Substances 0.000 claims description 134
- 150000001622 bismuth compounds Chemical class 0.000 claims description 101
- 239000006185 dispersion Substances 0.000 claims description 101
- 238000002156 mixing Methods 0.000 claims description 77
- 238000000576 coating method Methods 0.000 claims description 74
- 239000011248 coating agent Substances 0.000 claims description 73
- 150000007524 organic acids Chemical class 0.000 claims description 50
- 235000001014 amino acid Nutrition 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 45
- 150000001413 amino acids Chemical class 0.000 claims description 44
- 239000007787 solid Substances 0.000 claims description 43
- 239000003795 chemical substances by application Substances 0.000 claims description 41
- 239000002253 acid Substances 0.000 claims description 33
- 238000004519 manufacturing process Methods 0.000 claims description 33
- 239000000839 emulsion Substances 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 239000012948 isocyanate Substances 0.000 claims description 18
- 150000002513 isocyanates Chemical class 0.000 claims description 18
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 15
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- 239000004310 lactic acid Substances 0.000 claims description 7
- 235000014655 lactic acid Nutrition 0.000 claims description 7
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 2
- 235000003704 aspartic acid Nutrition 0.000 claims description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000001723 curing Methods 0.000 description 37
- 150000001412 amines Chemical class 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000003860 storage Methods 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- -1 amine compound Chemical class 0.000 description 12
- 239000003973 paint Substances 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 11
- 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 11
- 239000010959 steel Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 125000003277 amino group Chemical group 0.000 description 9
- 239000003822 epoxy resin Substances 0.000 description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 125000000466 oxiranyl group Chemical group 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 229910000416 bismuth oxide Inorganic materials 0.000 description 6
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 150000002611 lead compounds Chemical class 0.000 description 5
- 150000003141 primary amines Chemical class 0.000 description 5
- 150000003606 tin compounds Chemical class 0.000 description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- 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 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229940049676 bismuth hydroxide Drugs 0.000 description 3
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- OHJYHAOODFPJOD-UHFFFAOYSA-N 2-(2-ethylhexoxy)ethanol Chemical compound CCCCC(CC)COCCO OHJYHAOODFPJOD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
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- C08K2003/2241—Titanium dioxide
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Description
本発明は、電着塗料組成物、特にカチオン性電着塗料組成物に関する。 The present invention relates to an electrodeposition coating composition, and more particularly to a cationic electrodeposition coating composition.
カチオン性電着塗料組成物は一般に、樹脂エマルションからなり、所望により顔料分散ペーストが含まれる。このようなカチオン性電着塗料組成物においては、硬化触媒として、有機錫化合物が広く使用されてきたが、有機錫化合物は昨今の環境規制動向から今後、使用を制限される恐れがあり、代替触媒の開発が以前から行われている。 The cationic electrodeposition coating composition generally comprises a resin emulsion and optionally includes a pigment dispersion paste. In such cationic electrodeposition coating compositions, organotin compounds have been widely used as curing catalysts. However, the use of organotin compounds may be limited in the future due to recent trends in environmental regulations. Catalysts have been developed for some time.
ビスマス化合物は、カチオン性電着塗料組成物の硬化触媒となることが知られている。例えば、酸化ビスマスもしくは水酸化ビスマスなどのビスマス化合物を顔料分散ペーストに単に分散させる方法が開示されているが、その方法では、ビスマス化合物の触媒活性が低いため、塗膜の硬化を十分に達成することができなかった。また塗料や顔料分散ペーストの保存安定性が低下し、保存時に凝集が起こった。 Bismuth compounds are known to serve as curing catalysts for cationic electrodeposition coating compositions. For example, a method is disclosed in which a bismuth compound such as bismuth oxide or bismuth hydroxide is simply dispersed in a pigment dispersion paste. However, in this method, the catalytic activity of the bismuth compound is low, so that the coating film is sufficiently cured. I couldn't. In addition, the storage stability of paints and pigment dispersion pastes decreased, and aggregation occurred during storage.
そこでビスマス化合物をアミノ酸などのアミン含有カルボン酸と予め混合および溶解させた後、得られた混合物を顔料分散ペーストの調製に用いる方法が開示されている(特許文献1)。またビスマス化合物を乳酸と予め混合および溶解させた後、得られた混合物を塗料に添加する方法も開示されている(特許文献2)。しかしながら、上記いずれの方法でも、ビスマス化合物の溶解により触媒活性はいくらか上昇するものの、やはり塗膜の硬化を十分に達成することはできなかった。またビスマス化合物の溶解残渣が多く発生するという問題もあった。そこで必要量のビスマス化合物を溶解させるためには多量のアミノ酸または乳酸が必要であり、このことは塗膜の外観の悪化や塗膜の耐食性の低下といった悪影響を及ぼした。塗膜の外観の悪化は、膜厚が不均一になり、塗膜にムラが生じる現象である。 Thus, a method is disclosed in which a bismuth compound is mixed and dissolved in advance with an amine-containing carboxylic acid such as an amino acid, and the resulting mixture is used for preparing a pigment dispersion paste (Patent Document 1). Also disclosed is a method in which a bismuth compound is mixed and dissolved in advance with lactic acid, and then the resulting mixture is added to a paint (Patent Document 2). However, in any of the above methods, although the catalytic activity is somewhat increased by dissolution of the bismuth compound, the coating film cannot be sufficiently cured. There is also a problem that a large amount of bismuth compound dissolution residue occurs. Therefore, in order to dissolve the necessary amount of bismuth compound, a large amount of amino acid or lactic acid is required, and this has an adverse effect such as deterioration of the appearance of the coating film and deterioration of the corrosion resistance of the coating film. Deterioration of the appearance of the coating film is a phenomenon in which the film thickness becomes non-uniform and the coating film becomes uneven.
本発明は上記従来の課題を解決するものであり、その目的とするところは、ビスマス化合物の溶解性が十分に向上し、硬化性、膜厚均一性および耐食性に優れた塗膜を形成することができる電着塗料組成物を提供することにある。 The present invention solves the above-mentioned conventional problems, and the object is to form a coating film with sufficiently improved solubility of the bismuth compound and excellent curability, film thickness uniformity and corrosion resistance. It is an object of the present invention to provide an electrodeposition coating composition capable of producing
本発明はまた、ビスマス化合物の溶解性が十分に向上し、硬化性、膜厚均一性および耐食性に優れた塗膜を形成することができるとともに、電着塗料組成物の保存安定性および当該電着塗料組成物を構成する顔料分散ペーストの保存安定性に優れた電着塗料組成物を提供することを目的とする。 The present invention also has a sufficiently improved solubility of the bismuth compound, can form a coating film having excellent curability, film thickness uniformity, and corrosion resistance, and also has a storage stability of the electrodeposition coating composition and the electric charge. An object of the present invention is to provide an electrodeposition coating composition having excellent storage stability of a pigment dispersion paste constituting the coating composition.
上記課題を解決するため、本発明は下記態様を提供する。
本発明は、樹脂エマルション(1)および顔料分散ペースト(2)を含む電着塗料組成物であって、
前記樹脂エマルション(1)が、アミン化樹脂(A)およびブロックイソシアネート硬化剤(B)を含み、
前記顔料分散ペースト(2)が、ビスマス化合物(C)および有機酸(D)を予め混合し、次いで、得られた混合物、顔料分散樹脂(E)および顔料(F)を混合して調製され、
前記顔料分散ペースト(2)が下記条件を満たす電着塗料組成物を提供する:
(i)ビスマス化合物(C)におけるビスマス金属および有機酸(D)の含有量のモル比がBi:(D)で1:0.5〜1:4である;および
(ii)ビスマス化合物(C)、顔料分散樹脂(E)および顔料(F)の含有量の質量比が(C)+(F):(E)で1:0.2〜1:0.5である。
In order to solve the above problems, the present invention provides the following aspects.
The present invention is an electrodeposition coating composition comprising a resin emulsion (1) and a pigment dispersion paste (2),
The resin emulsion (1) contains an aminated resin (A) and a blocked isocyanate curing agent (B),
The pigment dispersion paste (2) is prepared by previously mixing the bismuth compound (C) and the organic acid (D), and then mixing the resulting mixture, the pigment dispersion resin (E) and the pigment (F),
An electrodeposition coating composition in which the pigment dispersion paste (2) satisfies the following conditions is provided:
(I) the molar ratio of the bismuth metal and organic acid (D) content in the bismuth compound (C) is 1: 0.5 to 1: 4 in Bi: (D); and (ii) the bismuth compound (C ), The mass ratio of the content of the pigment dispersion resin (E) and the pigment (F) is 1: 0.2 to 1: 0.5 in (C) + (F) :( E).
本発明の電着塗料組成物は、
前記顔料分散ペースト(2)が、アミノ酸(G)をさらに含み、
前記顔料分散ペースト(2)は、ビスマス化合物(C)、有機酸(D)およびアミノ酸(G)を予め混合し、得られた混合物と、顔料分散樹脂(E)および顔料(F)とを混合して調製されることが好ましい。
The electrodeposition coating composition of the present invention comprises:
The pigment dispersion paste (2) further comprises an amino acid (G),
In the pigment dispersion paste (2), the bismuth compound (C), the organic acid (D) and the amino acid (G) are mixed in advance, and the resulting mixture is mixed with the pigment dispersion resin (E) and the pigment (F). It is preferable to be prepared.
本発明の電着塗料組成物によれば、ビスマス化合物の溶解性が十分に向上するため、硬化性、膜厚均一性および耐食性に優れた塗膜を形成することができる。さらに本発明の電着塗料組成物および当該電着塗料組成物を構成する顔料分散ペーストは保存安定性が十分に優れている。 According to the electrodeposition coating composition of the present invention, since the solubility of the bismuth compound is sufficiently improved, a coating film excellent in curability, film thickness uniformity, and corrosion resistance can be formed. Furthermore, the electrodeposition coating composition of the present invention and the pigment dispersion paste constituting the electrodeposition coating composition are sufficiently excellent in storage stability.
本発明の電着塗料組成物は樹脂エマルション(1)および顔料分散ペースト(2)を含むものである。 The electrodeposition coating composition of the present invention comprises a resin emulsion (1) and a pigment dispersion paste (2).
[樹脂エマルション(1)]
樹脂エマルション(1)はアミン化樹脂(A)およびブロックイソシアネート硬化剤(B)を含み、所望により他の成分をさらに含んでも良い。
[Resin emulsion (1)]
The resin emulsion (1) contains an aminated resin (A) and a blocked isocyanate curing agent (B), and may further contain other components as desired.
<アミン化樹脂(A)>
アミン化樹脂(A)は電着塗膜を構成する塗膜形成樹脂である。アミン化樹脂(A)として、樹脂骨格中のオキシラン環を有機アミン化合物で変性して得られるカチオン変性エポキシ樹脂が好ましい。一般にカチオン変性エポキシ樹脂は、出発原料樹脂分子内のオキシラン環を1級アミン、2級アミンあるいは3級アミンおよび/またはその酸塩などのアミン類との反応によって開環して調製される。出発原料樹脂の典型例は、ビスフェノールA、ビスフェノールF、ビスフェノールS、フェノールノボラック、クレゾールノボラックなどの多環式フェノール化合物とエピクロルヒドリンとの反応生成物であるポリフェノールポリグリシジルエーテル型エポキシ樹脂である。また他の出発原料樹脂の例として、特開平5−306327号公報に記載のオキサゾリドン環含有エポキシ樹脂を挙げることができる。これらのエポキシ樹脂は、ジイソシアネート化合物、またはジイソシアネート化合物のイソシアネート基をメタノール、エタノールなどの低級アルコールでブロックして得られたビスウレタン化合物と、エピクロルヒドリンとの反応によって調製することができる。
<Aminated resin (A)>
The aminated resin (A) is a coating film forming resin constituting the electrodeposition coating film. As the aminated resin (A), a cation-modified epoxy resin obtained by modifying an oxirane ring in the resin skeleton with an organic amine compound is preferable. In general, a cation-modified epoxy resin is prepared by ring-opening an oxirane ring in a starting material resin molecule by a reaction with an amine such as a primary amine, secondary amine or tertiary amine and / or its acid salt. A typical example of the starting material resin is a polyphenol polyglycidyl ether type epoxy resin which is a reaction product of a polycyclic phenol compound such as bisphenol A, bisphenol F, bisphenol S, phenol novolak, cresol novolak and epichlorohydrin. Examples of other starting material resins include oxazolidone ring-containing epoxy resins described in JP-A-5-306327. These epoxy resins can be prepared by reacting a diisocyanate compound or a bisurethane compound obtained by blocking an isocyanate group of a diisocyanate compound with a lower alcohol such as methanol or ethanol, and epichlorohydrin.
上記出発原料樹脂は、アミン類によるオキシラン環の開環反応の前に、2官能性のポリエステルポリオール、ポリエーテルポリオール、ビスフェノール類、2塩基性カルボン酸などにより鎖延長して用いることができる。特にビスフェノール類は、アミン類によるオキシラン環の開環反応時に用いて、鎖延長してもよい。 The starting material resin can be used by extending the chain with a bifunctional polyester polyol, polyether polyol, bisphenol, dibasic carboxylic acid or the like before the ring-opening reaction of the oxirane ring with amines. In particular, bisphenols may be used for chain extension by opening the oxirane ring with amines.
また同じく、アミン類によるオキシラン環の開環反応の前に、分子量またはアミン当量の調節、熱フロー性の改良などを目的として、一部のオキシラン環に対して2−エチルヘキサノール、ノニルフェノール、エチレングリコールモノ−2−エチルヘキシルエーテル、エチレングリコールモノn−ブチルエーテル、プロピレングリコールモノ−2−エチルヘキシルエーテルなどのモノヒドロキシ化合物やオクチル酸などのモノカルボン酸化合物を付加して用いることもできる。 Similarly, before the oxirane ring-opening reaction with amines, 2-ethylhexanol, nonylphenol, ethylene glycol is used for some oxirane rings for the purpose of adjusting molecular weight or amine equivalent and improving heat flow. Monohydroxy compounds such as mono-2-ethylhexyl ether, ethylene glycol mono n-butyl ether, propylene glycol mono-2-ethylhexyl ether, and monocarboxylic acid compounds such as octylic acid can be added and used.
オキシラン環を開環し、アミノ基を導入する際に使用し得るアミン類の例としては、ブチルアミン、オクチルアミン、ジエチルアミン、ジブチルアミン、メチルブチルアミン、モノエタノールアミン、ジエタノールアミン、N−メチルエタノールアミン、トリエチルアミン、N,N−ジメチルベンジルアミン、N,N−ジメチルエタノールアミンなどの1級アミン、2級アミンまたは3級アミンおよび/もしくはその酸塩を挙げることができる。また、アミノエチルエタノールアミンメチルイソブチルケチミンなどのケチミンブロック1級アミノ基含有2級アミン、ジエチレントリアミンジケチミンも使用することができる。これらのアミン類は、全てのオキシラン環を開環させるために、オキシラン環に対して少なくとも当量で反応させる必要がある。 Examples of amines that can be used for opening an oxirane ring and introducing an amino group include butylamine, octylamine, diethylamine, dibutylamine, methylbutylamine, monoethanolamine, diethanolamine, N-methylethanolamine, triethylamine , N, N-dimethylbenzylamine, primary amines such as N, N-dimethylethanolamine, secondary amines or tertiary amines and / or their acid salts. Further, ketimine block primary amino group-containing secondary amine such as aminoethylethanolamine methyl isobutyl ketimine, diethylenetriamine diketimine can also be used. These amines must be reacted with at least an equivalent amount relative to the oxirane ring in order to open all the oxirane rings.
アミン化樹脂(A)の数平均分子量は、1,000〜5,000であるのが好ましい。数平均分子量が1,000以上であることにより、得られる硬化電着塗膜の耐溶剤性および耐食性などの物性が良好となる。一方で、数平均分子量が5,000以下であることにより、アミン化樹脂の粘度調整が容易となって円滑な合成が可能となり、また、得られたアミン化樹脂(A)の乳化分散の取扱いが容易になる。アミン化樹脂(A)の数平均分子量は1,600〜3,200の範囲であるのがより好ましい。 The number average molecular weight of the aminated resin (A) is preferably 1,000 to 5,000. When the number average molecular weight is 1,000 or more, physical properties such as solvent resistance and corrosion resistance of the obtained cured electrodeposition coating film are improved. On the other hand, when the number average molecular weight is 5,000 or less, the viscosity of the aminated resin can be easily adjusted to enable smooth synthesis, and handling of emulsified dispersion of the obtained aminated resin (A) is possible. Becomes easier. The number average molecular weight of the aminated resin (A) is more preferably in the range of 1,600 to 3,200.
なお、本明細書において、数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)で測定したポリスチレン換算の数平均分子量である。また本明細書において「硬化電着塗膜」は、単に「電着塗膜」と記載する場合もある。一方で、本明細書において、「電着皮膜」、「樹脂皮膜」は、電圧の印加によって被塗物上に析出する、樹脂を主体とする未硬化の皮膜を意味する。 In addition, in this specification, a number average molecular weight is a number average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC). Further, in this specification, “cured electrodeposition coating film” is sometimes simply referred to as “electrodeposition coating film”. On the other hand, in the present specification, “electrodeposited film” and “resin film” mean an uncured film mainly composed of a resin, which is deposited on an object to be coated by application of a voltage.
アミン化樹脂(A)のアミン価は、20〜100mgKOH/gの範囲内であるのが好ましい。アミン化樹脂(A)のアミン価が20mgKOH/g以上であることにより、電着塗料組成物中におけるアミン化樹脂(A)の乳化分散安定性が良好となる。一方で、アミン価が100mgKOH/g以下であることにより、硬化電着塗膜中のアミノ基の量が適正となり、塗膜の耐水性を低下させるおそれがない。アミン化樹脂(A)のアミン価は、20〜80mgKOH/gの範囲内であるのがより好ましい。 The amine value of the aminated resin (A) is preferably in the range of 20 to 100 mgKOH / g. When the amine value of the aminated resin (A) is 20 mgKOH / g or more, the emulsion dispersion stability of the aminated resin (A) in the electrodeposition coating composition is improved. On the other hand, when the amine value is 100 mgKOH / g or less, the amount of amino groups in the cured electrodeposition coating film becomes appropriate, and there is no possibility of reducing the water resistance of the coating film. The amine value of the aminated resin (A) is more preferably in the range of 20 to 80 mgKOH / g.
アミン化樹脂(A)の水酸基価は、50〜400mgKOH/gの範囲内であるのが好ましい。水酸基価が50mgKOH/g以上であることにより、硬化電着塗膜において硬化が良好となる。一方で、水酸基価が400mgKOH/g以下であることにより、硬化電着塗膜中に残存する水酸基の量が適正となり、塗膜の耐水性を低下させるおそれがない。アミン化樹脂(A)の水酸基価は、100〜300mgKOH/gの範囲内であるのがより好ましい。 The hydroxyl value of the aminated resin (A) is preferably in the range of 50 to 400 mgKOH / g. When the hydroxyl value is 50 mgKOH / g or more, the cured electrodeposition coating film is cured well. On the other hand, when the hydroxyl value is 400 mgKOH / g or less, the amount of the hydroxyl group remaining in the cured electrodeposition coating film becomes appropriate, and there is no possibility of reducing the water resistance of the coating film. The hydroxyl value of the aminated resin (A) is more preferably in the range of 100 to 300 mgKOH / g.
本発明の電着塗料組成物において、数平均分子量が1,000〜5,000であり、アミン価が20〜100mgKOH/gであり、かつ、水酸基価が50〜400mgKOH/gであるアミン化樹脂(A)を用いることによって、被塗物に優れた耐食性を付与することができるという利点がある。 In the electrodeposition coating composition of the present invention, an aminated resin having a number average molecular weight of 1,000 to 5,000, an amine value of 20 to 100 mgKOH / g, and a hydroxyl value of 50 to 400 mgKOH / g By using (A), there is an advantage that excellent corrosion resistance can be imparted to the article to be coated.
なおアミン化樹脂(A)としては、必要に応じて、アミン価および/または水酸基価の異なるアミン化樹脂を併用してもよい。2種以上の異なるアミン価、水酸基価のアミン化樹脂を併用する場合は、使用するアミン化樹脂の質量比に基づいて算出する平均アミン価および平均水酸基価が、上記の数値範囲であるのが好ましい。また、併用するアミン化樹脂(A)としては、アミン価が20〜50mgKOH/gであり、かつ、水酸基価が50〜300mgKOH/gであるアミン化樹脂と、アミン価が50〜200mgKOH/gであり、かつ、水酸基価が200〜500mgKOH/gであるアミン化樹脂との併用が好ましい。このような組合わせを用いると、エマルションのコア部がより疎水となりシェル部が親水となるため優れた耐食性を付与することができるという利点がある。 In addition, as an amination resin (A), you may use together the amination resin from which an amine value and / or a hydroxyl value differ as needed. When two or more kinds of amine resins having different amine values and hydroxyl values are used in combination, the average amine value and the average hydroxyl value calculated based on the mass ratio of the aminated resin used are within the above numerical range. preferable. The aminated resin (A) used in combination is an aminated resin having an amine value of 20 to 50 mgKOH / g and a hydroxyl value of 50 to 300 mgKOH / g, and an amine value of 50 to 200 mgKOH / g. And combined use with an aminated resin having a hydroxyl value of 200 to 500 mgKOH / g is preferred. When such a combination is used, since the core part of the emulsion becomes more hydrophobic and the shell part becomes hydrophilic, there is an advantage that excellent corrosion resistance can be imparted.
なおアミン化樹脂(A)は、必要に応じて、アミノ基含有アクリル樹脂、アミノ基含有ポリエステル樹脂などを含んでもよい。 The aminated resin (A) may contain an amino group-containing acrylic resin, an amino group-containing polyester resin, or the like as necessary.
<ブロックイソシアネート硬化剤(B)>
ブロックイソシアネート硬化剤(B)(以下、単に「硬化剤(B)」ということがある)も電着塗膜を構成する塗膜形成樹脂である。ブロックイソシアネート硬化剤(B)は、ポリイソシアネートを、封止剤でブロック化することによって調製することができる。
<Block isocyanate curing agent (B)>
The blocked isocyanate curing agent (B) (hereinafter sometimes simply referred to as “curing agent (B)”) is also a coating film forming resin constituting the electrodeposition coating film. The blocked isocyanate curing agent (B) can be prepared by blocking polyisocyanate with a sealing agent.
ポリイソシアネートの例としては、ヘキサメチレンジイソシアネート(3量体を含む)、テトラメチレンジイソシアネート、トリメチルヘキサメチレンジイシシアネートなどの脂肪族ジイソシアネート、イソホロンジイソシアネート、4,4’−メチレンビス(シクロヘキシルイソシアネート)などの脂環式ポリイソシアネート、4,4’−ジフェニルメタンジイソシアネート、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などの芳香族ジイソシアネートが挙げられる。 Examples of polyisocyanates include aliphatic diisocyanates such as hexamethylene diisocyanate (including trimers), tetramethylene diisocyanate, and trimethylhexamethylene diisocyanate, isophorone diisocyanate, and fats such as 4,4′-methylenebis (cyclohexyl isocyanate). Aromatic diisocyanates such as cyclic polyisocyanate, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate and the like can be mentioned.
封止剤の例としては、n−ブタノール、n−ヘキシルアルコール、2−エチルヘキサノール、ラウリルアルコール、フェノールカルビノール、メチルフェニルカルビノールなどの一価のアルキル(または芳香族)アルコール類;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などのセロソルブ類;ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレンエーテルグリコールフェノールなどのポリエーテル型両末端ジオール類;エチレングリコール、プロピレングリコール、1,4−ブタンジオールなどのジオール類と、シュウ酸、コハク酸、アジピン酸、スベリン酸、セバシン酸などのジカルボン酸類から得られるポリエステル型両末端ポリオール類;パラ−t−ブチルフェノール、クレゾールなどのフェノール類;ジメチルケトオキシム、メチルエチルケトオキシム、メチルイソブチルケトオキシム、メチルアミルケトオキシム、シクロヘキサノンオキシムなどのオキシム類;およびε−カプロラクタム、γ−ブチロラクタムに代表されるラクタム類が好ましく用いられる。 Examples of sealants include monovalent alkyl (or aromatic) alcohols such as n-butanol, n-hexyl alcohol, 2-ethylhexanol, lauryl alcohol, phenol carbinol, methylphenyl carbinol; ethylene glycol mono Cellosolves such as hexyl ether and ethylene glycol mono 2-ethylhexyl ether; Polyether type terminal diols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol phenol; ethylene glycol, propylene glycol, 1,4-butanediol, etc. Polyester type terminal polyols obtained from diols of the above and dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, suberic acid and sebacic acid; para-t-butyl Phenols such as enol and cresol; oximes such as dimethyl ketoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, methyl amyl ketoxime and cyclohexanone oxime; and lactams represented by ε-caprolactam and γ-butyrolactam are preferably used. .
ブロックイソシアネート硬化剤(B)のブロック化率は100%であるのが好ましい。これにより、電着塗料組成物の貯蔵安定性が良好になるという利点がある。 The blocking ratio of the blocked isocyanate curing agent (B) is preferably 100%. Thereby, there exists an advantage that the storage stability of an electrodeposition coating composition becomes favorable.
ブロックイソシアネート硬化剤(B)は、脂肪族ジイソシアネートを封止剤でブロック化することによって調製された硬化剤と、芳香族ジイソシアネートを封止剤でブロック化することによって調製された硬化剤とを併用することが好ましい。 The blocked isocyanate curing agent (B) is a combination of a curing agent prepared by blocking an aliphatic diisocyanate with a sealing agent and a curing agent prepared by blocking an aromatic diisocyanate with a sealing agent. It is preferable to do.
ブロックイソシアネート硬化剤(B)は、アミン化樹脂(A)の1級アミンと優先的に反応し、さらに水酸基と反応して硬化する。
硬化剤としては、メラミン樹脂またはフェノール樹脂などの有機硬化剤、シランカップリング剤、金属硬化剤からなる群から選ばれる少なくとも一種の硬化剤を、ブロックイソシアネート硬化剤(B)と併用してもよい。
The blocked isocyanate curing agent (B) preferentially reacts with the primary amine of the aminated resin (A), and further reacts with a hydroxyl group to be cured.
As the curing agent, at least one curing agent selected from the group consisting of an organic curing agent such as a melamine resin or a phenol resin, a silane coupling agent, and a metal curing agent may be used in combination with the blocked isocyanate curing agent (B). .
<樹脂エマルション(1)の製造>
樹脂エマルションは、アミン化樹脂(A)およびブロックイソシアネート硬化剤(B)をそれぞれ有機溶媒の溶液状態で混合した後、中和酸を用いて中和することにより、形成させることができる。中和酸として、例えば、メタンスルホン酸、スルファミン酸、乳酸、ジメチロールプロピオン酸、ギ酸、酢酸などの有機酸が挙げられる。本発明においては、アミン化樹脂(A)および硬化剤(B)を含む樹脂エマルションを、ギ酸、酢酸からなる群から選択される1種またはそれ以上の酸によって中和するのがより好ましい。
<Production of resin emulsion (1)>
The resin emulsion can be formed by mixing the aminated resin (A) and the blocked isocyanate curing agent (B) in a solution state of an organic solvent and then neutralizing with a neutralizing acid. Examples of the neutralizing acid include organic acids such as methanesulfonic acid, sulfamic acid, lactic acid, dimethylolpropionic acid, formic acid, and acetic acid. In the present invention, it is more preferable to neutralize the resin emulsion containing the aminated resin (A) and the curing agent (B) with one or more acids selected from the group consisting of formic acid and acetic acid.
硬化剤(B)の含有量は、硬化時にアミン化樹脂(A)中の1級、2級アミノ基、水酸基、などの活性水素含有官能基と反応して良好な硬化塗膜を与えるのに十分な量が必要とされる。好ましい硬化剤(B)の含有量は、アミン化樹脂(A)と硬化剤(B)との固形分質量比(アミン化樹脂(A)/硬化剤(B))で表して90/10〜50/50、より好ましくは80/20〜65/35の範囲である。アミン化樹脂(A)と硬化剤(B)との固形分質量比の調整により、造膜時の塗膜(析出膜)の流動性および硬化速度が改良され、塗装外観が向上する。 The content of the curing agent (B) reacts with active hydrogen-containing functional groups such as primary, secondary amino groups and hydroxyl groups in the aminated resin (A) during curing to give a good cured coating film. A sufficient amount is required. The preferable content of the curing agent (B) is 90/10 to 10 in terms of a solid content mass ratio (aminated resin (A) / curing agent (B)) of the aminated resin (A) and the curing agent (B). 50/50, more preferably in the range of 80/20 to 65/35. By adjusting the solid content mass ratio of the aminated resin (A) and the curing agent (B), the fluidity and curing rate of the coating film (deposition film) during film formation are improved, and the coating appearance is improved.
樹脂エマルションの固形分量は通常、樹脂エマルション全量に対して25〜50質量%、特に35〜45質量%であるのが好ましい。 The solid content of the resin emulsion is usually preferably 25 to 50% by mass, particularly preferably 35 to 45% by mass, based on the total amount of the resin emulsion.
本明細書中において「樹脂エマルションの固形分」とは、樹脂エマルション中に含まれる成分であって、溶媒の除去によっても固形となって残存する成分全ての質量を意味する。具体的には、樹脂エマルション中に含まれる、アミン化樹脂(A)、硬化剤(B)および必要に応じて添加される他の固形成分の質量の総量を意味する。 In the present specification, the “solid content of the resin emulsion” means the mass of all components that are contained in the resin emulsion and remain solid even after the solvent is removed. Specifically, it means the total amount of the mass of the aminated resin (A), the curing agent (B) and other solid components added as necessary, contained in the resin emulsion.
中和酸は、アミン化樹脂(A)が有するアミノ基の当量に対する中和酸の当量比率として、10〜100%となる量で用いるのがより好ましく、20〜70%となる量で用いるのがさらに好ましい。本明細書において、アミン化樹脂(A)が有するアミノ基の当量に対する中和酸の当量比率を、中和率とする。中和率が10%以上であることにより、水への親和性が確保され、水分散性が良好となる。 The neutralizing acid is more preferably used in an amount of 10 to 100% as an equivalent ratio of the neutralizing acid to the equivalent of the amino group of the aminated resin (A), and is used in an amount of 20 to 70%. Is more preferable. In this specification, the equivalent ratio of the neutralized acid to the equivalent of the amino group of the aminated resin (A) is defined as the neutralization rate. When the neutralization rate is 10% or more, affinity for water is ensured and water dispersibility is improved.
[顔料分散ペースト(2)]
顔料分散ペースト(2)は、ビスマス化合物(C)、有機酸(D)、顔料分散樹脂(E)および顔料(F)を含むものであり、好ましくはアミノ酸(G)をさらに含む。
[Pigment dispersion paste (2)]
The pigment dispersion paste (2) contains a bismuth compound (C), an organic acid (D), a pigment dispersion resin (E) and a pigment (F), and preferably further contains an amino acid (G).
<ビスマス化合物(C)>
ビスマス化合物(C)はビスマス金属を含有する化合物であり、例えば、酸化ビスマス、水酸化ビスマス、硝酸ビスマスまたはそれらの混合物が挙げられる。好ましいビスマス化合物(C)は酸化ビスマス、水酸化ビスマスである。
<Bismuth compound (C)>
The bismuth compound (C) is a compound containing a bismuth metal, and examples thereof include bismuth oxide, bismuth hydroxide, bismuth nitrate, and mixtures thereof. Preferred bismuth compounds (C) are bismuth oxide and bismuth hydroxide.
ビスマス化合物(C)は粉体形態で使用され、その平均粒子径は通常、0.5〜20μm、好ましくは1〜3μmである。平均粒子径は体積平均粒子径D50であり、後述する方法で測定された値を用いている。 The bismuth compound (C) is used in a powder form, and its average particle size is usually 0.5 to 20 μm, preferably 1 to 3 μm. The average particle diameter is a volume average particle diameter D50, and a value measured by a method described later is used.
<有機酸(D)>
有機酸(D)はアミノ基を有さない有機酸であり、例えば、ヒドロキシカルボン酸およびスルホン酸からなる群から選択される1種以上の化合物である。
<Organic acid (D)>
The organic acid (D) is an organic acid having no amino group, and is, for example, one or more compounds selected from the group consisting of hydroxycarboxylic acids and sulfonic acids.
ヒドロキシカルボン酸としては、例えば、以下の化合物が挙げられる;
(d1)乳酸、グリコール酸などの全炭素原子数2〜5、好ましくは2〜4のモノヒドロキシモノカルボン酸、特に脂肪族モノヒドロキシモノカルボン酸;
(d2)ヒドロキシマロン酸、リンゴ酸などの全炭素原子数2〜5、好ましくは2〜4のモノヒドロキシジカルボン酸、特に脂肪族モノヒドロキシジカルボン酸;
(d3)ジメチロールプロピオン酸(DMPA)、グリセリン酸などの全炭素原子数3〜7、好ましくは3〜6のジヒドロキシモノカルボン酸、特に脂肪族ジヒドロキシモノカルボン酸;
(d4)酒石酸、ブドウ酸などの全炭素原子数3〜6、好ましくは3〜5のジヒドロキシジカルボン酸、特に脂肪族ジヒドロキシジカルボン酸。
Examples of the hydroxycarboxylic acid include the following compounds:
(D1) Monohydroxymonocarboxylic acids having 2 to 5 carbon atoms, preferably 2 to 4 carbon atoms, particularly aliphatic monohydroxymonocarboxylic acids such as lactic acid and glycolic acid;
(D2) monohydroxy dicarboxylic acids having 2 to 5 carbon atoms, preferably 2 to 4 carbon atoms, particularly aliphatic monohydroxy dicarboxylic acids, such as hydroxymalonic acid and malic acid;
(D3) Dihydroxymonocarboxylic acids having 3 to 7 carbon atoms, preferably 3 to 6 carbon atoms, particularly aliphatic dihydroxymonocarboxylic acids such as dimethylolpropionic acid (DMPA) and glyceric acid;
(D4) Dihydroxy dicarboxylic acids having 3 to 6 carbon atoms, preferably 3 to 5 carbon atoms, such as tartaric acid and glucose, especially aliphatic dihydroxy dicarboxylic acids.
スルホン酸は有機スルホン酸であり、例えば、メタンスルホン酸、エタンスルホン酸などの全炭素原子数1〜5、好ましくは1〜3のアルカンスルホン酸が挙げられる。 The sulfonic acid is an organic sulfonic acid, and examples thereof include alkanesulfonic acids having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms such as methanesulfonic acid and ethanesulfonic acid.
好ましい有機酸(D)は、モノヒドロキシモノカルボン酸、ジヒドロキシモノカルボン酸、アルカンスルホン酸からなる群から選択される1種以上の化合物である。 Preferred organic acid (D) is one or more compounds selected from the group consisting of monohydroxymonocarboxylic acid, dihydroxymonocarboxylic acid, and alkanesulfonic acid.
有機酸(D)の分子量は特に限定されず、通常は60〜200であり、好ましくは70〜150である。有機酸の分子量は分子式より算出される値である。 The molecular weight of the organic acid (D) is not particularly limited, and is usually 60 to 200, preferably 70 to 150. The molecular weight of the organic acid is a value calculated from the molecular formula.
有機酸(D)の使用形態は特に限定されず、例えば、固体形態、液体形態、溶媒に溶解してなる溶液形態、特に水溶液形態が挙げられる。 The usage form of the organic acid (D) is not particularly limited, and examples thereof include a solid form, a liquid form, a solution form dissolved in a solvent, and particularly an aqueous solution form.
<顔料分散樹脂(E)>
顔料分散樹脂(E)は、顔料(F)を分散させるための樹脂であり、水性媒体中に分散されて使用される。顔料分散樹脂として、4級アンモニウム基、3級スルホニウム基および1級アミン基から選択される少なくとも1種またはそれ以上を有する変性エポキシ樹脂などの、カチオン基を有する顔料分散樹脂を用いることができる。水性溶媒としてはイオン交換水または少量のアルコール類を含む水などを用いる。
<Pigment dispersion resin (E)>
The pigment dispersion resin (E) is a resin for dispersing the pigment (F), and is used by being dispersed in an aqueous medium. As the pigment dispersion resin, a pigment dispersion resin having a cationic group such as a modified epoxy resin having at least one selected from a quaternary ammonium group, a tertiary sulfonium group, and a primary amine group can be used. As the aqueous solvent, ion-exchanged water or water containing a small amount of alcohol is used.
<顔料(F)>
顔料(F)は、電着塗料組成物において通常用いられる顔料である。顔料として、例えば、通常使用される無機顔料および有機顔料、例えば、チタンホワイト(二酸化チタン)、カーボンブラックおよびベンガラのような着色顔料;カオリン、タルク、ケイ酸アルミニウム、炭酸カルシウム、マイカおよびクレーのような体質顔料;リン酸鉄、リン酸アルミニウム、リン酸カルシウム、トリポリリン酸アルミニウム、およびリンモリブデン酸アルミニウム、リンモリブデン酸アルミニウム亜鉛のような防錆顔料など、が挙げられる。
<Pigment (F)>
The pigment (F) is a pigment usually used in an electrodeposition coating composition. As pigments, for example, commonly used inorganic and organic pigments, eg colored pigments such as titanium white (titanium dioxide), carbon black and bengara; like kaolin, talc, aluminum silicate, calcium carbonate, mica and clay And extender pigments such as iron phosphate, aluminum phosphate, calcium phosphate, aluminum tripolyphosphate, and rust preventive pigments such as aluminum phosphomolybdate and zinc aluminum phosphomolybdate.
<アミノ酸(G)>
アミノ酸(G)は1分子中、1以上のアミノ基および1以上のカルボキシル基を有する有機化合物である。好ましいアミノ酸(G)は、1分子中、1〜3、特に1のアミノ基および1〜3、特に1〜2のカルボキシル基を有する有機化合物である。
<Amino acid (G)>
The amino acid (G) is an organic compound having one or more amino groups and one or more carboxyl groups in one molecule. A preferred amino acid (G) is an organic compound having 1 to 3, particularly 1 amino group and 1 to 3, particularly 1 to 2 carboxyl groups in one molecule.
アミノ酸(G)は全炭素原子数2〜6、特に2〜4のアミノ酸、特に脂肪族アミノ酸が好ましい。
アミノ酸(G)の分子量は特に限定されず、通常は60〜200であり、好ましくは70〜150である。アミノ酸の分子量は分子式より算出される値である。
The amino acid (G) is preferably an amino acid having 2 to 6 carbon atoms, particularly 2 to 4 carbon atoms, particularly an aliphatic amino acid.
The molecular weight of the amino acid (G) is not particularly limited, and is usually 60 to 200, preferably 70 to 150. The molecular weight of the amino acid is a value calculated from the molecular formula.
アミノ酸(G)としては、例えば、グリシン、アスパラギン酸またはそれらの混合物が使用できる。 As the amino acid (G), for example, glycine, aspartic acid or a mixture thereof can be used.
アミノ酸(G)の使用形態は特に限定されず、例えば、固体形態、液体形態、溶媒に溶解してなる溶液形態が挙げられる。 The usage form of the amino acid (G) is not particularly limited, and examples thereof include a solid form, a liquid form, and a solution form dissolved in a solvent.
<顔料分散ペースト(2)の製造>
顔料分散ペースト(2)は、ビスマス化合物(C)および有機酸(D)を予め混合し、次いで、得られた混合物、顔料分散樹脂(E)および顔料(F)をさらに混合して調製される。これにより、本発明の電着塗料組成物は、ビスマス化合物の溶解性が十分に向上し、硬化性、膜厚均一性および耐食性に優れた塗膜を形成することができる。さらに本発明の電着塗料組成物および顔料分散ペーストは保存安定性が十分に向上する。ビスマス化合物(C)および有機酸(D)を、他の成分に先立って、予備混合することによりビスマス化合物の溶解性、塗膜の硬化性、膜厚均一性および耐食性、ならびに保存安定性が向上するメカニズムの詳細は明らかではないが、以下のメカニズムに基づくものと考えられる。予備混合における良溶解配合によりBiを十分に溶解できる。僅かな溶解残渣は、顔料と共に分散され、さらに分散樹脂により安定化される。
<Production of pigment dispersion paste (2)>
The pigment dispersion paste (2) is prepared by previously mixing the bismuth compound (C) and the organic acid (D) and then further mixing the resulting mixture, the pigment dispersion resin (E) and the pigment (F). . Thereby, the electrodeposition coating composition of this invention can form the coating film which the solubility of the bismuth compound fully improved and was excellent in sclerosis | hardenability, film thickness uniformity, and corrosion resistance. Furthermore, the electrodeposition coating composition and the pigment dispersion paste of the present invention are sufficiently improved in storage stability. Premixing bismuth compound (C) and organic acid (D) prior to other components improves solubility of bismuth compound, film curability, film thickness uniformity and corrosion resistance, and storage stability The details of the mechanism are not clear, but are thought to be based on the following mechanism. Bi can be sufficiently dissolved by the good dissolution blending in the preliminary mixing. A slight dissolution residue is dispersed together with the pigment and further stabilized by the dispersing resin.
ビスマス化合物(C)および有機酸(D)を予備混合することなく、他の成分とともに一括混合すると、ビスマス化合物(C)は十分に溶解しないため、得られる塗膜の硬化性、膜厚均一性および耐食性が低下する。さらに本発明の電着塗料組成物および顔料分散ペーストは保存安定性が低下する。 When the bismuth compound (C) and the organic acid (D) are mixed together with other components without premixing, the bismuth compound (C) is not sufficiently dissolved, so that the curability and film thickness uniformity of the resulting coating film are obtained. And corrosion resistance is reduced. Furthermore, the electrodeposition coating composition and the pigment dispersion paste of the present invention have low storage stability.
ビスマス化合物(C)および有機酸(D)の予備混合(以下、単に「第1混合」ということがある)は、ビスマス化合物(C)粒子を、有機酸(D)水溶液中、撹拌により分散させることにより達成される。 In the premixing of the bismuth compound (C) and the organic acid (D) (hereinafter sometimes simply referred to as “first mixing”), the bismuth compound (C) particles are dispersed in the organic acid (D) aqueous solution by stirring. Is achieved.
第1混合時におけるビスマス化合物(C)および有機酸(D)の混合比率は、得られる顔料分散ペーストが下記条件(i)を満たすような比率である。
(i)ビスマス化合物(C)におけるビスマス金属および有機酸(D)の含有量のモル比がBi:(D)で1:0.5〜1:4、好ましくは1:1〜1:2である。
The mixing ratio of the bismuth compound (C) and the organic acid (D) during the first mixing is such that the resulting pigment dispersion paste satisfies the following condition (i).
(I) The molar ratio of the bismuth metal and organic acid (D) content in the bismuth compound (C) is 1: 0.5 to 1: 4 in Bi: (D), preferably 1: 1 to 1: 2. is there.
上記条件(i)において、ビスマス化合物(C)におけるビスマス金属の含有量は第1混合において混合されるビスマス化合物(C)におけるビスマス金属の量(モル数)である。
有機酸(D)の含有量は第1混合において混合される有機酸の量(モル数)であり、有機酸(D)が溶液形態で使用される場合は、溶液中の有機酸単独の量(モル数)である。
In the said condition (i), content of the bismuth metal in a bismuth compound (C) is the quantity (mole number) of the bismuth metal in the bismuth compound (C) mixed in 1st mixing.
The content of the organic acid (D) is the amount (number of moles) of the organic acid mixed in the first mixing. When the organic acid (D) is used in the form of a solution, the amount of the organic acid alone in the solution (Number of moles).
上記条件(i)において、ビスマス化合物(C)におけるビスマス金属に対する有機酸(D)の含有量のモル比が小さすぎると、ビスマス化合物(C)は十分に溶解しないため、得られる塗膜の硬化性が低下する。さらに電着塗料組成物の保存安定性が低下することがある。このため、ビスマス化合物(C)を増量させると、塗膜の硬化性は回復するものの、ビスマス化合物(C)の溶解性の低下のため、溶解残渣量が増加し、顔料分散ペーストおよび電着塗料組成物の保存安定性が低下する。また塗膜の均一性が低下する。一方で、ビスマス化合物(C)におけるビスマス金属に対する有機酸(D)の含有量のモル比が大きすぎても、ビスマス化合物(C)は十分に溶解しないため、塗膜の硬化性および電着塗料組成物の保存安定性が低下する傾向があり、塗膜の均一性が低下する。 In the above condition (i), if the molar ratio of the content of the organic acid (D) to the bismuth metal in the bismuth compound (C) is too small, the bismuth compound (C) is not sufficiently dissolved, so that the resulting coating film is cured. Sex is reduced. Furthermore, the storage stability of the electrodeposition coating composition may be reduced. For this reason, when the amount of the bismuth compound (C) is increased, the curability of the coating film is recovered, but the dissolution residue amount increases due to the decrease in the solubility of the bismuth compound (C), and the pigment dispersion paste and the electrodeposition paint The storage stability of the composition decreases. In addition, the uniformity of the coating film decreases. On the other hand, even if the molar ratio of the content of the organic acid (D) to the bismuth metal in the bismuth compound (C) is too large, the bismuth compound (C) is not sufficiently dissolved. The storage stability of the composition tends to decrease, and the uniformity of the coating film decreases.
第1混合により得られる混合物中の有機酸(D)の含有割合は通常、当該混合物全量に対する有機酸(D)水溶液中の有機酸(D)単独の割合で、1〜20質量%であり、好ましくは3〜15質量%である。第1混合に際しては、通常、ビスマス化合物(C)、有機酸(D)水溶液およびイオン交換水が混合されるため、イオン交換水の使用量によって、上記有機酸(D)単独の含有割合が調整される。有機酸(D)単独の含有割合が小さすぎると、ビスマス化合物(C)は十分に溶解しないため、得られる塗膜の硬化性が低下する。一方で、有機酸(D)単独の含有割合が大きすぎても、ビスマス化合物(C)は十分に溶解しないため、塗膜の硬化性が低下する。 The content ratio of the organic acid (D) in the mixture obtained by the first mixing is usually 1 to 20% by mass of the organic acid (D) alone in the aqueous solution of the organic acid (D) with respect to the total amount of the mixture, Preferably it is 3-15 mass%. In the first mixing, since the bismuth compound (C), the organic acid (D) aqueous solution and the ion exchange water are usually mixed, the content ratio of the organic acid (D) alone is adjusted by the amount of ion exchange water used. Is done. If the content ratio of the organic acid (D) alone is too small, the bismuth compound (C) is not sufficiently dissolved, so that the curability of the resulting coating film is lowered. On the other hand, even if the content ratio of the organic acid (D) alone is too large, the bismuth compound (C) is not sufficiently dissolved, so that the curability of the coating film is lowered.
第1混合時における混合物の温度は、ビスマス化合物(C)の溶解性に影響を与えるものではなく、通常、10〜30℃であり、好ましくは室温である。 The temperature of the mixture during the first mixing does not affect the solubility of the bismuth compound (C), and is usually 10 to 30 ° C., preferably room temperature.
第1混合時の撹拌速度は、撹拌流が生じる程度の撹拌が達成される限り特に限定されない。 The stirring speed at the time of the first mixing is not particularly limited as long as stirring to such an extent that a stirring flow is generated is achieved.
第1混合は、ビスマス化合物(C)の体積平均粒子径D50が100nm以下、好ましくは50nm以下、より好ましくは20nm以下になるまで行うことが好ましい。本発明においてはビスマス化合物(C)の溶解性が十分に向上するため、溶解速度が十分に速くなる。その結果、本発明において上記平均粒子径を達成するための第1混合の時間は約1.5時間以内であり、好ましくは0.5〜1.2時間である。 The first mixing is preferably performed until the volume average particle diameter D50 of the bismuth compound (C) is 100 nm or less, preferably 50 nm or less, more preferably 20 nm or less. In the present invention, the solubility of the bismuth compound (C) is sufficiently improved, so that the dissolution rate is sufficiently high. As a result, in the present invention, the first mixing time for achieving the average particle size is within about 1.5 hours, preferably 0.5 to 1.2 hours.
第1混合を行った後は、得られた混合物、顔料分散樹脂(E)および顔料(F)をさらに混合して、顔料分散ペーストが調製される。第1混合で得られた混合物、顔料分散樹脂(E)および顔料(F)の混合(以下、単に「第2混合」ということがある)は、これらの混合物を撹拌することにより達成される。 After the first mixing, the obtained mixture, the pigment dispersion resin (E) and the pigment (F) are further mixed to prepare a pigment dispersion paste. Mixing of the mixture obtained by the first mixing, the pigment dispersion resin (E) and the pigment (F) (hereinafter sometimes simply referred to as “second mixing”) is achieved by stirring these mixtures.
第2混合時における顔料分散樹脂(E)および顔料(F)の混合量は、得られる顔料分散ペーストが下記条件(ii)を満たすような量である。
(ii)ビスマス化合物(C)、顔料分散樹脂(E)および顔料(F)の含有量の質量比が(C)+(F):(E)で1:0.2〜1:0.5、好ましくは1:0.25〜1:0.4である。
The mixing amount of the pigment dispersion resin (E) and the pigment (F) at the time of the second mixing is such an amount that the obtained pigment dispersion paste satisfies the following condition (ii).
(Ii) The mass ratio of the contents of the bismuth compound (C), the pigment dispersion resin (E), and the pigment (F) is 1: 0.2 to 1: 0.5 when (C) + (F) :( E). The ratio is preferably 1: 0.25 to 1: 0.4.
上記条件(ii)において、ビスマス化合物(C)の含有量は第1混合で混合されるビスマス化合物(C)の量(質量)である。
顔料分散樹脂(E)の含有量は第2混合で混合される顔料分散樹脂の量(質量)であり、当該顔料分散樹脂が溶液形態の場合は、当該溶液中の固形分の量(質量)である。
顔料(F)の含有量は第2混合で混合される顔料の質量である。
In said condition (ii), content of a bismuth compound (C) is the quantity (mass) of the bismuth compound (C) mixed by 1st mixing.
The content of the pigment dispersion resin (E) is the amount (mass) of the pigment dispersion resin mixed in the second mixing. When the pigment dispersion resin is in the form of a solution, the amount (mass) of the solid content in the solution It is.
The content of the pigment (F) is the mass of the pigment mixed in the second mixing.
上記条件(ii)において、ビスマス化合物(C)および顔料(F)に対する顔料分散樹脂(E)の含有量の質量比が小さすぎると、塗膜の硬化性および均一性、ならびに顔料分散ペーストおよび電着塗料組成物の保存安定性が低下する。ビスマス化合物(C)および顔料(F)に対する顔料分散樹脂(E)の含有量の質量比が大きすぎても、塗膜の硬化性および均一性、ならびに顔料分散ペーストおよび電着塗料組成物の保存安定性が低下する。 In the above condition (ii), if the mass ratio of the content of the pigment dispersion resin (E) to the bismuth compound (C) and the pigment (F) is too small, the curability and uniformity of the coating film, as well as the pigment dispersion paste and the electricity The storage stability of the coating composition decreases. Even if the mass ratio of the content of the pigment dispersion resin (E) to the bismuth compound (C) and the pigment (F) is too large, the curability and uniformity of the coating film, and the preservation of the pigment dispersion paste and the electrodeposition coating composition Stability is reduced.
顔料分散ペースト中の顔料分散樹脂(E)の含有量は通常、顔料(F)100質量部に対して樹脂固形分比で20〜40質量部である。 The content of the pigment-dispersed resin (E) in the pigment-dispersed paste is usually 20 to 40 parts by mass in terms of resin solid content with respect to 100 parts by mass of the pigment (F).
第2混合時における混合物の温度は、特に限定されるものではないが、顔料分散ペースト安定性の観点から、20〜50℃、特に30〜40℃が好ましい。 Although the temperature of the mixture at the time of the 2nd mixing is not specifically limited, 20-50 degreeC, especially 30-40 degreeC is preferable from a viewpoint of pigment dispersion paste stability.
第2混合は通常、顔料の分散粒度が10μm以下となるまで行われる。 The second mixing is usually performed until the dispersed particle size of the pigment is 10 μm or less.
本発明においては、第2混合直前の混合物、すなわち顔料分散樹脂(E)および顔料(F)を混合する直前の混合物は、5%以下、特に1.5質量%以下のビスマス化合物溶解残渣量を示すことが好ましい。
ビスマス化合物溶解残渣量は、混合物におけるビスマス化合物(C)の含有量(仕込み量)に対する割合で示すものとし、後述の方法により測定された値を用いている。
In the present invention, the mixture immediately before the second mixing, that is, the mixture immediately before mixing the pigment dispersion resin (E) and the pigment (F) has a bismuth compound dissolution residue amount of 5% or less, particularly 1.5% by mass or less. It is preferable to show.
The amount of the bismuth compound dissolution residue is shown as a ratio with respect to the content (charge amount) of the bismuth compound (C) in the mixture, and a value measured by the method described later is used.
本発明においては、塗膜の硬化性のより一層の向上の観点から、顔料分散ペーストに含まれるビスマス化合物(C)の含有量は、顔料分散ペーストの固形分に対して、金属元素換算で0.5〜5質量%、好ましくは1〜3質量%、より好ましくは1〜2質量%であることが好ましい。ビスマス化合物(C)の含有量は第1混合で混合されるビスマス化合物(C)の量(質量)である。 In the present invention, from the viewpoint of further improving the curability of the coating film, the content of the bismuth compound (C) contained in the pigment dispersion paste is 0 in terms of metal elements with respect to the solid content of the pigment dispersion paste. 0.5 to 5% by mass, preferably 1 to 3% by mass, more preferably 1 to 2% by mass. The content of the bismuth compound (C) is the amount (mass) of the bismuth compound (C) mixed in the first mixing.
本明細書中において「顔料分散ペーストの固形分」とは、顔料分散ペースト中に含まれる成分であって、溶媒の除去によっても固形となって残存する成分全ての質量を意味する。具体的には、顔料分散ペースト中に含まれる、ビスマス化合物(C)、顔料分散樹脂(E)および顔料(F)および必要に応じて添加される他の固形成分の質量の総量を意味する。 In the present specification, the “solid content of the pigment dispersion paste” means the mass of all components that are contained in the pigment dispersion paste and remain solid even after removal of the solvent. Specifically, it means the total mass of the bismuth compound (C), the pigment dispersion resin (E) and the pigment (F) and other solid components added as necessary, contained in the pigment dispersion paste.
「金属元素換算」とは、金属化合物の含有量に金属元素換算係数(金属化合物量を金属元素量に換算するための係数であり、具体的には、金属化合物中の金属元素の原子量を、金属化合物の分子量で除算した値を意味する。)を積算することにより、目的の金属元素量を求めることである。例えば、ビスマス化合物(C)が酸化ビスマス(Bi2O3、分子量466)である場合、酸化ビスマスを0.1質量%含む電着塗料組成物における、ビスマスの金属元素換算含有量は、0.1質量%×(418÷466)の計算により0.0897質量%と算出される。 “Metal element conversion” is a metal element conversion coefficient (a coefficient for converting a metal compound amount into a metal element amount to the content of the metal compound. Specifically, the atomic weight of the metal element in the metal compound is It means a value obtained by dividing the molecular weight of the metal compound.) To obtain the target metal element amount. For example, when the bismuth compound (C) is bismuth oxide (Bi 2 O 3 , molecular weight 466), the metal element equivalent content of bismuth in the electrodeposition coating composition containing 0.1% by mass of bismuth oxide is 0.8. It is calculated as 0.0897% by mass by the calculation of 1% by mass × (418 ÷ 466).
顔料分散ペーストの固形分量は通常、顔料分散ペースト全量に対して40〜70質量%、特に50〜60質量%であるのが好ましい。 The solid content of the pigment dispersion paste is usually 40 to 70% by mass, particularly 50 to 60% by mass, based on the total amount of the pigment dispersion paste.
本発明においては、顔料分散ペーストの調製に際し、ビスマス化合物(C)および有機酸(D)の予備混合(第1混合)時において、さらにアミノ酸(G)を同時に混合することが好ましい。すなわち、ビスマス化合物(C)および有機酸(D)とともに、アミノ酸(G)を予め混合することが好ましい。ビスマス化合物の溶解性がより一層、向上するためである。これは、キレート性の強いアミノ酸(G)がBiに配位することで、Biの溶解安定性を向上させるためであると考えられる。 In the present invention, when preparing the pigment dispersion paste, it is preferable that the amino acid (G) is further mixed at the same time when the bismuth compound (C) and the organic acid (D) are premixed (first mixing). That is, it is preferable to mix the amino acid (G) in advance together with the bismuth compound (C) and the organic acid (D). This is because the solubility of the bismuth compound is further improved. This is considered to be because the amino acid (G) having a strong chelating property is coordinated to Bi, thereby improving the dissolution stability of Bi.
アミノ酸(G)を混合する場合、第1混合時におけるアミノ酸(G)の混合比率は、顔料分散ペーストが下記条件(iii)を満たすような比率である。
(iii)ビスマス化合物(C)におけるビスマス金属およびアミノ酸(G)の含有量のモル比がBi:(G)で1:0.5〜1:4.0、好ましくは1:1〜1:2である。
When the amino acid (G) is mixed, the mixing ratio of the amino acid (G) during the first mixing is such that the pigment dispersion paste satisfies the following condition (iii).
(Iii) The molar ratio of the content of bismuth metal and amino acid (G) in the bismuth compound (C) is Bi: (G) 1: 0.5-1: 4.0, preferably 1: 1-1: 2. It is.
上記条件(iii)において、ビスマス化合物(C)におけるビスマス金属の含有量は、前記条件(i)においてと同様である。
アミノ酸(G)の含有量は第1混合において混合されるアミノ酸の量(モル数)であり、アミノ酸(G)が溶液形態で使用される場合は、溶液中のアミノ酸単独の量(モル数)である。
In the condition (iii), the bismuth metal content in the bismuth compound (C) is the same as in the condition (i).
The content of amino acid (G) is the amount (number of moles) of amino acid mixed in the first mixture. When amino acid (G) is used in the form of a solution, the amount of amino acid alone in the solution (number of moles) It is.
上記条件(iii)において、ビスマス化合物(C)におけるビスマス金属に対するアミノ酸(G)の含有量のモル比が小さすぎても、大きすぎても、ビスマス化合物(C)の溶解性についてさらなる向上効果は得られない。 In the above condition (iii), whether the molar ratio of the content of the amino acid (G) to the bismuth metal in the bismuth compound (C) is too small or too large, the effect of further improving the solubility of the bismuth compound (C) is I can't get it.
第1混合時にアミノ酸(G)が混合される場合、第1混合により得られる混合物中のアミノ酸(G)の含有割合は通常、当該混合物全量に対するアミノ酸(G)単独の割合で、1〜16質量%であり、好ましくは1.5〜8質量%である。アミノ酸(G)単独の含有割合が小さすぎても、大きすぎても、ビスマス化合物(C)の溶解性についてさらなる向上効果は得られない。 When the amino acid (G) is mixed at the time of the first mixing, the content ratio of the amino acid (G) in the mixture obtained by the first mixing is usually 1 to 16 masses in the ratio of the amino acid (G) alone to the total amount of the mixture. %, Preferably 1.5 to 8% by mass. If the content ratio of the amino acid (G) alone is too small or too large, no further effect of improving the solubility of the bismuth compound (C) can be obtained.
[電着塗料組成物の製造]
本発明の電着塗料組成物は、前記した樹脂エマルション(1)および顔料分散ペースト(2)を混合することによって調製することができる。
[Production of electrodeposition coating composition]
The electrodeposition coating composition of the present invention can be prepared by mixing the resin emulsion (1) and the pigment dispersion paste (2).
樹脂エマルション(1)および顔料分散ペースト(2)の混合比率は、電着塗料組成物に含まれるビスマス化合物(C)の含有量が、電着塗料組成物の固形分に対して、金属元素換算で0.05〜2.00質量%、好ましくは0.10〜1.50質量%、より好ましくは0.1〜1.0質量%となるような比率であることが好ましい。ビスマス化合物(C)の含有量は第1混合で混合されるビスマス化合物(C)の量(質量)である。 The mixing ratio of the resin emulsion (1) and the pigment dispersion paste (2) is such that the content of the bismuth compound (C) contained in the electrodeposition coating composition is a metal element conversion with respect to the solid content of the electrodeposition coating composition. The ratio is preferably 0.05 to 2.00% by mass, preferably 0.10 to 1.50% by mass, more preferably 0.1 to 1.0% by mass. The content of the bismuth compound (C) is the amount (mass) of the bismuth compound (C) mixed in the first mixing.
本明細書中において「電着塗料組成物の固形分」とは、電着塗料組成物中に含まれる成分であって、溶媒の除去によっても固形となって残存する成分全ての質量を意味する。具体的には、電着塗料組成物中に含まれる、アミン化樹脂(A)、硬化剤(B)、ビスマス化合物(C)、顔料分散樹脂(E)および顔料(F)および必要に応じて添加される他の固形成分の質量の総量を意味する。 In the present specification, the “solid content of the electrodeposition coating composition” means the mass of all components that are contained in the electrodeposition coating composition and remain solid even after removal of the solvent. . Specifically, the aminated resin (A), the curing agent (B), the bismuth compound (C), the pigment dispersion resin (E) and the pigment (F) contained in the electrodeposition coating composition, and as necessary It means the total mass of other solid components to be added.
樹脂エマルション(1)および顔料分散ペースト(2)の混合比率は通常、(1):(2)の固形分質量比率で、1:0.1〜1:0.4であり、好ましくは1:0.15〜1:0.3である。 The mixing ratio of the resin emulsion (1) and the pigment dispersion paste (2) is usually from 1: 0.1 to 1: 0.4 in terms of the solid content mass ratio of (1) :( 2), preferably 1: 0.15 to 1: 0.3.
本発明の電着塗料組成物の固形分量は、電着塗料組成物全量に対し、1〜30質量%であるのが好ましい。電着塗料組成物の固形分量が1質量%未満である場合は、電着皮膜析出量が少なくなり、十分な耐食性を確保することが困難となるおそれがある。また電着塗料組成物の樹脂固形分量が30質量%を超える場合は、つきまわり性または塗装外観が悪くなるおそれがある。 The solid content of the electrodeposition coating composition of the present invention is preferably 1 to 30% by mass with respect to the total amount of the electrodeposition coating composition. When the amount of the solid content of the electrodeposition coating composition is less than 1% by mass, the amount of electrodeposition coating deposited decreases, and it may be difficult to ensure sufficient corrosion resistance. Moreover, when the resin solid content of an electrodeposition coating composition exceeds 30 mass%, there exists a possibility that throwing power or a coating external appearance may worsen.
本発明の電着塗料組成物は、pHが4.5〜7であることが好ましい。電着塗料組成物のpHが4.5未満である場合は、耐食性が劣り、また電着塗装においてスラッジの発生が生じるという不具合がある。電着塗料組成物のpHは、用いる中和酸の量、遊離酸の添加量などの調整によって、上記範囲に設定することができる。 The electrodeposition coating composition of the present invention preferably has a pH of 4.5-7. When the pH of the electrodeposition coating composition is less than 4.5, there is a problem that the corrosion resistance is inferior and sludge is generated in the electrodeposition coating. The pH of the electrodeposition coating composition can be set in the above range by adjusting the amount of neutralizing acid used, the amount of free acid added, and the like.
電着塗料組成物のpHは、温度補償機能を有する市販のpHメーターを用いて測定することができる。 The pH of the electrodeposition coating composition can be measured using a commercially available pH meter having a temperature compensation function.
電着塗料組成物の固形分100gに対する酸のミリグラム当量(MEQ(A))は40〜120であるのが好ましい。なお、電着塗料組成物の樹脂固形分100gに対する酸のミリグラム当量(MEQ(A))は、中和酸量および遊離酸の量によって調整することができる。 It is preferable that the milligram equivalent (MEQ (A)) of the acid with respect to 100 g of solid content of the electrodeposition coating composition is 40-120. In addition, the milligram equivalent (MEQ (A)) of the acid with respect to 100 g of the resin solid content of the electrodeposition coating composition can be adjusted by the amount of neutralized acid and the amount of free acid.
ここでMEQ(A)とは、mg equivalent(acid)の略であり、塗料の固形分100g当たりのすべての酸のmg当量の合計である。このMEQ(A)は、電着塗料組成物の固形分を約10g精秤し約50mlの溶剤(THF:テトラヒドロフラン)に溶解した後、1/10NのNaOH溶液を用いて電位差滴定を行うことによって、電着塗料組成物中の含有酸量を定量して測定することができる。 Here, MEQ (A) is an abbreviation for mg equivalent (acid), and is the sum of mg equivalents of all acids per 100 g of solid content of the paint. This MEQ (A) is obtained by accurately weighing about 10 g of the solid content of the electrodeposition coating composition and dissolving it in about 50 ml of a solvent (THF: tetrahydrofuran), followed by potentiometric titration using a 1/10 N NaOH solution. The amount of acid contained in the electrodeposition coating composition can be quantified and measured.
電着塗料組成物は、実質的に錫化合物および鉛化合物の何れも含まないものであるのが好ましい。本明細書において「電着塗料組成物が実質的に錫化合物および鉛化合物の何れも含まない」とは、電着塗料組成物に含まれる鉛化合物の濃度が鉛金属元素として50ppmを超えず、かつ、有機錫化合物の濃度が錫金属元素として50ppmを超えないことを意味する。本発明の電着塗料組成物においては、ビスマス化合物(C)が含まれる。そのため、硬化触媒としての鉛化合物、有機錫化合物を用いる必要がない。これにより、実質的に錫化合物および鉛化合物の何れも含まない電着塗料組成物を調製することができる。 It is preferable that the electrodeposition coating composition contains substantially neither a tin compound nor a lead compound. In the present specification, “the electrodeposition coating composition is substantially free of both a tin compound and a lead compound” means that the concentration of the lead compound contained in the electrodeposition coating composition does not exceed 50 ppm as a lead metal element, And it means that the concentration of the organic tin compound does not exceed 50 ppm as a tin metal element. The electrodeposition coating composition of the present invention contains a bismuth compound (C). Therefore, it is not necessary to use a lead compound or an organic tin compound as a curing catalyst. Thereby, the electrodeposition coating composition which does not contain any of a tin compound and a lead compound can be prepared.
本発明の電着塗料組成物は、塗料分野において一般的に用いられている添加剤、例えば、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エチルヘキシルエーテル、プロピレングリコールモノブチルエーテル、ジプロピ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フェニルエーテルなどの有機溶媒、乾き防止剤、消泡剤などの界面活性剤、アクリル樹脂微粒子などの粘度調整剤、はじき防止剤、バナジウム塩、銅、鉄、マンガン、マグネシウム、カルシウム塩などの無機防錆剤など、を必要に応じて含んでもよい。またこれら以外に、目的に応じて公知の補助錯化剤、緩衝剤、平滑剤、応力緩和剤、光沢剤、半光沢剤、酸化防止剤、および紫外線吸収剤などを配合してもよい。これらの添加剤は、樹脂エマルションの製造時に添加されてもよいし、顔料分散ペースト製造の際の第2混合時に添加されてもよいし、または樹脂エマルションと顔料分散ペーストとの混合時または混合後に添加されてもよい。 The electrodeposition coating composition of the present invention comprises additives generally used in the coating field, such as ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monoethyl hexyl ether, propylene glycol monobutyl ether, dipropylene glycol. Organic solvents such as monobutyl ether and propylene glycol monophenyl ether, surfactants such as anti-drying agents and antifoaming agents, viscosity modifiers such as acrylic resin fine particles, anti-fogging agents, vanadium salts, copper, iron, manganese, magnesium, An inorganic rust preventive agent such as a calcium salt may be included as necessary. In addition to these, known auxiliary complexing agents, buffering agents, smoothing agents, stress relaxation agents, brighteners, semi-brightening agents, antioxidants, ultraviolet absorbers, and the like may be blended depending on the purpose. These additives may be added during the production of the resin emulsion, may be added during the second mixing during the production of the pigment dispersion paste, or during or after the mixing of the resin emulsion and the pigment dispersion paste. It may be added.
本発明の電着塗料組成物は、上記アミン化樹脂(A)以外にも、他の塗膜形成樹脂成分を含んでもよい。他の塗膜形成樹脂成分として、例えば、アクリル樹脂、ポリエステル樹脂、ウレタン樹脂、ブタジエン系樹脂、フェノール樹脂、キシレン樹脂などが挙げられる。上述したようなアミン化樹脂(A)に該当しないアミン化樹脂であってもよい。電着塗料組成物に含まれうる他の塗膜形成樹脂成分として、フェノール樹脂、キシレン樹脂が好ましい。フェノール樹脂、キシレン樹脂として、例えば、2以上10以下の芳香族環を有するキシレン樹脂が挙げられる。 The electrodeposition coating composition of the present invention may contain other film-forming resin components in addition to the aminated resin (A). Examples of other film forming resin components include acrylic resin, polyester resin, urethane resin, butadiene resin, phenol resin, xylene resin, and the like. The aminated resin which does not correspond to the aminated resin (A) as described above may be used. Phenol resins and xylene resins are preferred as other film-forming resin components that can be included in the electrodeposition coating composition. Examples of the phenol resin and xylene resin include xylene resins having 2 or more and 10 or less aromatic rings.
[電着塗装および電着塗膜形成]
本発明の電着塗料組成物を用いて被塗物に対し電着塗装および電着塗膜形成を行うことができる。
本発明の電着塗料組成物を用いる電着塗装においては、被塗物を陰極とし、陽極との間に、電圧を印加する。これにより、電着皮膜が被塗物上に析出する。
[Electrodeposition coating and electrodeposition coating formation]
The electrodeposition coating composition of the present invention can be used for electrodeposition coating and electrodeposition coating film formation on an object to be coated.
In the electrodeposition coating using the electrodeposition coating composition of the present invention, a voltage is applied between an object to be coated and a cathode. Thereby, an electrodeposition film deposits on a to-be-coated article.
電着塗装工程において、電着塗料組成物中に被塗物を浸漬した後、50〜450Vの電圧を印加することによって、電着塗装が行われる。印加電圧が50V未満であると電着が不充分となるおそれがあり、450Vを超えると、塗膜が破壊され異常外観となるおそれがある。電着塗装時、塗料組成物の浴液温度は、通常10〜45℃に調節される。 In the electrodeposition coating step, the electrodeposition coating is performed by applying a voltage of 50 to 450 V after the object to be coated is immersed in the electrodeposition coating composition. If the applied voltage is less than 50V, electrodeposition may be insufficient, and if it exceeds 450V, the coating film may be destroyed and an abnormal appearance may be obtained. At the time of electrodeposition coating, the bath temperature of the coating composition is usually adjusted to 10 to 45 ° C.
電圧を印加する時間は、電着条件によって異なるが、一般には、2〜5分とすることができる。 The time for applying the voltage varies depending on the electrodeposition conditions, but can generally be 2 to 5 minutes.
電着皮膜の膜厚は、加熱硬化により最終的に得られる電着塗膜の膜厚が好ましくは5〜40μm、より好ましくは10〜25μmとなるような膜厚とする。電着塗膜の膜厚が5μm未満であると、耐食性が不充分となるおそれがある。一方40μmを超えると、塗料の浪費につながる。 The film thickness of the electrodeposition film is such that the film thickness of the electrodeposition film finally obtained by heat curing is preferably 5 to 40 μm, more preferably 10 to 25 μm. If the film thickness of the electrodeposition coating film is less than 5 μm, the corrosion resistance may be insufficient. On the other hand, if it exceeds 40 μm, it leads to waste of paint.
上述のようにして得られる電着皮膜を、電着過程の終了後、そのまま、または水洗した後、120〜260℃、好ましくは140〜220℃で、10〜30分間加熱することによって、加熱硬化した電着塗膜が形成される。 The electrodeposition film obtained as described above is heat-cured by heating at 120 to 260 ° C., preferably 140 to 220 ° C. for 10 to 30 minutes after completion of the electrodeposition process or after washing with water. An electrodeposition coating film is formed.
本発明の電着塗料組成物を塗装する被塗物としては、通電可能な種々の被塗物を用いることができる。使用できる被塗物として例えば、冷延鋼板、熱延鋼板、ステンレス、電気亜鉛めっき鋼板、溶融亜鉛めっき鋼板、亜鉛−アルミニウム合金系めっき鋼板、亜鉛−鉄合金系めっき鋼板、亜鉛−マグネシウム合金系めっき鋼板、亜鉛−アルミニウム−マグネシウム合金系めっき鋼板、アルミニウム系めっき鋼板、アルミニウム−シリコン合金系めっき鋼板、錫系めっき鋼板などが挙げられる。 As an object to be coated with the electrodeposition coating composition of the present invention, various objects that can be energized can be used. Examples of coatings that can be used include cold-rolled steel sheets, hot-rolled steel sheets, stainless steel, electrogalvanized steel sheets, hot-dip galvanized steel sheets, zinc-aluminum alloy plated steel sheets, zinc-iron alloy plated steel sheets, zinc-magnesium alloy based plating. Examples include steel plates, zinc-aluminum-magnesium alloy plated steel plates, aluminum-based plated steel plates, aluminum-silicon alloy-plated steel plates, and tin-based plated steel plates.
以下の実施例により本発明をさらに具体的に説明するが、本発明はこれらに限定されない。実施例中、「部」および「%」は、ことわりのない限り、質量基準による。 The following examples further illustrate the present invention, but the present invention is not limited thereto. In the examples, “parts” and “%” are based on mass unless otherwise specified.
製造例1 顔料分散樹脂の製造
撹拌機、冷却管、窒素導入管、温度計を備えた反応容器にビスフェノールA型エポキシ樹脂(商品名DER−331J、ダウケミカル社製)385部、ビスフェノールA120部、オクチル酸95部、2−エチル−4−メチルイミダゾール1%溶液1部を仕込んで、窒素雰囲気下160〜170℃で1時間反応させ、ついで120℃まで冷却後、2−エチルヘキサノール化ハーフブロック化トリレンジイソシアネートのメチルイソブチルケトン溶液(固形分95%)198部を加えた。反応混合物を120〜130℃で1時間保持した後、エチレングリコールモノn−ブチルエーテル157部を加えた。そして85〜95℃に冷却して均一化させた。つぎにジエチレントリアミンジケチミン(固形分73%のメチルイソブチルケトン溶液)277部を加え120℃で1時間撹拌しエチレングリコールモノn−ブチルエーテル13部を加え、アミン化樹脂を製造した。ついで18部のイオン交換水とギ酸8部を仕込み上記アミン化樹脂を混合し15分撹拌し、イオン交換水200部を混合して、顔料分散樹脂(平均分子量2,200)の樹脂溶液(樹脂固形分25%)を得た。
Production Example 1 Production of Pigment Dispersion Resin 385 parts of bisphenol A type epoxy resin (trade name DER-331J, manufactured by Dow Chemical Company), 120 parts of bisphenol A in a reaction vessel equipped with a stirrer, a cooling pipe, a nitrogen introduction pipe, and a thermometer, Charge 95 parts octyl acid and 1 part 2-ethyl-4-methylimidazole 1% solution, react at 160-170 ° C. for 1 hour in a nitrogen atmosphere, then cool to 120 ° C., then 2-ethylhexanolated half-blocked 198 parts of a methyl isobutyl ketone solution of tolylene diisocyanate (solid content 95%) was added. After maintaining the reaction mixture at 120 to 130 ° C. for 1 hour, 157 parts of ethylene glycol mono n-butyl ether was added. And it cooled to 85-95 degreeC and made it uniform. Next, 277 parts of diethylenetriamine diketimine (a methyl isobutyl ketone solution having a solid content of 73%) was added and stirred at 120 ° C. for 1 hour, and 13 parts of ethylene glycol mono-n-butyl ether was added to produce an aminated resin. Next, 18 parts of ion-exchanged water and 8 parts of formic acid were added, the aminated resin was mixed and stirred for 15 minutes, 200 parts of ion-exchanged water was mixed, and a resin solution (resin of pigment dispersion resin (average molecular weight 2,200)) 25% solids) was obtained.
製造例2 アミン化樹脂の製造
メチルイソブチルケトン92部、ビスフェノールA型エポキシ樹脂(商品名DER−331J、ダウケミカル社製)940部、ビスフェノールA325部、オクチル酸65部、ジメチルベンジルアミン2部を加え、反応容器内の温度を140℃に保持し、エポキシ当量が1220g/eqになるまで反応させた後、反応容器内の温度が120℃になるまで冷却した。ついでジエチレントリアミンジケチミン(固形分73%のメチルイソブチルケトン溶液)52部とジエタノールアミン83部の混合物を添加し、120℃で1時間反応させることにより、アミン化樹脂(カチオン変性エポキシ樹脂)を得た。
この樹脂の数平均分子量は2,560、アミン価は50mgKOH/g(うち1級アミンに由来するアミン価は14mgKOH/g)、水酸基価は240mgKOH/gであった。
Production Example 2 Production of aminated resin 92 parts of methyl isobutyl ketone, 940 parts of bisphenol A type epoxy resin (trade name DER-331J, manufactured by Dow Chemical Company), 325 parts of bisphenol A, 65 parts of octylic acid, and 2 parts of dimethylbenzylamine were added. The temperature in the reaction vessel was maintained at 140 ° C., and the reaction was continued until the epoxy equivalent reached 1220 g / eq, and then cooled until the temperature in the reaction vessel reached 120 ° C. Next, a mixture of 52 parts of diethylenetriamine diketimine (methyl isobutyl ketone solution having a solid content of 73%) and 83 parts of diethanolamine was added and reacted at 120 ° C. for 1 hour to obtain an aminated resin (cation-modified epoxy resin).
The number average molecular weight of this resin was 2,560, the amine value was 50 mgKOH / g (of which the amine value derived from the primary amine was 14 mgKOH / g), and the hydroxyl value was 240 mgKOH / g.
製造例3−1 ブロックイソシアネート硬化剤(1)の製造
ヘキサメチレンジイソシアネート(HDI)1680部およびMIBK732部を反応容器に仕込み、これを60℃まで加熱した。ここに、トリメチロールプロパン346部をMEKオキシム1067部に溶解させたものを60℃で2時間かけて滴下した。さらに75℃で4時間加熱した後、IRスペクトルの測定において、イソシアネート基に基づく吸収が消失したことを確認し、放冷後、MIBK27部を加えて固形分が78%のブロックイソシアネート硬化剤(1)を得た。イソシアネート基価は252mgKOH/gであった。
Production Example 3-1 Production of Blocked Isocyanate Curing Agent (1) 1680 parts of hexamethylene diisocyanate (HDI) and 732 parts of MIBK were charged into a reaction vessel and heated to 60 ° C. A solution obtained by dissolving 346 parts of trimethylolpropane in 1067 parts of MEK oxime was added dropwise at 60 ° C. over 2 hours. Further, after heating at 75 ° C. for 4 hours, in the measurement of IR spectrum, it was confirmed that the absorption based on the isocyanate group disappeared, and after standing to cool, 27 parts of MIBK was added to add a blocked isocyanate curing agent (1 ) The isocyanate group value was 252 mgKOH / g.
製造例3−2 ブロックイソシアネート硬化剤(2)の製造
4,4’−ジフェニルメタンジイソシアナート1340部およびMIBK277部を反応容器に仕込み、これを80℃まで加熱した後、ε−カプロラクタム226部をブチルセロソルブ944部に溶解させたものを80℃で2時間かけて滴下した。さらに100℃で4時間加熱した後、IRスペクトルの測定において、イソシアネート基に基づく吸収が消失したことを確認し、放冷後、MIBK349部を加えてブロックイソシアネート硬化剤(2)を得た(固形分80%)。イソシアネート基価は251mgKOH/gであった。
Production Example 3-2 Production of Blocked Isocyanate Curing Agent (2) 1,340 parts of 4,4′-diphenylmethane diisocyanate and 277 parts of MIBK were charged into a reaction vessel and heated to 80 ° C., and then 226 parts of ε-caprolactam was added to butyl cellosolve. What was dissolved in 944 parts was dripped at 80 degreeC over 2 hours. Furthermore, after heating at 100 degreeC for 4 hours, in the measurement of IR spectrum, it confirmed that the absorption based on an isocyanate group disappeared, and after standing to cool, MIBK349 parts were added and block isocyanate hardening | curing agent (2) was obtained (solid). Min 80%). The isocyanate group value was 251 mgKOH / g.
製造例4 樹脂エマルションの製造
製造例2で得たアミン化樹脂350g(固形分)と、製造例3−1で得たブロックイソシアネート硬化剤(1)75g(固形分)および製造例3−2で得たブロックイソシアネート硬化剤(2)75g(固形分)とを混合し、エチレングリコールモノ−2−エチルヘキシルエーテルを固形分に対して3%(15g)になるように添加した。次に、ギ酸および酢酸を等モルで、それらの合計添加量が樹脂中和率40%相当分になるように加えて中和し、イオン交換水を加えてゆっくり希釈し、次いで固形分が40%になるように減圧下でメチルイソブチルケトンを除去して、樹脂エマルションを得た。
Production Example 4 Production of Resin Emulsion 350 g (solid content) of the aminated resin obtained in Production Example 2, 75 g (solid content) of the blocked isocyanate curing agent (1) obtained in Production Example 3-1, and Production Example 3-2 75 g (solid content) of the obtained blocked isocyanate curing agent (2) was mixed, and ethylene glycol mono-2-ethylhexyl ether was added to 3% (15 g) based on the solid content. Next, formic acid and acetic acid are equimolarly added so that the total addition amount thereof is equivalent to a resin neutralization rate of 40%, neutralized, and slowly diluted with ion-exchanged water. %, Methyl isobutyl ketone was removed under reduced pressure to obtain a resin emulsion.
(実施例1)
顔料分散ペーストの製造
表1に示す配合に基づき、イオン交換水、50%乳酸水溶液を混合および撹拌しながら、これに酸化ビスマスを添加し、室温で1時間、1000rpmにて攪拌した(第1混合)。その後、混合物を508meshでろ過し、溶解残渣を除き、均一な混合物を得た。得られた混合物に対して、サンドミルを用いて、製造例1で得られた顔料分散樹脂および顔料を、表1に示す配合に基づき、さらに混合し、40℃で1時間、2000rpmにて撹拌した(第2混合)。
この際、顔料分散樹脂および顔料が混合される直前の混合物におけるビスマス化合物の平均粒子径を測定した。なお、顔料分散樹脂および顔料が混合される直前の混合物としては、第1混合直後であってろ過前の混合物を用いた。
本明細書中、平均粒子径は体積平均粒子径D50であり、レーザードップラー式粒度分析計(日機装社製、「マイクロトラックUPA150」)を用いて、分散体を信号レベルが適性になるようイオン交換水で希釈して測定した。
Example 1
Manufacture of pigment dispersion paste Based on the formulation shown in Table 1, while mixing and stirring ion exchange water and 50% aqueous lactic acid solution, bismuth oxide was added thereto and stirred at 1000 rpm for 1 hour at room temperature (first mixing) ). Thereafter, the mixture was filtered with 508 mesh to remove the dissolution residue, thereby obtaining a uniform mixture. Using the sand mill, the pigment dispersion resin and pigment obtained in Production Example 1 were further mixed based on the formulation shown in Table 1, and stirred at 2000 rpm for 1 hour at 40 ° C. (Second mixture).
Under the present circumstances, the average particle diameter of the bismuth compound in the mixture just before mixing a pigment dispersion resin and a pigment was measured. In addition, as the mixture immediately before the pigment dispersion resin and the pigment were mixed, the mixture immediately after the first mixing and before the filtration was used.
In this specification, the average particle size is a volume average particle size D50, and ion exchange is performed using a laser Doppler particle size analyzer (manufactured by Nikkiso Co., Ltd., “Microtrac UPA150”) so that the signal level is appropriate. Diluted with water and measured.
電着塗料組成物の製造
ステンレス容器に、イオン交換水504g、製造例4で得た樹脂エマルション370gおよび上記顔料分散ペースト81gを添加し、その後、40℃で16時間エージングして、電着塗料組成物を得た。
Production of electrodeposition paint composition To a stainless steel container, 504 g of ion-exchanged water, 370 g of the resin emulsion obtained in Production Example 4 and 81 g of the pigment dispersion paste are added, and then aged at 40 ° C. for 16 hours to obtain an electrodeposition paint composition. I got a thing.
(実施例2〜7および比較例1〜8)
顔料分散ペーストの製造において、ビスマス化合物および有機酸の種類および配合量ならびにイオン交換水、顔料分散樹脂の溶液および顔料の配合量を表1に示すように変更したこと、および電着塗料組成物の製造において、樹脂エマルションと顔料分散ペーストとの配合比を、表1に示す「電着塗料組成物におけるビスマス化合物の含有量」が達成されるような比率に変更したこと以外、実施例1と同様の方法により、電着塗料組成物を得た。
なお、アミノ酸を使用する場合、アミノ酸は有機酸と同時に混合した。
(Examples 2-7 and Comparative Examples 1-8)
In the production of the pigment dispersion paste, the types and blending amounts of the bismuth compound and the organic acid, the ion exchange water, the pigment dispersion resin solution and the pigment blending amount were changed as shown in Table 1, and the electrodeposition coating composition In production, the blending ratio of the resin emulsion and the pigment dispersion paste was changed to such a ratio that “the content of the bismuth compound in the electrodeposition coating composition” shown in Table 1 was achieved. By this method, an electrodeposition coating composition was obtained.
In addition, when using an amino acid, the amino acid was mixed simultaneously with the organic acid.
表中の注釈を以下に示す。
(I):モル比の算出において(C)のBiは第1混合で混合されたビスマス化合物(C)におけるビスマス金属のモル数であり、(D)は第1混合で混合された有機酸水溶液中の有機酸単独のモル数である。
(II):質量比の算出において(C)は第1混合で混合されたビスマス化合物の質量、(F)は第2混合で混合された顔料の質量、(E)は第2混合で混合された顔料分散樹脂溶液中の固形分の質量である。
(III):モル比の算出において(C)のBiは第1混合で混合されたビスマス化合物(C)におけるビスマス金属のモル数であり、(G)は第1混合で混合されたアミノ酸水溶液中のアミノ酸単独のモル数である。
(IV):第1混合時の有機酸(D)の含有割合は、第1混合時の混合物全量に対する、有機酸(D)水溶液中の有機酸(D)単独の割合である。
(V):第1混合時のアミノ酸(G)の含有割合は、第1混合時の混合物全量に対する、アミノ酸(G)水溶液中のアミノ酸(G)単独の割合である。
(VI):ビスマス化合物(C)の含有量は、顔料分散ペースト(2)の固形分に対する割合であって、金属元素換算での値である。
(VII):ビスマス化合物(C)の含有量は、電着塗料組成物の固形分に対する割合であって、金属元素換算での値である。
(VIII):ビスマス化合物の粒子径は、第1混合直前のビスマス化合物(C)の平均粒子径である。
(IX):ビスマス化合物の粒子径は、溶解残渣除去直前の混合物におけるビスマス化合物(C)の平均粒子径である。
The annotations in the table are shown below.
(I): In the calculation of the molar ratio, Bi in (C) is the number of moles of bismuth metal in the bismuth compound (C) mixed in the first mixing, and (D) is an organic acid aqueous solution mixed in the first mixing. It is the number of moles of the organic acid alone.
(II): In calculating the mass ratio, (C) is the mass of the bismuth compound mixed in the first mixing, (F) is the mass of the pigment mixed in the second mixing, and (E) is mixed in the second mixing. The mass of the solid content in the pigment-dispersed resin solution.
(III): In calculation of the molar ratio, Bi in (C) is the number of moles of bismuth metal in the bismuth compound (C) mixed in the first mixing, and (G) is in the aqueous amino acid solution mixed in the first mixing. The number of moles of amino acid alone.
(IV): The content ratio of the organic acid (D) at the time of the first mixing is a ratio of the organic acid (D) alone in the aqueous solution of the organic acid (D) to the total amount of the mixture at the time of the first mixing.
(V): The content ratio of the amino acid (G) at the time of the first mixing is a ratio of the amino acid (G) alone in the amino acid (G) aqueous solution to the total amount of the mixture at the time of the first mixing.
(VI): The content of the bismuth compound (C) is a ratio with respect to the solid content of the pigment dispersion paste (2) and is a value in terms of a metal element.
(VII): The content of the bismuth compound (C) is a ratio to the solid content of the electrodeposition coating composition, and is a value in terms of a metal element.
(VIII): The particle diameter of the bismuth compound is the average particle diameter of the bismuth compound (C) immediately before the first mixing.
(IX): The particle diameter of the bismuth compound is the average particle diameter of the bismuth compound (C) in the mixture immediately before removal of the dissolved residue.
(評価方法)
冷延鋼板(JIS G3141、SPCC−SD)を、サーフクリーナーEC90(日本ペイント社製)中に50℃で2分間浸漬して、脱脂処理した。次にサーフファインGL1(日本ペイント社製)に常温30秒浸漬し、サーフダイン6350(日本ペイント社製)に35℃×2分間浸漬した。脱イオン水による水洗を行った。
一方、得られた電着塗料組成物に、硬化後の電着塗膜の膜厚が15μmとなるように2−エチルヘキシルグリコールを必要量添加した。その後、電着塗料組成物に鋼板を全て埋没させた後、直ちに電圧の印加を開始し、30秒間昇圧し180Vに達してから150秒間保持する条件で電圧を印加して、被塗物(冷延鋼板)上に未硬化の電着皮膜を析出させた。得られた未硬化の電着皮膜を、160℃で15分間加熱硬化させて、電着塗膜を有する電着塗装板を得た。
(Evaluation method)
A cold-rolled steel plate (JIS G3141, SPCC-SD) was immersed in Surf Cleaner EC90 (manufactured by Nippon Paint Co., Ltd.) at 50 ° C. for 2 minutes for degreasing treatment. Next, it was immersed in Surffine GL1 (manufactured by Nippon Paint Co., Ltd.) at room temperature for 30 seconds and immersed in Surfdyne 6350 (manufactured by Nippon Paint Co., Ltd.) at 35 ° C. for 2 minutes. Washed with deionized water.
On the other hand, a necessary amount of 2-ethylhexyl glycol was added to the obtained electrodeposition coating composition so that the film thickness of the electrodeposition coating film after curing was 15 μm. Then, after all the steel sheets were buried in the electrodeposition coating composition, voltage application was started immediately, and the voltage was applied under the condition that the voltage was increased for 30 seconds and reached 180 V and then held for 150 seconds. An uncured electrodeposition film was deposited on the steel sheet. The obtained uncured electrodeposition film was heat-cured at 160 ° C. for 15 minutes to obtain an electrodeposition coated plate having an electrodeposition film.
ビスマス化合物の溶解性
顔料分散ペーストの製造において、顔料分散樹脂および顔料を混合する直前の混合物におけるビスマス化合物の平均粒子径を測定した。平均粒子径は、体積平均粒子径D50であり、レーザードップラー式粒度分析計(日機装社製、「マイクロトラックUPA150」)を用いて、分散体を信号レベルが適性になるようイオン交換水で希釈して測定し、下記基準にてビスマス化合物の溶解性を評価した。
評価基準
◎;D50 10nm以下。
○;D50 10nm超20nm以下;
○△;D50 20nm超50nm以下;
△;D50 50nm超100nm以下(実用上問題なし);
×;D50 100nm超500nm以下(実用上問題あり);
××;D50 500nm超。
In the production of the bismuth compound soluble pigment dispersion paste, the average particle size of the bismuth compound in the mixture immediately before mixing the pigment dispersion resin and the pigment was measured. The average particle diameter is a volume average particle diameter D50, and the dispersion is diluted with ion-exchanged water so that the signal level is appropriate using a laser Doppler particle size analyzer (manufactured by Nikkiso Co., Ltd., “Microtrac UPA150”). And the solubility of the bismuth compound was evaluated according to the following criteria.
Evaluation criteria A: D50 10 nm or less.
○: D50 more than 10 nm and 20 nm or less;
○ △; D50 more than 20 nm and less than 50 nm;
Δ: D50 more than 50 nm and less than 100 nm (no problem in practical use);
X: D50 more than 100 nm and 500 nm or less (practical problem);
XX; D50 More than 500 nm.
顔料分散ペーストの保存安定性
40℃で1ヵ月間保管した顔料分散ペーストの状態を目視にて評価した。評価基準は以下の通りとした。
評価基準
○;分離や沈降が見られない;
△;柔らかい沈降があるが、攪拌で均一な状態に戻る(実用上問題なし);
×;硬い沈降が発生し、攪拌しても均一にならない(実用上問題あり)。
Storage Stability of Pigment Dispersion Paste The state of the pigment dispersion paste stored for 1 month at 40 ° C. was visually evaluated. The evaluation criteria were as follows.
Evaluation criteria ○: No separation or sedimentation is observed;
Δ: Soft sedimentation, but returns to a uniform state by stirring (no problem in practical use);
X: Hard sediment occurs and does not become uniform even with stirring (practically problematic).
塗料の保存安定性
40℃で1ヵ月間保管した塗料の状態を塗料のろ過性にて評価した。評価基準は以下の通りとした。
評価基準
○;508mesh(NBC製)を容易に通過する;
△;508meshを通過しにくい(実用上問題なし);
×;508meshを通過することができない(実用上問題あり)。
Storage stability of paint The state of the paint stored at 40 ° C. for 1 month was evaluated by the filterability of the paint. The evaluation criteria were as follows.
Evaluation criteria: pass easily through 508 mesh (manufactured by NBC);
Δ: Difficult to pass through 508 mesh (no problem in practical use);
X: Cannot pass 508 mesh (practical problem).
硬化性
上記評価方法に従い塗装した電着塗膜を、アセトンに浸漬し、56℃で4時間加熱還流させた。還流後の電着塗膜を乾燥させ、アセトン浸漬前後での塗膜質量から、下記式より塗膜残存率を求め、硬化性の評価を行った。評価基準は以下の通りとした。
塗膜残存率=Y/X
X=アセトン浸漬前の塗膜質量;
Y=アセトン浸漬後の塗膜質量。
評価基準
○;塗膜残存率 90%以上;
△;塗膜残存率 85%以上90%未満(実用上問題なし);
×;塗膜残存率 85%未満(実用上問題あり)。
Curability The electrodeposition coating film coated in accordance with the above evaluation method was immersed in acetone and heated to reflux at 56 ° C. for 4 hours. The electrodeposition coating film after reflux was dried, and the coating film residual ratio was determined from the following formula from the coating film mass before and after the acetone immersion, and the curability was evaluated. The evaluation criteria were as follows.
Coating film residual ratio = Y / X
X = coating mass before immersion in acetone;
Y = coating film mass after acetone immersion.
Evaluation criteria ○; coating film residual ratio 90% or more;
Δ: Residual rate of coating film 85% or more and less than 90% (no problem in practical use);
X: Coating film remaining rate is less than 85% (practically problematic).
硬化電着塗膜外観(塗装外観)
上記評価方法により得られた電着塗膜を有する電着塗装板について、塗膜外観における異常の有無を目視で評価した。評価基準は以下の通りとした。
評価基準
○:均一な塗膜外観を有している;
○△:ややムラがあると視認される部分があるものの、全体としてほぼ均一な塗膜外観を有している;
△:ムラが視認されるものの、実用上問題なし;
×:塗膜外観が明らかに不均一である(実用上問題あり)。
Cured electrodeposition coating appearance (paint appearance)
About the electrodeposition coating plate which has the electrodeposition coating film obtained by the said evaluation method, the presence or absence of abnormality in a coating-film external appearance was evaluated visually. The evaluation criteria were as follows.
Evaluation criteria ○: having a uniform coating film appearance;
○ △: Although there is a portion that is visually recognized if there is some unevenness, it has a substantially uniform coating appearance as a whole;
Δ: Unevenness is visible, but there is no practical problem;
X: The coating film appearance is clearly non-uniform (practically problematic).
耐食性
塩水浸漬試験(Salt−solution Dipping Test(SDT))
冷延鋼板を用いた硬化後の電着塗装板の塗膜に、基材に達するようにナイフで傷を入れ、この塗装板を、5%食塩水中に50℃で480時間浸漬した後、直線状の傷部からの錆やフクレ発生を観察し、評価した。評価基準は以下の通りである。
評価基準
◎:錆またはフクレが生じていない
○:錆またはフクレの最大幅がカット部より2.5mm未満(両側)
○△:錆またはフクレの最大幅がカット部より2.5mm以上5mm未満(両側)
△:錆またはフクレの最大幅がカット部より5mm以上10mm未満(両側)
△×:錆またはフクレの最大幅がカット部より10mm以上15mm未満(両側)
×:錆またはフクレの最大幅がカット部より15mm以上(両側)
Corrosion resistance
Salt water immersion test (Salt-solution Dipping Test (SDT))
The coating film of the electrodeposition coating plate after hardening using a cold-rolled steel plate was scratched with a knife so as to reach the base material, and this coated plate was immersed in 5% salt water at 50 ° C. for 480 hours. The occurrence of rust and blisters from the scratches was observed and evaluated. The evaluation criteria are as follows.
Evaluation standard ◎: No rust or blisters ○: Maximum width of rust or blisters is less than 2.5 mm from the cut (both sides)
○ △: The maximum width of rust or swelling is 2.5mm or more and less than 5mm from the cut part (both sides)
Δ: The maximum width of rust or swelling is 5 mm or more and less than 10 mm from the cut part (both sides)
Δ: The maximum width of rust or swelling is 10 mm or more and less than 15 mm from the cut part (both sides)
X: The maximum width of rust or blister is 15mm or more from the cut part (both sides)
本発明の電着塗料組成物は、例えば、自動車用塗料の下塗り塗料として有用である。 The electrodeposition coating composition of the present invention is useful, for example, as an undercoat paint for automobiles.
Claims (17)
前記樹脂エマルション(1)が、アミン化樹脂(A)およびブロックイソシアネート硬化剤(B)を含み、
前記顔料分散ペースト(2)が、ビスマス化合物(C)および有機酸(D)を予め混合し、次いで、得られた混合物、顔料分散樹脂(E)および顔料(F)を混合して調製され、
前記顔料分散ペースト(2)が下記条件を満たす電着塗料組成物:
(i)ビスマス化合物(C)におけるビスマス金属および有機酸(D)の含有量のモル比がBi:(D)で1:0.5〜1:4である;
前記ビスマス化合物(C)の平均粒子径が100nm以下である;および
(ii)ビスマス化合物(C)、顔料分散樹脂(E)および顔料(F)の含有量の質量比が(C)+(F):(E)で1:0.2〜1:0.5である。 An electrodeposition coating composition comprising a resin emulsion (1) and a pigment dispersion paste (2),
The resin emulsion (1) contains an aminated resin (A) and a blocked isocyanate curing agent (B),
The pigment dispersion paste (2) is prepared by previously mixing the bismuth compound (C) and the organic acid (D) and then mixing the resulting mixture, the pigment dispersion resin (E) and the pigment (F),
An electrodeposition coating composition in which the pigment dispersion paste (2) satisfies the following conditions:
(I) The molar ratio of the content of bismuth metal and organic acid (D) in the bismuth compound (C) is 1: 0.5 to 1: 4 in Bi: (D);
The average particle size of the bismuth compound (C) is 100 nm or less; and (ii) the mass ratio of the contents of the bismuth compound (C), the pigment dispersion resin (E) and the pigment (F) is (C) + (F ): It is 1: 0.2 to 1: 0.5 in (E).
前記スルホン酸が全炭素原子数1〜3のアルカンスルホン酸である、請求項4記載の電着塗料組成物。 The hydroxycarboxylic acid is a monohydroxymonocarboxylic acid having 2 to 4 carbon atoms and a dihydroxymonocarboxylic acid having 3 to 6 carbon atoms;
The electrodeposition coating composition according to claim 4 , wherein the sulfonic acid is an alkanesulfonic acid having 1 to 3 carbon atoms in total.
前記スルホン酸が、メタンスルホン酸である、請求項5記載の電着塗料組成物。 The hydroxycarboxylic acid is one or more selected from the group consisting of lactic acid and dimethylolpropionic acid;
The electrodeposition coating composition according to claim 5 , wherein the sulfonic acid is methanesulfonic acid.
前記顔料分散ペースト(2)は、ビスマス化合物(C)、有機酸(D)およびアミノ酸(G)を予め混合し、得られた混合物と、顔料分散樹脂(E)および顔料(F)とを混合して調製される、請求項1〜6のいずれかに記載の電着塗料組成物。 The pigment dispersion paste (2) further comprises an amino acid (G),
In the pigment dispersion paste (2), the bismuth compound (C), the organic acid (D) and the amino acid (G) are mixed in advance, and the resulting mixture is mixed with the pigment dispersion resin (E) and the pigment (F). The electrodeposition coating composition according to any one of claims 1 to 6 , which is prepared as described above.
(iii)ビスマス化合物(C)におけるビスマス金属およびアミノ酸(G)の含有量のモル比がBi:(G)で1:0.5〜1:4.0である。 The electrodeposition coating composition according to claim 7, wherein the pigment dispersion paste (2) further satisfies the following conditions:
(Iii) The molar ratio of the bismuth metal and amino acid (G) content in the bismuth compound (C) is 1: 0.5 to 1: 4.0 in terms of Bi: (G).
前記樹脂エマルション(1)は、アミン化樹脂(A)およびブロックイソシアネート硬化剤(B)をそれぞれ有機溶媒の溶液状態で混合した後、中和酸を用いて中和する工程により形成され、 The resin emulsion (1) is formed by a step of neutralizing with a neutralizing acid after mixing the aminated resin (A) and the blocked isocyanate curing agent (B) in a solution state of an organic solvent,
前記顔料分散ペースト(2)は、ビスマス化合物(C)および有機酸(D)を予め混合する第1混合工程、および、得られた混合物、顔料分散樹脂(E)および顔料(F)をさらに混合する第2混合工程により調製され、 The pigment dispersion paste (2) is a first mixing step in which the bismuth compound (C) and the organic acid (D) are mixed in advance, and the resulting mixture, the pigment dispersion resin (E), and the pigment (F) are further mixed Prepared by a second mixing step,
前記第1混合におけるビスマス化合物(C)および有機酸(D)の混合比率は、得られる顔料分散ペーストが下記条件(i)、 The mixing ratio of the bismuth compound (C) and the organic acid (D) in the first mixing is such that the resulting pigment dispersion paste has the following condition (i):
(i)ビスマス化合物(C)におけるビスマス金属および有機酸(D)の含有量のモル比がBi:(D)で1:0.5〜1:4、(I) The molar ratio of the content of bismuth metal and organic acid (D) in the bismuth compound (C) is Bi: (D) 1: 0.5-1: 4,
を満たす比率であり、A ratio that satisfies
前記第1混合は、ビスマス化合物(C)の体積平均粒子径D50が100nm以下になるまで行われ、 The first mixing is performed until the volume average particle diameter D50 of the bismuth compound (C) is 100 nm or less,
前記第2混合時における顔料分散樹脂(E)および顔料(F)の混合量は、得られる顔料分散ペーストが下記条件(ii)、 The mixing amount of the pigment dispersion resin (E) and the pigment (F) at the time of the second mixing is such that the resulting pigment dispersion paste has the following condition (ii):
(ii)ビスマス化合物(C)、顔料分散樹脂(E)および顔料(F)の含有量の質量比が(C)+(F):(E)で1:0.2〜1:0.5、(Ii) The mass ratio of the contents of the bismuth compound (C), the pigment dispersion resin (E), and the pigment (F) is 1: 0.2 to 1: 0.5 when (C) + (F) :( E). ,
を満たす量である、Is an amount that satisfies
製造方法。Production method.
前記スルホン酸が全炭素原子数1〜3のアルカンスルホン酸である、請求項14記載の電着塗料組成物の製造方法。 The method for producing an electrodeposition coating composition according to claim 14, wherein the sulfonic acid is an alkanesulfonic acid having 1 to 3 carbon atoms in total.
前記スルホン酸が、メタンスルホン酸である、請求項15記載の電着塗料組成物の製造方法。 The method for producing an electrodeposition coating composition according to claim 15, wherein the sulfonic acid is methanesulfonic acid.
前記顔料分散ペースト(2)は、ビスマス化合物(C)、有機酸(D)およびアミノ酸(G)を予め混合する第1混合工程、および、得られた混合物と、顔料分散樹脂(E)および顔料(F)とを混合する第2混合工程により調製される、請求項11に記載の電着塗料組成物の製造方法。 The pigment dispersion paste (2) includes a first mixing step in which a bismuth compound (C), an organic acid (D), and an amino acid (G) are mixed in advance, and the resulting mixture, a pigment dispersion resin (E), and a pigment. The manufacturing method of the electrodeposition coating material composition of Claim 11 prepared by the 2nd mixing process of mixing (F).
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