JP2020147703A - Pulverulent body coating composition and catalyst for the composition - Google Patents
Pulverulent body coating composition and catalyst for the composition Download PDFInfo
- Publication number
- JP2020147703A JP2020147703A JP2019047767A JP2019047767A JP2020147703A JP 2020147703 A JP2020147703 A JP 2020147703A JP 2019047767 A JP2019047767 A JP 2019047767A JP 2019047767 A JP2019047767 A JP 2019047767A JP 2020147703 A JP2020147703 A JP 2020147703A
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- JP
- Japan
- Prior art keywords
- group
- bismuth
- catalyst
- powder coating
- coating composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000008199 coating composition Substances 0.000 title claims abstract description 40
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
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- 239000000126 substance Substances 0.000 claims abstract description 28
- 239000003446 ligand Substances 0.000 claims abstract description 26
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- 125000000524 functional group Chemical group 0.000 claims description 33
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- 150000001622 bismuth compounds Chemical class 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000005594 diketone group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
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- 125000003277 amino group Chemical group 0.000 claims description 4
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- SSJKDUAYUOEFSU-UHFFFAOYSA-N 2-chloro-1,1,3,3,4,4,5,6,6,6-decafluorohex-1-ene Chemical compound FC(C(F)(F)F)C(C(C(=C(F)F)Cl)(F)F)(F)F SSJKDUAYUOEFSU-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 description 1
- QFWPBJXURCOOEQ-UHFFFAOYSA-N 4-[2-[2-(4-hydroxycyclohexyl)ethenoxy]ethenyl]cyclohexan-1-ol Chemical compound C1CC(O)CCC1C=COC=CC1CCC(O)CC1 QFWPBJXURCOOEQ-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- 229920005789 ACRONAL® acrylic binder Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229920005692 JONCRYL® Polymers 0.000 description 1
- 229920005933 JONCRYL® 587 Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000007610 electrostatic coating method Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- HJVKTYVDOZVQPA-UHFFFAOYSA-N ethenoxycyclopentane Chemical compound C=COC1CCCC1 HJVKTYVDOZVQPA-UHFFFAOYSA-N 0.000 description 1
- BLANBUKUVIWWGZ-UHFFFAOYSA-N ethenyl 2-hydroxyacetate Chemical compound OCC(=O)OC=C BLANBUKUVIWWGZ-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000000346 malonyl group Chemical group C(CC(=O)*)(=O)* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000004458 methylaminocarbonyl group Chemical group [H]N(C(*)=O)C([H])([H])[H] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 1
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical group CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 125000002801 octanoyl group Chemical group C(CCCCCCC)(=O)* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- GYBMSOFSBPZKCX-UHFFFAOYSA-N sodium;ethanol;ethanolate Chemical compound [Na+].CCO.CC[O-] GYBMSOFSBPZKCX-UHFFFAOYSA-N 0.000 description 1
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000002730 succinyl group Chemical group C(CCC(=O)*)(=O)* 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KNPRLIQQQKEOJN-UHFFFAOYSA-N tri(propan-2-yloxy)bismuthane Chemical compound [Bi+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] KNPRLIQQQKEOJN-UHFFFAOYSA-N 0.000 description 1
- YARYADVWFXCHJI-UHFFFAOYSA-N tributoxybismuthane Chemical compound [Bi+3].CCCC[O-].CCCC[O-].CCCC[O-] YARYADVWFXCHJI-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、有機錫化合物を含まず、現行と同等の焼付条件にて良好な塗膜の硬化性を確保できる有機錫フリーの粉体塗料組成物、及び、この組成物に含有され且つ架橋反応を促進する触媒に関する。 The present invention is an organic tin-free powder coating composition that does not contain an organic tin compound and can ensure good curability of a coating film under the same baking conditions as the current one, and an organic tin-free powder coating composition contained in this composition and a crosslinking reaction. With respect to catalysts that promote.
粉体塗料は、有機溶剤を含有しないため、従来の溶剤系塗料と比較して環境衛生上非常に好ましく、
また、塗着効率が良くかつ余剰塗料を回収再利用できる等の利点があり、自動車部品、産業機械、建築物内外装、家電製品等の保護、美観装飾性、耐久性が要求される幅広い分野で使用されている。
Since the powder paint does not contain an organic solvent, it is very preferable in terms of environmental hygiene as compared with the conventional solvent-based paint.
In addition, it has the advantages of high coating efficiency and the ability to collect and reuse surplus paint, and is a wide range of fields that require protection of automobile parts, industrial machinery, interior and exterior of buildings, home appliances, etc., aesthetic decoration, and durability. Used in.
このような粉体塗料は、熱硬化性樹脂をバインダーとし、硬化剤、顔料、その他の添加剤を混合し、実質的に樹脂と硬化剤の架橋反応が進行しない条件下で溶融混練し、ペレット状にした後、粉砕して製造される。このようにして製造された粉体塗料は、静電塗装法、浸漬流動塗装法等の手段により、被塗物に塗布した後、焼き付けることにより塗膜を形成させるものである。 In such powder coating materials, a thermosetting resin is used as a binder, a curing agent, a pigment, and other additives are mixed, and the resin and the curing agent are melt-kneaded under conditions where the cross-linking reaction does not substantially proceed, and pellets are obtained. After being shaped, it is crushed and manufactured. The powder coating material produced in this manner is applied to an object to be coated by means such as an electrostatic coating method and a dip-flow coating method, and then baked to form a coating film.
なかでも、水酸基を含有する熱硬化性樹脂と、ブロックポリイソシアネート化合物とポリウレトジオン化合物の少なくとも一方を硬化剤として組み合わせた粉体塗料は汎用されている。これらの粉体塗料では、樹脂と硬化剤による架橋反応を促進する触媒を添加することが行われ、代表的な触媒として、ジブチル錫オキシド等の粉体の有機錫化合物が使用されてきた。 Among them, a powder coating material in which a thermosetting resin containing a hydroxyl group and at least one of a blocked polyisocyanate compound and a polyuretdione compound are combined as a curing agent is widely used. In these powder coating materials, a catalyst that promotes a cross-linking reaction between a resin and a curing agent is added, and a powdered organic tin compound such as dibutyltin oxide has been used as a typical catalyst.
しかし、有機錫化合物は、塗装ラインの焼き付け炉の脱臭触媒被毒の原因となり得、また、昨今の有機錫化合物に対する環境規制動向から今後の使用が制限される可能性もあるため、有機錫化合物に代わる触媒を使用する粉体塗料組成物の開発が強く望まれてきた。 However, organotin compounds can cause deodorizing catalyst poisoning in the baking furnaces of painting lines, and future use may be restricted due to recent trends in environmental regulations for organotin compounds. There has been a strong desire to develop powder coating compositions that use alternative catalysts.
前記有機錫化合物の代替触媒として、特許文献１では、アルミン酸ビスマス等の粉体のビスマス化合物が提案されている。また、特許文献２では、ビスマストリス（２−エチルヘキサネート）等の有機酸ビスマス塩が提案されている。 As an alternative catalyst for the organic tin compound, Patent Document 1 proposes a powdered bismuth compound such as bismuth aluminate. Further, Patent Document 2 proposes an organic acid bismuth salt such as bismuth tris (2-ethylhexanate).
しかし、本発明者が特許文献１〜２の触媒を評価したところ、これらの触媒は、触媒性能が十分でないことが分かった。 However, when the present inventor evaluated the catalysts of Patent Documents 1 and 2, it was found that these catalysts did not have sufficient catalytic performance.
本発明はこのような事情に鑑みてなされたものであり、触媒性能に優れた粉体塗料組成物用触媒を提供するものである。 The present invention has been made in view of such circumstances, and provides a catalyst for a powder coating composition having excellent catalytic performance.
本発明によれば、ビスマス組成物（Ａ）で構成された粉体塗料組成物用触媒であって、前記ビスマス組成物（Ａ）は、芳香族カルボン酸配位子の数／ビスマス原子の数で定義される芳香族カルボン酸平均配位数が０．１〜２．０であり、前記芳香族カルボン酸配位子は、化学式（１）で表される芳香族カルボン酸から調製した配位子である、粉体塗料組成物用触媒が提供される。 According to the present invention, the catalyst for a powder coating composition composed of the bismuth composition (A), wherein the bismuth composition (A) has the number of aromatic carboxylic acid ligands / the number of bismuth atoms. The average coordination number of the aromatic carboxylic acid defined in is 0.1 to 2.0, and the aromatic carboxylic acid ligand is a coordination prepared from the aromatic carboxylic acid represented by the chemical formula (1). A child catalyst for a powder coating composition is provided.
本発明者らは、上記課題を解決すべく、多くの物質について触媒性能を評価したところ、上記ビスマス組成物（Ａ）で構成された粉体塗料組成物用触媒が触媒性能に優れることを見出し、本発明の完成に到った。 The present inventors evaluated the catalytic performance of many substances in order to solve the above problems, and found that the catalyst for a powder coating composition composed of the bismuth composition (A) was excellent in catalytic performance. , The present invention has been completed.
以下、本発明について詳細を説明する。 Hereinafter, the present invention will be described in detail.
１．粉体塗料組成物用触媒
本発明の粉体塗料組成物用触媒は、粉体塗料組成物の硬化反応を促進する触媒である。粉体塗料組成物の詳細は後述する。
1. 1. Catalyst for powder coating composition The catalyst for powder coating composition of the present invention is a catalyst that accelerates the curing reaction of the powder coating composition. Details of the powder coating composition will be described later.
本発明の粉体塗料組成物用触媒は、ビスマス組成物（Ａ）で構成されている。以下、ビスマス組成物（Ａ）について詳細に説明する。 The catalyst for a powder coating composition of the present invention is composed of the bismuth composition (A). Hereinafter, the bismuth composition (A) will be described in detail.
ビスマス組成物（Ａ）は、好ましくは、常温で固体である。これによって、粉体塗料組成物用触媒として取り扱い性に優れている。一方、特許文献２に記載のビスマストリス（２−エチルヘキサネート）は、常温液体であるので、粉体塗料組成物用触媒として扱いにくい。 The bismuth composition (A) is preferably solid at room temperature. As a result, it is excellent in handleability as a catalyst for powder coating compositions. On the other hand, since bismuth tris (2-ethylhexanate) described in Patent Document 2 is a liquid at room temperature, it is difficult to handle as a catalyst for a powder coating composition.
ビスマス組成物（Ａ）は、芳香族カルボン酸配位子の数／ビスマス原子の数で定義される芳香族カルボン酸平均配位数が０．１〜２．０である。前記芳香族カルボン酸配位子は、下記化学式（１）で表される芳香族カルボン酸から調製した配位子である。ビスマス原子の数は、ＥＤＴＡキレート滴定等で決定することができる。芳香族カルボン酸配位子の数は、ＧＣ分析等で決定することができる。 The bismuth composition (A) has an average aromatic carboxylic acid coordination number of 0.1 to 2.0, which is defined by the number of aromatic carboxylic acid ligands / the number of bismuth atoms. The aromatic carboxylic acid ligand is a ligand prepared from an aromatic carboxylic acid represented by the following chemical formula (1). The number of bismuth atoms can be determined by EDTA chelatometric titration or the like. The number of aromatic carboxylic acid ligands can be determined by GC analysis or the like.
式中、Ｒ１は、互いに同一又は異なって、水素原子、炭化水素基、アルコキシ基、アリールオキシ基、アミノ基、アルキルアミノ基、アルコキシカルボニル基、アミド基、又はアルキルカルバモイル基であり、Ｒ１同士が繋がり環構造を有していても良い。 In the formula, R 1 is the same or different from each other and is a hydrogen atom, a hydrocarbon group, an alkoxy group, an aryloxy group, an amino group, an alkylamino group, an alkoxycarbonyl group, an amide group, or an alkylcarbamoyl group, and R 1 They may be connected to each other and have a ring structure.
Ｒ１の炭素数は、１〜１８が好ましい。炭化水素基は、飽和炭化水素基と不飽和炭化水素基のどちらであってもよい。飽和炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基、オクチル基、オクタデカニル基などが挙げられる。不飽和炭化水素基としては、ビニル基、アリル基、プレニル基、クロチル基、シクロペンタジエニル基、フェニル基、トリル基、キシリル基や、メトキシ基等の種々置換基を有するアリール基が挙げられる。 The carbon number of R 1 is preferably 1 to 18. The hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of the saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an octyl group and an octadecanol group. Examples of the unsaturated hydrocarbon group include an aryl group having various substituents such as a vinyl group, an allyl group, a prenyl group, a crotyl group, a cyclopentadienyl group, a phenyl group, a trill group, a xsilyl group and a methoxy group. ..
アルコキシ基としては、メトキシ基、エトキシ基、イソプロポキシ基、ブトキシ基などが挙げられる。 Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group and the like.
アリールオキシ基としては、フェノキシ基、ｐ−メトキシフェノキシ基、ナフチルオキシ基が挙げられる。 Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and a naphthyloxy group.
アルキルアミノ基としては、メチルアミノ基などのモノアルキルアミノ基や、ジメチルアミノ基、ジエチルアミノ基などのジアルキルアミノ基が挙げられる。 Examples of the alkylamino group include a monoalkylamino group such as a methylamino group and a dialkylamino group such as a dimethylamino group and a diethylamino group.
アルコキシカルボニル基としては、メトキシカルボニル基、エトキシカルボニル基、ブトキシカルボニル基、オクチルオキシカルボニル基が挙げられる。 Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, and an octyloxycarbonyl group.
アルキルカルバモイル基としては、メチルアミノカルボニル基、ジメチルアミノカルボニル基、ジブチルアミノカルボニル基などが挙げられる。 Examples of the alkylcarbamoyl group include a methylaminocarbonyl group, a dimethylaminocarbonyl group, and a dibutylaminocarbonyl group.
Ｒ１同士が繋がり環構造を有する化合物としては、１−ナフトエ酸、２−ナフトエ酸、メトキシ基等の種々置換基を有するナフトエ酸等の芳香族カルボン酸が挙げられる。 Examples of the compound R 1 each other has a connection ring structure, 1-naphthoic acid, 2-naphthoic acid, and aromatic carboxylic acids such as naphthoic acid having various substituent groups such as methoxy group.
芳香族カルボン酸平均配位数は、好ましくは０．１〜１．０であり、さらに好ましくは０．３〜１．０であり、具体的には例えば、０．１、０．２、０．３、０．４、０．５、０．６、０．７、０．８、０．９、０．９９、１．０、１．１、１．２、１．３、１．４、１．５、１．６、１．７、１．８、１．９、２．０であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The average number of aromatic carboxylic acid coordinations is preferably 0.1 to 1.0, more preferably 0.3 to 1.0, and specifically, for example, 0.1, 0.2, 0. .3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 0.99, 1.0, 1.1, 1.2, 1.3, 1.4 , 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, and may be within the range between any two of the numerical values exemplified here.
また、ビスマス組成物（Ａ）は、ジケトン配位子の数／ビスマス原子の数で定義されるジケトン平均配位数が０．１〜２．０であることが好ましい。前記ジケトン配位子は、下記化学式（３）で表されるβジケトンから調製した配位子である。ジケトン配位子の数は、ＧＣ分析等で決定することができる。 Further, in the bismuth composition (A), the average coordination number of the diketone defined by the number of diketone ligands / the number of bismuth atoms is preferably 0.1 to 2.0. The diketone ligand is a ligand prepared from β-diketone represented by the following chemical formula (3). The number of diketone ligands can be determined by GC analysis or the like.
式中、Ｒ２は、互いに同一又は異なって、水素原子、炭化水素基、又はアルコキシ基である。炭化水素基としては、メチル基、エチル基、t-ブチル基などが挙げられる。アルコキシ基としては、メトキシ基、エトキシ基、ブトキシ基などが挙げられる。Ｒ２は、水素原子であることが好ましい。 In the formula, R 2 is the same or different from each other and is a hydrogen atom, a hydrocarbon group, or an alkoxy group. Examples of the hydrocarbon group include a methyl group, an ethyl group and a t-butyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group and the like. R 2 is preferably a hydrogen atom.
ジケトン平均配位数は、好ましくは０．１〜１．０であり、さらに好ましくは０．３〜１．０であり、具体的には例えば、０．１、０．２、０．３、０．４、０．５、０．６、０．７、０．８、０．９、０．９９、１．０、１．１、１．２、１．３、１．４、１．５、１．６、１．７、１．８、１．９、２．０であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The average number of diketone coordinates is preferably 0.1 to 1.0, more preferably 0.3 to 1.0, and specifically, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 0.99, 1.0, 1.1, 1.2, 1.3, 1.4, 1. It is 5, 1.6, 1.7, 1.8, 1.9, 2.0, and may be within the range between any two of the numerical values exemplified here.
ビスマス組成物（Ａ）は、下記化学式（２）で表される基を有するビスマス化合物を含有することが好ましい。また、このビスマス化合物は、下記化学式（４）で表される構造を有することが好ましい。このようなビスマス化合物としては、ビスマスモノカルボキシレートオキシドが挙げられる。
化学式（２）及び（４）中のＲ１及びＲ２は、化学式（１）及び（３）に関連して説明した通りである。化学式（４）中のＲ３は、水素原子、アルキル基、ヒドロキシアルキル基、アシル基、又は−Ｂｉ−（Ｏ−Ｒ３)２である。aは、１以上の整数を表し、ｂ，ｃは、０以上の整数を表す。添字ａ，ｂ，ｃを付した構造部位は、任意の順序で並ぶ。 R 1 and R 2 in the chemical formulas (2) and (4) are as described in relation to the chemical formulas (1) and (3). R 3 in the chemical formula (4) is a hydrogen atom, an alkyl group, a hydroxyalkyl group, an acyl group, or -Bi- (OR 3 ) 2 . a represents an integer of 1 or more, and b and c represent an integer of 0 or more. The structural parts with the subscripts a, b, and c are arranged in any order.
Ｒ３で表されるアルキル基としては、例えば、メチル基、エチル基、ブチル基、オクチル基、２-エチルヘキシル基、オクタデカニル基などが挙げられ、炭素数１〜１８のものが好ましい。 Examples of the alkyl group represented by R 3 include a methyl group, an ethyl group, a butyl group, an octyl group, a 2-ethylhexyl group, an octadecanyl group and the like, and those having 1 to 18 carbon atoms are preferable.
Ｒ３で表されるヒドロキシアルキル基としては、ヒドロキシエチル基、２−ヒドロキシプロピル基、２−ヒドロキシブチル基、２−ヒドロキシフェネチル基などが挙げられる。 Examples of the hydroxyalkyl group represented by R 3 include a hydroxyethyl group, a 2-hydroxypropyl group, a 2-hydroxybutyl group, and a 2-hydroxyphenethyl group.
Ｒ３で示されるアシル基としては、例えば、アセチル基、グルコロイル基、プロピオニル基、ラクトイル基、ブチリル基、ベンゾイル基、置換基を有する芳香族アシル基、オクタノイル基、２−エチルヘキサノイル基、ステアロイル基などが挙げられ、炭素数１〜１８のものが好ましい。また、マロニル基、スクシニル基、アジポイル基等の二塩基酸アシル基として同じＢｉ原子に結合していても良く、異なるＢｉ原子間に結合していても良い。 Examples of the acyl group represented by R 3 include an acetyl group, a glucoloyl group, a propionyl group, a lactoyl group, a butyryl group, a benzoyl group, an aromatic acyl group having a substituent, an octanoyl group, a 2-ethylhexanoyl group and a stearoyl group. Examples thereof include groups, and those having 1 to 18 carbon atoms are preferable. Further, it may be bonded to the same Bi atom as a dibasic acid acyl group such as a malonyl group, a succinyl group, or an adipoil group, or may be bonded between different Bi atoms.
Ｒ３で示される−Ｂｉ−（Ｏ−Ｒ３)２としては、例えば、ビスマス原子を介して、水酸基、アルコキシ基、アシルオキシ基を有するものが挙げられる。また、２つのＲ３がＢｉ原子で置換されて２つの酸素原子を連結することによって架橋又は環化されてもよい。 The -Bi- (O-R 3) 2 represented by R 3, for example, via a bismuth atom, a hydroxyl group, an alkoxy group include those having an acyloxy group. May also be crosslinked or cyclized by two R 3 connecting the two oxygen atoms are substituted with Bi atoms.
ａ／（ａ＋ｂ＋ｃ）の値は、例えば０．１〜１．０であり、具体的には例えば、０．１、０．２、０．３、０．４、０．５、０．６、０．７、０．８、０．９、１．０であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The value of a / (a + b + c) is, for example, 0.1 to 1.0, and specifically, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, It is 0.7, 0.8, 0.9, 1.0, and may be within the range between any two of the numerical values exemplified here.
ｂ／（ａ＋ｂ＋ｃ）の値は、例えば０．０〜０．９であり、具体的には例えば、０．０、０．１、０．２、０．３、０．４、０．５、０．６、０．７、０．８、０．９であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The value of b / (a + b + c) is, for example, 0.0 to 0.9, and specifically, for example, 0.0, 0.1, 0.2, 0.3, 0.4, 0.5, It is 0.6, 0.7, 0.8, 0.9, and may be in the range between any two of the numerical values exemplified here.
ｃ／（ａ＋ｂ＋ｃ）の値は、例えば０．０〜０．９であり、具体的には例えば、０．０、０．１、０．２、０．３、０．４、０．５、０．６、０．７、０．８、０．９であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The value of c / (a + b + c) is, for example, 0.0 to 0.9, and specifically, for example, 0.0, 0.1, 0.2, 0.3, 0.4, 0.5, It is 0.6, 0.7, 0.8, 0.9, and may be in the range between any two of the numerical values exemplified here.
各ビスマス化合物中のビスマス原子数は、特に限定されないが、例えば、１〜１０１６であり、好ましくは、１〜１０１０であり、さらに好ましくは、１〜１０００である。このビスマス原子数を１０ｐで表現すると、ｐは、例えば０〜１６であり、具体的には例えば、０、１、２、３、４、５、６、７、８、９、１０、１１、１２、１３、１４、１５、１６であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The number of bismuth atoms in each bismuth compound is not particularly limited, but is, for example, 1 to 10 16 , preferably 1 to 10 10 , and more preferably 1 to 1000. When the number of bismuth atoms is expressed by 10 p , p is, for example, 0 to 16, and specifically, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16 and may be within the range between any two of the numerical values exemplified here.
化学式（４）で表されるビスマスモノカルボキシレートオキシドは、芳香族カルボン酸平均配位数の上限が１．０である。一方、芳香族カルボン酸配位子が３つ配位したビスマストリスカルボキシレートは、芳香族カルボン酸平均配位数が３．０である。従って、ビスマス組成物（Ａ）がビスマスモノカルボキシレートオキシドのみを含む場合、芳香族カルボン酸平均配位数の上限は１．０であるが、ビスマス組成物（Ａ）がビスマストリスカルボキシレートを含有することにより、芳香族カルボン酸平均配位数を１．０よりも大きい値にすることができる。 The bismuth monocarboxylate oxide represented by the chemical formula (4) has an upper limit of the average coordination number of aromatic carboxylic acids of 1.0. On the other hand, the bismastris carboxylate in which three aromatic carboxylic acid ligands are coordinated has an average aromatic carboxylic acid coordination number of 3.0. Therefore, when the bismuth composition (A) contains only bismuth monocarboxylate oxide, the upper limit of the average coordination number of aromatic carboxylic acids is 1.0, but the bismuth composition (A) contains bismuth triscarboxylate. By doing so, the average coordination number of aromatic carboxylic acids can be set to a value larger than 1.0.
ビスマス組成物（Ａ）中の（ビスマスモノカルボキシレートオキシド中のビスマス原子の数）／（ビスマスモノカルボキシレートオキシド中のビスマス原子の数＋ビスマストリスカルボキシレート中のビスマス原子の数）の値は、０．１〜１．０が好ましく、０．５〜１．０がさらに好ましい。この値は、具体的には例えば、０．１、０．２、０．３、０．４、０．５、０．６、０．７、０．８、０．９、１．０であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。ビスマストリスカルボキシレートよりもビスマスモノカルボキシレートオキシドの方が触媒活性が高いので、ビスマスモノカルボキシレートオキシドの割合が大きい方が好ましい。 The value of (number of bismuth atoms in bismuth monocarboxylate oxide) / (number of bismuth atoms in bismuth monocarboxylate oxide + number of bismuth atoms in bismuth triscarboxylate) in the bismuth composition (A) is 0.1 to 1.0 is preferable, and 0.5 to 1.0 is more preferable. Specifically, this value is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0. Yes, it may be within the range between any two of the numerical values exemplified here. Since bismuth monocarboxylate oxide has higher catalytic activity than bismuth triscarboxylate, a larger proportion of bismuth monocarboxylate oxide is preferable.
前記ビスマス組成物（Ａ）の製造方法は、特に限定されないが、例えば、上記化学式（１）で表される芳香族カルボン酸と酸化ビスマス、又は、ビスマスアルコキシドとを反応させることによって製造することができる。ビスマス組成物（Ａ）は、具体的には、以下の方法により製造することができる。 The method for producing the bismuth composition (A) is not particularly limited, but for example, it can be produced by reacting the aromatic carboxylic acid represented by the chemical formula (1) with bismuth oxide or bismuth alkoxide. it can. Specifically, the bismuth composition (A) can be produced by the following method.
例えば、酸化ビスマスと前記芳香族カルボン酸をモル比（芳香族カルボン酸のモル数／酸化ビスマス中のビスマス原子のモル数）０．１〜１０、好ましくは０．５〜１．５、より好ましくは、０．９〜１．１の範囲で反応させる。反応溶媒は特に制限がないが、例えば、水、メタノール、エタノール、イソプロパノール、１−ブタノール、２−ブタノール、２，２−ジメチルプロパノール等のアルコール系溶媒、ヘキサン、ヘプタン、シクロヘキサン、トルエン、キシレン等の炭化水素系溶媒、ジエチルエーテル、ジブチルエーテル、テトラヒドロフラン等のエーテル系溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒、酢酸エチル、酢酸ブチル等のエステル系溶媒、ＤＭＦ等のアミド系溶媒、ＤＭＳＯ等のスルホキシド系溶媒等の単独溶媒、それらの混合溶媒が挙げられる。反応温度は特に制限がないが、２０〜２００℃の範囲、好ましくは５０〜１５０℃で反応させる。このようにして得られた反応スラリー溶液を濾過、遠心分離等の固液分離操作でビスマス組成物（Ａ）を得ることができる。必要に応じて、昇華、溶媒による洗浄、再沈殿、再結晶等により精製することもできる。 For example, the molar ratio of bismuth oxide to the aromatic carboxylic acid (number of moles of aromatic carboxylic acid / number of moles of bismuth atom in bismuth oxide) is 0.1 to 10, preferably 0.5 to 1.5, more preferably. Reacts in the range of 0.9 to 1.1. The reaction solvent is not particularly limited, and examples thereof include alcohol solvents such as water, methanol, ethanol, isopropanol, 1-butanol, 2-butanol, and 2,2-dimethylpropanol, hexane, heptane, cyclohexane, toluene, xylene and the like. Hydrocarbon solvents, ether solvents such as diethyl ether, dibutyl ether and tetrahydrofuran, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, amide solvents such as DMF, DMSO Examples thereof include a single solvent such as a sulfoxide-based solvent such as, and a mixed solvent thereof. The reaction temperature is not particularly limited, but the reaction is carried out in the range of 20 to 200 ° C., preferably 50 to 150 ° C. The bismuth composition (A) can be obtained by a solid-liquid separation operation such as filtration and centrifugation of the reaction slurry solution thus obtained. If necessary, it can be purified by sublimation, washing with a solvent, reprecipitation, recrystallization and the like.
或いは、ビスマスアルコキシドと前記芳香族カルボン酸をモル比、０．１〜５、好ましくは０．２〜２、より好ましくは０．３〜１．０の範囲で反応させる。ビスマストリアルコキシドとしては、例えば、ビスマストリメトキシド、ビスマストリエトキシド、ビスマストリイソプロポキシド、ビスマストリブトキシド等が挙げられる。反応溶媒は特に制限がないが、例えば、メタノール、エタノール、イソプロパノール、ブタノール等のアルコール系溶媒、ヘキサン、ヘプタン、シクロヘキサン、トルエン、キシレン等の炭化水素系溶媒、ジエチルエーテル、ジブチルエーテル、テトラヒドロフラン等のエーテル系溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒、酢酸エチル、酢酸ブチル等のエステル系溶媒、ＤＭＦ等のアミド系溶媒、ＤＭＳＯ等のスルホキシド系溶媒等の単独溶媒、それらの混合溶媒が挙げられる。反応温度は特に制限がないが、通常、０〜２００℃の範囲で反応させる。反応系で生成するアルコールを反応系外に留出させても良い。また、反応液に水や化学式（３）で表されるβジケトンを添加しても良い。このようにして得られた反応液を濃縮してビスマス組成物（Ａ）を得ることができる。必要に応じて、蒸留、昇華、溶媒による洗浄、再沈殿、再結晶等により精製することもできる。ビスマス組成物（Ａ）は、反応条件等によって実質的に単一のビスマス化合物になる場合もあれば、複数のビスマス化合物の混合物になる場合もある。このような混合物から特定の化合物を単離して触媒として用いてもよく、混合物をそのまま触媒として用いてもよい。どちらの場合であっても触媒として機能する。 Alternatively, the bismuth alkoxide is reacted with the aromatic carboxylic acid in a molar ratio of 0.1 to 5, preferably 0.2 to 2, more preferably 0.3 to 1.0. Examples of the bismuth trialkoxide include bismuth trimethoxydo, bismuth triethoxydo, bismuth triisopropoxide, bismuth tributoxide and the like. The reaction solvent is not particularly limited, and is, for example, an alcohol solvent such as methanol, ethanol, isopropanol and butanol, a hydrocarbon solvent such as hexane, heptane, cyclohexane, toluene and xylene, and an ether such as diethyl ether, dibutyl ether and tetrahydrofuran. System solvents, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, amide solvents such as DMF, single solvents such as sulfoxide solvents such as DMSO, and mixed solvents thereof. Can be mentioned. The reaction temperature is not particularly limited, but usually the reaction is carried out in the range of 0 to 200 ° C. The alcohol produced in the reaction system may be distilled out of the reaction system. Further, water or β-diketone represented by the chemical formula (3) may be added to the reaction solution. The reaction solution thus obtained can be concentrated to obtain the bismuth composition (A). If necessary, it can be purified by distillation, sublimation, washing with a solvent, reprecipitation, recrystallization and the like. The bismuth composition (A) may be substantially a single bismuth compound depending on reaction conditions and the like, or may be a mixture of a plurality of bismuth compounds. A specific compound may be isolated from such a mixture and used as a catalyst, or the mixture may be used as it is as a catalyst. In either case, it functions as a catalyst.
２．粉体塗料組成物
本発明者の粉体塗料組成物は、ビスマス組成物（Ａ）で構成された粉体塗料組成物用触媒と、硬化性官能基を有する樹脂（Ｂ）を含む。
2. 2. Powder coating composition The powder coating composition of the present inventor contains a catalyst for a powder coating composition composed of the bismuth composition (A) and a resin (B) having a curable functional group.
本発明の粉体塗料組成物中におけるビスマス組成物（Ａ）の含有量は、特に制限されないが、通常、粉体塗料組成物中の樹脂（Ｂ）と硬化剤（Ｃ）の合計固形分１００質量部に対して、０．１〜１０質量部、好ましくは、０．２〜５．０質量部である。添加量が前記範囲外であっても特に塗料性能に大きな問題は生じないが、上記０．１〜１０質量部の範囲内であれば、硬化性、防食性、仕上がり性に優れた粉体塗料組成物が得られる。 The content of the bismas composition (A) in the powder coating composition of the present invention is not particularly limited, but usually, the total solid content of the resin (B) and the curing agent (C) in the powder coating composition is 100. It is 0.1 to 10 parts by mass, preferably 0.2 to 5.0 parts by mass with respect to parts by mass. Even if the addition amount is out of the above range, there is no particular problem in the coating performance, but if it is within the above range of 0.1 to 10 parts by mass, the powder coating material has excellent curability, corrosion resistance and finish. The composition is obtained.
＜樹脂（Ｂ）＞
樹脂（Ｂ）は、硬化性官能基を有する樹脂である。硬化性官能基とは、ブロックイソシアネート基、ウレトジオン基等のイソシアネート基を母体とする基と、イソシアネート基の少なくとも一方と反応することができる官能基をいう。硬化性官能基としては、例えば、水酸基、アミノ基、アルキルアミノ基、チオール基、カルボン酸基等が挙げられる。
<Resin (B)>
The resin (B) is a resin having a curable functional group. The curable functional group refers to a group based on an isocyanate group such as a blocked isocyanate group or a uretdione group, and a functional group capable of reacting with at least one of the isocyanate groups. Examples of the curable functional group include a hydroxyl group, an amino group, an alkylamino group, a thiol group, a carboxylic acid group and the like.
硬化性官能基を含有する樹脂（Ｂ）は、分子内に硬化性官能基を含有している熱硬化性樹脂であれば特に限定されず、例えば、ポリエステル樹脂、アクリル樹脂、含フッ素共重合体、エポキシ樹脂、エポキシ−ポリエステル樹脂、アクリルーポリエステル樹脂等が挙げられる。樹脂（Ｂ）は、常温で固体、軟化点が６０〜１５０℃、好ましくは、軟化点が１００〜１４０℃であることが好適である。軟化点が６０℃未満であると、粉体塗料組成物のブロッキングが発生するために好ましくなく、１５０℃を超えると溶融混練を行う際に、粘度が高すぎて分散が十分行われず、塗膜性能が発揮されにくい。 The resin (B) containing a curable functional group is not particularly limited as long as it is a thermosetting resin containing a curable functional group in the molecule. For example, a polyester resin, an acrylic resin, or a fluorine-containing copolymer. , Epoxy resin, epoxy-polyester resin, acrylic-polyester resin and the like. The resin (B) is preferably solid at room temperature and has a softening point of 60 to 150 ° C., preferably a softening point of 100 to 140 ° C. If the softening point is less than 60 ° C., blocking of the powder coating composition occurs, which is not preferable. If the softening point is more than 150 ° C., the viscosity is too high to sufficiently disperse the coating film when melt-kneading is performed. Performance is difficult to demonstrate.
前記ポリエステル樹脂は、分子内に硬化性官能基を含有していれば特に限定されず、例えば、エチレングリコール、プロパンジオール、ペンタンジオール、ヘキサンジオール、ネオペンチルグリコール、トリメチロールプロパン、ペンタエリスリトール等の多価アルコールと、テレフタル酸、イソフタル酸、フタル酸、トリメリット酸、ヘキサヒドロフタル酸、メチルヘキサヒドロフタル酸、コハク酸、マレイン酸、フマル酸、グルタル酸、アジピン酸、セバシン酸等の多価カルボン酸、及び、それらの酸無水物を通常行われている方法で重合させたものが挙げられる。硬化性官能基が水酸基の場合、水酸基価は、特に限定されないが、通常は１０〜１５０ｍｇＫＯＨ／ｇが好ましく、２０〜８０ｍｇＫＯＨ／ｇであることがより好ましい。水酸基含有ポリエステル樹脂を具体的に例示すると、日本ユピカ社製ＧＶ−１１０，ＧＶ−５００，ＤＩＣ社製ファインディックＭ−８０２０，Ｍ−８１００、Ａｌｌｎｅｘ社製ＣＲＹＬＣＯＡＴ２８６８−０、ＤＳＭ社製Ｕｒａｌａｃ Ｐ １５８０等が挙げられる。 The polyester resin is not particularly limited as long as it contains a curable functional group in the molecule, and for example, a large amount of ethylene glycol, propanediol, pentanediol, hexanediol, neopentylglycol, trimethylpropane, pentaerythritol and the like. Hydrate alcohols and polyvalent carboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, and sebacic acid. Examples thereof include acids and those obtained by polymerizing their acid anhydrides by a usual method. When the curable functional group is a hydroxyl group, the hydroxyl value is not particularly limited, but is usually preferably 10 to 150 mgKOH / g, more preferably 20 to 80 mgKOH / g. Specific examples of the hydroxyl group-containing polyester resin include GV-110 and GV-500 manufactured by Japan U-Pica Company, Findick M-8020 and M-8100 manufactured by DIC Corporation, CRYLCOT2868-0 manufactured by Allnex, and Urarac P 1580 manufactured by DSM Corporation. Can be mentioned.
前記アクリル樹脂は、分子内に硬化性官能基を含有していれば特に限定されず、例えば、スチレン、（メタ）アクリル酸、（メタ）アクリル酸アルキルエステル、（メタ）アクリロニトリル、硬化性官能基含む（メタ）アクリル酸エステル、（メタ）アクリル酸（２−ヒドロキシエチル）のカプロラクトン付加体、（メタ）アクリル酸（２−ヒドロキシエチル）のエチレンイミン付加体等のモノマーを通常行われている方法により重合させたものが挙げられる。（メタ）アクリル酸アルキルエステルとしては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸（２−エチルヘキシル）等が挙げられる。硬化性官能基含む（メタ）アクリル酸エステルとしては、（メタ）アクリル酸（２−ヒドロキシエチル）、（メタ）アクリル酸（２−ヒドロキシプロピル）、（メタ）アクリル酸（４−ヒドロキシブチル）、（メタ）アクリル酸（２−ヒドロキシブチル）が挙げられる。硬化性官能基が水酸基の場合、水酸基価は、特に限定されないが、通常は１０〜２００ｍｇＫＯＨ／ｇが好ましく、２０〜１１０ｍｇＫＯＨ／ｇであることがより好ましい。水酸基含有アクリル樹脂を具体的に例示するとＢＡＳＦ社製Ｊｏｎｃｒｙｌ ５８７、Ｊｏｎｃｒｙｌ ８０４、ＤＩＣ社製Ａ−２５１等が挙げられる。 The acrylic resin is not particularly limited as long as it contains a curable functional group in the molecule, and for example, styrene, (meth) acrylic acid, (meth) acrylic acid alkyl ester, (meth) acrylonitrile, and curable functional group. Methods in which monomers such as (meth) acrylic acid ester, caprolactone adduct of (meth) acrylic acid (2-hydroxyethyl), and ethyleneimine adduct of (meth) acrylic acid (2-hydroxyethyl) are usually used. Examples thereof include those polymerized by. Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid (2-ethylhexyl) and the like. Examples of the (meth) acrylic acid ester containing a curable functional group include (meth) acrylic acid (2-hydroxyethyl), (meth) acrylic acid (2-hydroxypropyl), (meth) acrylic acid (4-hydroxybutyl), and the like. (Meta) acrylic acid (2-hydroxybutyl) can be mentioned. When the curable functional group is a hydroxyl group, the hydroxyl value is not particularly limited, but is usually preferably 10 to 200 mgKOH / g, and more preferably 20 to 110 mgKOH / g. Specific examples of the hydroxyl group-containing acrylic resin include BASF's Joncryl 587, Joncryl 804, and DIC's A-251.
前記含フッ素共重合体は、分子内に硬化性官能基を含有していれば特に限定されず、例えば、フルオロオレフィンと、その他のモノマーを公知の方法で重合させたものが挙げられる。フルオロオレフィンとしては、クロロトリフルオロエチレン、テトラフルオロエチレン、フッ化ビニリデン、トリフルオロエチレン、ヘキサフルオロプロピレン等が挙げられる。その他のモノマーとしては、硬化性官能基を含有するモノマー、シクロヘキシルビニルエーテル、シクロペンチルビニルエーテル、２−エチルヘキシルビニルエーテル、イソブチルビニルエーテル等が挙げられる。硬化性官能基を含有するモノマーとしては、アリルアルコール、２−ヒドロキシエチルビニルエーテル、４−ヒドロキシブチルビニルエーテル、４−ヒドロキシシクロヘキシルビニルエーテル、２−ヒドロキシエチルアリルエーテル、４−ヒドロキシブチルアリルエーテル、２−ヒドロキシエチル（メタ）アクリレート、（メタ）アクリル酸、無水マレイン酸、ヒドロキシ酢酸ビニル等が挙げられる。硬化性官能基が水酸基の場合、水酸基価は、特に限定されないが、通常は１０〜１５０ｍｇＫＯＨ／ｇであることが好ましく、２０〜８０ｍｇＫＯＨ／ｇであることがより好ましい。水酸基含有フッ素共重合体を具体的に例示すると、ＡＧＣ社製ルミフロンＬＦ７１０Ｆ等が挙げられる。 The fluorine-containing copolymer is not particularly limited as long as it contains a curable functional group in the molecule, and examples thereof include those obtained by polymerizing fluoroolefin and other monomers by a known method. Examples of the fluoroolefin include chlorotrifluoroethylene, tetrafluoroethylene, vinylidene fluoride, trifluoroethylene, hexafluoropropylene and the like. Examples of other monomers include monomers containing a curable functional group, cyclohexyl vinyl ether, cyclopentyl vinyl ether, 2-ethylhexyl vinyl ether, isobutyl vinyl ether and the like. Examples of the monomer containing a curable functional group include allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxycyclohexylvinyl ether, 2-hydroxyethylallyl ether, 4-hydroxybutylallyl ether, and 2-hydroxyethyl. Examples thereof include (meth) acrylate, (meth) acrylic acid, maleic anhydride, vinyl hydroxyacetate and the like. When the curable functional group is a hydroxyl group, the hydroxyl value is not particularly limited, but is usually preferably 10 to 150 mgKOH / g, and more preferably 20 to 80 mgKOH / g. Specific examples of the hydroxyl group-containing fluorine copolymer include Lumiflon LF710F manufactured by AGC Inc.
前記エポキシ樹脂、前記エポキシ−ポリエステル樹脂、前記アクリルーポリエステル樹脂は、分子内に硬化性官能基を含有していれば特に限定されず、公知の方法で製造される。 The epoxy resin, the epoxy-polyester resin, and the acrylic-polyester resin are not particularly limited as long as they contain a curable functional group in the molecule, and are produced by a known method.
硬化性官能基含有樹脂（Ｂ）は、外部架橋型及び内部（又は自己）架橋型のいずれのタイプのものであってもよい。架橋反応は、架橋部と、これと反応する硬化性官能基が必要であるので、架橋部と硬化性官能基の両方が樹脂（Ｂ）に含まれている場合には内部架橋型となり、架橋部を含まず硬化性官能基のみが含まれている樹脂（Ｂ）の場合には外部架橋型となる。 The curable functional group-containing resin (B) may be of any type, an external crosslinked type and an internal (or self) crosslinked type. Since the cross-linking reaction requires a cross-linked portion and a curable functional group that reacts with the cross-linked portion, if both the cross-linked portion and the curable functional group are contained in the resin (B), it becomes an internal cross-linking type and is cross-linked. In the case of the resin (B) which does not contain a portion and contains only a curable functional group, it is an external crosslinked type.
内部架橋型のタイプとしては、例えば、硬化性官能基含有樹脂（Ｂ）の分子中に、ブロックイソシアネート基、ウレトジオン基等を導入したものが挙げられる。樹脂（Ｂ）中へのブロックイソシアネート基の導入方法は、既知の方法を用いることができ、例えば、部分ブロックしたポリイソシアネート化合物中の遊離のイソシアネート基と樹脂（Ｂ）中の硬化性官能基を反応させることによって導入することができる。 Examples of the internally crosslinked type include those in which a blocked isocyanate group, a uretdione group, or the like is introduced into the molecule of the curable functional group-containing resin (B). As a method for introducing the blocked isocyanate group into the resin (B), a known method can be used. For example, a free isocyanate group in the partially blocked polyisocyanate compound and a curable functional group in the resin (B) can be used. It can be introduced by reacting.
＜硬化剤（Ｃ）＞
前記硬化性官能基を含有する樹脂（Ｂ）が外部架橋型の樹脂の場合、併用される硬化剤（Ｃ）としては、ブロックポリイソシアネート化合物、及び又は、ポリウレトジオン化合物が挙げられる。
<Hardener (C)>
When the resin (B) containing the curable functional group is an externally crosslinked resin, examples of the curing agent (C) to be used in combination include a blocked polyisocyanate compound and a polyuretdione compound.
ブロックポリイソシアネート化合物は、各々理論量のポリイソシアネート化合物とイソシアネートブロック剤とを付加反応させて得ることができる。 The blocked polyisocyanate compound can be obtained by addition-reacting a theoretical amount of the polyisocyanate compound with an isocyanate blocking agent.
ポリイソシアネート化合物としては、例えば、イソホロンジイソシアネート、４，４'−ジシクロヘキシルメタンジイソシアネート、ビス（イソシアネートメチル）シクロヘキサン、シクロヘキサンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、フェニレンジイソシアネート、ポリメチレンポリフェニルポリイソシアネートなどの脂肪族又は芳香族のポリイソシアネート化合物、これらの３量体、及び、これらのイソシアネート化合物の過剰量にエチレングリコール、プロピレングリコール、トリメチロールプロパン、ヘキサントリオール、ヒマシ油などの低分子活性水素含有化合物を反応させて得られる末端イソシアネート含有化合物等を挙げることができる。 Examples of the polyisocyanate compound include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, bis (isocyanatemethyl) cyclohexane, cyclohexanediisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, phenylenedi isocyanate, and poly. Lipid or aromatic polyisocyanate compounds such as methylenepolyphenylpolyisocyanate, trimerics thereof, and excess amounts of these isocyanate compounds include ethylene glycol, propylene glycol, trimethylolpropane, hexanetriol, castor oil, etc. Examples thereof include terminal isocyanate-containing compounds obtained by reacting low-molecular-weight active hydrogen-containing compounds.
イソシアネートブロック剤とは、ポリイソシアネート化合物のイソシアネート基に付加してブロックするものであり、付加によって生成するブロックポリイソシアネート化合物は常温において安定で且つ約１４０〜２１０℃に加熱した際、ブロック剤を解離して遊離のイソシアネート基を再生しうるものであることが望ましい。 The isocyanate blocking agent is one that is added to the isocyanate group of the polyisocyanate compound to block it, and the blocked polyisocyanate compound produced by the addition is stable at room temperature and dissociates the blocking agent when heated to about 140 to 210 ° C. It is desirable that the free isocyanate group can be regenerated.
ブロック剤としては、例えば、ε−カプロラクタム等のラクタム類、メチルエチルケトオキシム等のオキシム類、フェノール、２−エチルヘキサノール、ベンジルアルコール等のアルコール類、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル等のグリコールエーテル類等を挙げることができる。 Examples of the blocking agent include lactams such as ε-caprolactam, oximes such as methylethylketooxime, alcohols such as phenol, 2-ethylhexanol and benzyl alcohol, glycol ethers such as ethylene glycol monobutyl ether and diethylene glycol monomethyl ether and the like. Can be mentioned.
粉体塗料用の市販ブロックポリイソシアネート系硬化剤としては、例えば、イソシアネート基をε−カプロラクタムでブロックした硬化剤、Ｃｏｖｅｓｔｒｏ社のＣｒｅｌａｎ ＵＩ， Ｃｒｅｌａｎ ＮＩ−２， Ｃｒｅｌａｎ ＮＷ−５， Ｅｖｏｎｉｋ社のＶｅｓｔａｇｏｎ Ｂ １５３０、Ｖｅｓｔａｇｏｎ Ｂ１０６５， Ｖｅｓｔａｇｏｎ Ｂ１４００等が挙げられる。 Examples of commercially available blocked polyisocyanate-based curing agents for powder coatings include curing agents in which isocyanate groups are blocked with ε-caprolactam, Covestro's Cleran UI, Crelan NI-2, Crelan NW-5, and Evonik's Vestagon B. 1530, Vestagon B1065, Vestagon B1400 and the like.
ポリウレトジオン化合物は、分子内にウレトジオン基を２個以上有するものである。これらは、ポリイソシアネート化合物のイソシアネート基を２量化し自己ブロックすることにより、ブロック剤と同様の機能を果たすものである。 A polyuretdione compound has two or more uretdione groups in the molecule. These perform the same function as the blocking agent by dimerizing the isocyanate group of the polyisocyanate compound and self-blocking.
ポリウレトジオン化合物の製造に使用されるポリイソシアネート化合物は、例えば、イソホロンジイソシアネート、４，４'−ジシクロヘキシルメタンジイソシアネート、ビス（イソシアネートメチル）シクロヘキサン、シクロヘキサンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、フェニレンジイソシアネート、ポリメチレンポリフェニルポリイソシアネートなどの脂肪族又は芳香族のジイソシアネートが挙げられる。ポリイソシアネート化合物は、脂肪族化合物、中でも脂環式化合物が良く、イソホロンジイソシアネートが特に好ましい。 Polyisocyanate compounds used in the production of polyuretdione compounds include, for example, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, bis (isocyanatemethyl) cyclohexane, cyclohexanediisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, etc. Examples thereof include aliphatic or aromatic diisocyanates such as xylylene diisocyanate, phenylenedi isocyanate and polymethylene polyphenyl polyisocyanate. The polyisocyanate compound is preferably an aliphatic compound, particularly an alicyclic compound, and isophorone diisocyanate is particularly preferable.
ポリウレトジオン系硬化剤の具体的な製造法は、ポリイソシアネート化合物を重付加することにより得られるウレトジオン基を有するポリイソシアネートとイソシアネート基との反応性を有する官能基を１個又は２個有する炭化水素化合物と反応させる方法である。ウレトジオン基を有するポリイソシアネートとしては、ウレトジオン基を有するジイソシアネートが好ましい。イソシアネート基との反応性を有する官能基としては、水酸基、アミノ基等が挙げられる。イソシアネート基との反応性を有する官能基を１個又は２個有する炭化水素化合物としては、例えば、エチレングルコール、プロパンジオール、ブタンジオール、ヘキサンジオール、オクタンジオール、シクロヘキサンジオール、シクロヘキサンジメタノール等のアルコール類、エチレンジアミン、ヘキサメチレンジアミン等のアミン類、前記アルコール類とジカルボン酸、ジカルボン酸無水物、又は、ラクトンと反応させて得られるエステル基含有ジオール類、カーボネート基含有ジオール類等が挙げられる。ジカルボン酸としては、フタル酸、イソフタル酸、マロン酸、コハク酸、アジピン酸、セバシン酸等が挙げられる。ラクトンとしては、γ−ブチロラクトン、γ−バレロラクトン、ε−カプロラクトン等が挙げられる。 A specific method for producing a polyuretdione-based curing agent is a hydrocarbon having one or two functional groups having a reactivity between a polyisocyanate having a uretdione group and an isocyanate group obtained by double-adding a polyisocyanate compound. This is a method of reacting with a compound. As the polyisocyanate having a uretdione group, a diisocyanate having a uretdione group is preferable. Examples of the functional group having reactivity with the isocyanate group include a hydroxyl group and an amino group. Examples of the hydrocarbon compound having one or two functional groups reactive with an isocyanate group include alcohols such as ethylene glycol, propanediol, butanediol, hexanediol, octanediol, cyclohexanediol, and cyclohexanedimethanol. Examples thereof include amines such as ethylenediamine and hexamethylenediamine, ester group-containing diols obtained by reacting the alcohols with dicarboxylic acids, dicarboxylic acid anhydrides, or lactones, carbonate group-containing diols, and the like. Examples of the dicarboxylic acid include phthalic acid, isophthalic acid, malonic acid, succinic acid, adipic acid, sebacic acid and the like. Examples of the lactone include γ-butyrolactone, γ-valerolactone, ε-caprolactone and the like.
粉体塗料用の市販ポリウレトジオン系硬化剤としては、例えば、Ｃｏｖｅｓｔｒｏ社のＣｒｅｌａｎ ＥＦ４０３， Ｅｖｏｎｉｋ社のＶｅｓｔａｇｏｎ ＢＦ １５４０、Ｖｅｓｔａｇｏｎ ＢＦ１３２０等が挙げられる。 Examples of commercially available polyuretdione-based curing agents for powder coatings include Covestro's Crelan EF403, Evonik's Vestagon BF 1540, and Vestagon BF1320.
樹脂（Ｂ）／硬化剤（Ｃ）の固形分質量比は、好ましくは２０／８０〜９８／２、より好ましくは３０／７０〜９０／１０である。 The solid content mass ratio of the resin (B) / curing agent (C) is preferably 20/80 to 98/2, more preferably 30/70 to 90/10.
＜その他の添加剤＞
本発明の粉体塗料組成物は、必要に応じて、上記各成分に加えて通常の粉体塗料組成物に用いられる着色含量、体質顔料、流動性調整剤、ブロッキング防止剤、表面調整剤、ワキ防止剤、帯電制御剤、脱泡剤等のその他の添加剤を配合することができる。
<Other additives>
The powder coating composition of the present invention contains, if necessary, a coloring content, extender pigment, fluidity adjusting agent, blocking inhibitor, surface adjusting agent, which are used in ordinary powder coating compositions in addition to the above components. Other additives such as armpit inhibitor, charge control agent, and defoaming agent can be blended.
以下、実施例を挙げて本発明をさらに詳細に説明する。本発明はこれによって限定されるものではない。尚、「部」及び「％」は「質量部」及び「質量％」を示す。 Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited thereto. In addition, "part" and "%" indicate "part by mass" and "mass%".
＜ビスマス組成物（Ａ）の製造＞
（製造例１）ビスマス組成物（Ａ１）の製造
攪拌装置、温度計、冷却器を備えた５００ｍＬ４つ口丸底フラスコに、酸化ビスマス（Ｂｉ２Ｏ３）：４６．６ｇ（０．１００ｍｏｌ）、化学式（５）で表される安息香酸：２４．４ｇ（０．２００ｍｏｌ）、イオン交換水：２００ｇを仕込み攪拌した。攪拌しながら加熱し内温を９０℃まで昇温し、９０℃〜９５℃を保ち４時間反応させた。その後、攪拌しながら６０℃まで冷却し、吸引濾過、減圧乾燥し白色固体のビスマス組成物（Ａ１）：６７．１ｇを得た。ＥＤＴＡキレート滴定を用いてビスマス含量を測定したところ、６０．５％であった。ＧＣ分析を用いて安息香酸を定量したところ、３５．０％であった。質量％をモル換算するとモル比（安息香酸／ビスマス）＝１．００となる。ＩＲ測定すると１５１６ｃｍ−１に、ＣＯＯＢiのＣＯ伸縮に相当するピークを確認した。安息香酸のＣＯ伸縮ピークは１６８７ｃｍ−１であり、ビスマス組成物（Ａ１）には、安息香酸から調製した配位子が存在していることが示唆される。
<Manufacturing of bismuth composition (A)>
(Production Example 1) Production of bismuth composition (A1) Bismuth oxide (Bi 2 O 3 ): 46.6 g (0.100 mol), in a 500 mL four-necked round bottom flask equipped with a stirrer, a thermometer, and a cooler. 24.4 g (0.200 mol) of benzoic acid represented by the chemical formula (5) and 200 g of ion-exchanged water were charged and stirred. The mixture was heated with stirring to raise the internal temperature to 90 ° C., and the reaction was carried out at 90 ° C. to 95 ° C. for 4 hours. Then, the mixture was cooled to 60 ° C. with stirring, suction filtered and dried under reduced pressure to obtain 67.1 g of a white solid bismuth composition (A1). The bismuth content was measured using EDTA chelatometric titration and found to be 60.5%. When benzoic acid was quantified using GC analysis, it was 35.0%. When the mass% is converted into moles, the molar ratio (benzoic acid / bismuth) = 1.00. When IR measurement was performed, a peak corresponding to CO expansion and contraction of COOBi was confirmed at 1516 cm -1 . The CO expansion and contraction peak of benzoic acid is 1687 cm -1 , suggesting that a ligand prepared from benzoic acid is present in the bismuth composition (A1).
（製造例２）ビスマス組成物（Ａ２）の製造
攪拌装置、温度計、冷却器を備えた５００ｍＬ４つ口丸底フラスコに、酸化ビスマス（Ｂｉ２Ｏ３）：４６．６ｇ（０．１００ｍｏｌ）、化学式（６）で表されるｍ−トリル酸：２７．２ｇ（０．２００ｍｏｌ）、イオン交換水：２００ｇを仕込み、攪拌しながら加熱し内温を９０℃まで昇温し、９０℃〜９５℃を保ち４時間反応させた。その後、攪拌しながら６０℃まで冷却し、吸引濾過、減圧乾燥し白色固体のビスマス組成物（Ａ２）：７０．０ｇを得た。ＥＤＴＡキレート滴定を用いてビスマス含量を測定したところ、５８．３％であった。ＧＣ分析を用いてｍ−トリル酸を定量したところ、３７．５％であった。質量％をモル換算するとモル比（ｍ−トリル酸／ビスマス）＝０．９９となる。ＩＲ測定すると１５１８ｃｍ−１に、ＣＯＯＢiのＣＯ伸縮に相当するピークを確認した。ビスマス組成物（Ａ２）には、ｍ−トリル酸から調製した配位子が存在していることが示唆される。
(Production Example 2) Production of bismuth composition (A2) Bismuth oxide (Bi 2 O 3 ): 46.6 g (0.100 mol), in a 500 mL four-necked round-bottom flask equipped with a stirrer, a thermometer, and a cooler. M-trilic acid represented by the chemical formula (6): 27.2 g (0.200 mol) and ion-exchanged water: 200 g were charged, heated with stirring to raise the internal temperature to 90 ° C., and 90 ° C. to 95 ° C. Was kept and reacted for 4 hours. Then, the mixture was cooled to 60 ° C. with stirring, suction filtered and dried under reduced pressure to obtain 70.0 g of a white solid bismuth composition (A2). The bismuth content was measured using EDTA chelatometric titration and found to be 58.3%. When m-trilic acid was quantified using GC analysis, it was 37.5%. When the mass% is converted into moles, the molar ratio (m-trilic acid / bismuth) = 0.99. When IR measurement was performed, a peak corresponding to CO expansion and contraction of COOBi was confirmed at 1518 cm- 1 . It is suggested that the bismuth composition (A2) has a ligand prepared from m-trilic acid.
（製造例３）ビスマス組成物（Ａ３）の製造
攪拌装置、温度計、冷却器を備えた５００ｍＬ４つ口丸底フラスコに、酸化ビスマス（Ｂｉ２Ｏ３）：４６．６ｇ（０．１００ｍｏｌ）、化学式（７）で表される３，５−ジメチル安息香酸：３０．０ｇ（０．２００ｍｏｌ）、イオン交換水：１７０ｇ、２−ブタノール：３０ｇを仕込み、攪拌しながら加熱し内温を９０℃まで昇温し、９０℃〜９５℃を保ち４．５時間反応させた。その後、攪拌しながら６０℃まで冷却し、吸引濾過、減圧乾燥し白色固体のビスマス組成物（Ａ３）：７２．５ｇを得た。ＥＤＴＡキレート滴定を用いてビスマス含量を測定したところ、５６．１％であった。ＧＣ分析を用いて３，５−ジメチル安息香酸を定量したところ、３９．７％であった。質量％をモル換算するとモル比（３，５−ジメチル安息香酸／ビスマス）＝０．９８となる。ＩＲ測定すると１５１８ｃｍ−１に、ＣＯＯＢiのＣＯ伸縮に相当するピークを確認した。ビスマス組成物（Ａ３）には、３，５−ジメチル安息香酸から調製した配位子が存在していることが示唆される。
(Production Example 3) Production of bismuth composition (A3) Bismuth oxide (Bi 2 O 3 ): 46.6 g (0.100 mol), in a 500 mL four-necked round-bottom flask equipped with a stirrer, a thermometer, and a cooler. 3,5-Dimethylbenzoic acid represented by the chemical formula (7): 30.0 g (0.200 mol), ion-exchanged water: 170 g, 2-butanol: 30 g are charged and heated with stirring to raise the internal temperature to 90 ° C. The temperature was raised and the reaction was carried out at 90 ° C. to 95 ° C. for 4.5 hours. Then, the mixture was cooled to 60 ° C. with stirring, suction filtered and dried under reduced pressure to obtain 72.5 g of a white solid bismuth composition (A3). The bismuth content was measured using EDTA chelatometric titration and found to be 56.1%. When 3,5-dimethylbenzoic acid was quantified using GC analysis, it was 39.7%. When the mass% is converted into moles, the molar ratio (3,5-dimethylbenzoic acid / bismuth) = 0.98. When IR measurement was performed, a peak corresponding to CO expansion and contraction of COOBi was confirmed at 1518 cm- 1 . It is suggested that the bismuth composition (A3) has a ligand prepared from 3,5-dimethylbenzoic acid.
（製造例４）ビスマス組成物（Ａ４）の製造
攪拌装置、温度計、冷却器を備えた５００ｍＬ４つ口丸底フラスコに、酸化ビスマス（Ｂｉ２Ｏ３）：４６．６ｇ（０．１００ｍｏｌ）、化学式（８）で表されるｐ−トリル酸：２７．２ｇ（０．２００ｍｏｌ）、イオン交換水：１５０ｇ、２−ブタノール：５０ｇを仕込み、攪拌しながら加熱し内温を９０℃まで昇温し、９０℃〜９５℃を保ち４．５時間反応させた。その後、攪拌しながら６０℃まで冷却し、吸引濾過、減圧乾燥し白色固体のビスマス組成物（Ａ４）：６９．５ｇを得た。ＥＤＴＡキレート滴定を用いてビスマス含量を測定したところ、５８．３％であった。ＧＣ分析を用いてｐ−トリル酸を定量したところ、３７．７％であった。質量％をモル換算するとモル比（ｐ−トリル酸／ビスマス）＝０．９９となる。ＩＲ測定すると１５１８ｃｍ−１に、ＣＯＯＢiのＣＯ伸縮に相当するピークを確認した。ビスマス組成物（Ａ４）には、ｐ−トリル酸から調製した配位子が存在していることが示唆される。
(Production Example 4) Production of bismuth composition (A4) Bismuth oxide (Bi 2 O 3 ): 46.6 g (0.100 mol), in a 500 mL four-necked round-bottom flask equipped with a stirrer, a thermometer, and a cooler. P-trilic acid represented by the chemical formula (8): 27.2 g (0.200 mol), ion-exchanged water: 150 g, 2-butanol: 50 g were charged and heated with stirring to raise the internal temperature to 90 ° C. , 90 ° C to 95 ° C and reacted for 4.5 hours. Then, the mixture was cooled to 60 ° C. with stirring, suction filtered and dried under reduced pressure to obtain 69.5 g of a white solid bismuth composition (A4). The bismuth content was measured using EDTA chelatometric titration and found to be 58.3%. When p-trilic acid was quantified using GC analysis, it was 37.7%. When the mass% is converted into moles, the molar ratio (p-trilic acid / bismuth) = 0.99. When IR measurement was performed, a peak corresponding to CO expansion and contraction of COOBi was confirmed at 1518 cm- 1 . It is suggested that the bismuth composition (A4) has a ligand prepared from p-trilic acid.
（製造例５）ビスマス組成物（Ａ５）の製造
攪拌装置、温度計、冷却器を備えた５００ｍＬ４つ口丸底フラスコに、酸化ビスマス（Ｂｉ２Ｏ３）：４６．６ｇ（０．１００ｍｏｌ）、化学式（９）で表される４−メトキシ安息香酸：３０．４ｇ（０．２００ｍｏｌ）、イオン交換水：１７０ｇ、２−プロパノール：３０ｇを仕込み、攪拌しながら加熱し内温を９０℃まで昇温し、９０℃〜９５℃を保ち４．５時間反応させた。その後、攪拌しながら６０℃まで冷却し、吸引濾過、減圧乾燥し白色固体のビスマス組成物（Ａ５）：７３．２ｇを得た。ＥＤＴＡキレート滴定を用いてビスマス含量を測定したところ、５６．０％であった。ＧＣ分析を用いて４−メトキシ安息香酸を定量したところ、４０．３％であった。質量％をモル換算するとモル比（４−メトキシ安息香酸／ビスマス）＝０．９９となる。ＩＲ測定すると１５１８ｃｍ−１に、ＣＯＯＢiのＣＯ伸縮に相当するピークを確認した。ビスマス組成物（Ａ５）には、４−メトキシ安息香酸から調製した配位子が存在していることが示唆される。
(Production Example 5) Production of bismuth composition (A5) Bismuth oxide (Bi 2 O 3 ): 46.6 g (0.100 mol), in a 500 mL 4-neck round bottom flask equipped with a stirrer, a thermometer, and a cooler. 4-methoxybenzoic acid represented by the chemical formula (9): 30.4 g (0.200 mol), ion-exchanged water: 170 g, 2-propanol: 30 g are charged and heated with stirring to raise the internal temperature to 90 ° C. Then, the reaction was carried out at 90 ° C. to 95 ° C. for 4.5 hours. Then, the mixture was cooled to 60 ° C. with stirring, suction filtered and dried under reduced pressure to obtain 73.2 g of a white solid bismuth composition (A5). The bismuth content was measured using EDTA chelatometric titration and found to be 56.0%. When 4-methoxybenzoic acid was quantified using GC analysis, it was 40.3%. When the mass% is converted into molars, the molar ratio (4-methoxybenzoic acid / bismuth) = 0.99. When IR measurement was performed, a peak corresponding to CO expansion and contraction of COOBi was confirmed at 1518 cm- 1 . It is suggested that the bismuth composition (A5) contains a ligand prepared from 4-methoxybenzoic acid.
（製造例６）ビスマス組成物（Ａ６）の製造
攪拌装置、温度計、冷却器を備えた５００ｍＬ４つ口丸底フラスコに、酸化ビスマス（Ｂｉ２Ｏ３）：４６．６ｇ（０．１００ｍｏｌ）、化学式（１０）で表される４−アミノ安息香酸：２７．４ｇ（０．２００ｍｏｌ）、イオン交換水：２０ｇ、１，１−ジメチルプロパノール：１８０ｇを仕込み、攪拌しながら加熱し内温を９０℃まで昇温し、９０℃〜９５℃を保ち８時間反応させた。その後、攪拌しながら２５℃まで冷却し、吸引濾過、減圧乾燥し白色固体のビスマス組成物（Ａ６）：６９．３ｇを得た。ＥＤＴＡキレート滴定を用いてビスマス含量を測定したところ、５８．２％であった。ＧＣ分析を用いて４−アミノ安息香酸を定量したところ、３８．０％であった。質量％をモル換算するとモル比（４−アミノ安息香酸／ビスマス）＝１．００となる。ＩＲ測定すると１５１４ｃｍ−１に、ＣＯＯＢiのＣＯ伸縮に相当するピークを確認した。ビスマス組成物（Ａ６）には、４−アミノ安息香酸から調製した配位子が存在していることが示唆される。
(Production Example 6) Production of bismuth composition (A6) Bismuth oxide (Bi 2 O 3 ): 46.6 g (0.100 mol), in a 500 mL four-necked round-bottom flask equipped with a stirrer, a thermometer, and a cooler. 4-Aminobenzoic acid represented by the chemical formula (10): 27.4 g (0.200 mol), ion-exchanged water: 20 g, 1,1-dimethylpropanol: 180 g were charged and heated with stirring to raise the internal temperature to 90 ° C. The temperature was raised to 90 ° C. to 95 ° C. and the reaction was carried out for 8 hours. Then, the mixture was cooled to 25 ° C. with stirring, suction filtered and dried under reduced pressure to obtain 69.3 g of a white solid bismuth composition (A6). The bismuth content was measured using EDTA chelatometric titration and found to be 58.2%. When 4-aminobenzoic acid was quantified using GC analysis, it was 38.0%. When the mass% is converted into moles, the molar ratio (4-aminobenzoic acid / bismuth) = 1.00. When IR measurement was performed, a peak corresponding to CO expansion and contraction of COOBi was confirmed at 1514 cm- 1 . It is suggested that the bismuth composition (A6) has a ligand prepared from 4-aminobenzoic acid.
（製造例７）ビスマス組成物（Ａ７）の製造
攪拌装置、温度計、冷却器を備えた５００ｍＬ４つ口丸底フラスコに、酸化ビスマス（Ｂｉ２Ｏ３）：４６．６ｇ（０．１００ｍｏｌ）、化学式（１１）で表される４−メトキシカルボニル安息香酸：３６．０ｇ（０．２００ｍｏｌ）、イオン交換水：１００ｇ、１，１−ジメチルプロパノール：１００ｇを仕込み、攪拌しながら加熱し内温を９０℃まで昇温し、９０℃〜９５℃を保ち８時間反応させた。その後、攪拌しながら２５℃まで冷却し、吸引濾過、減圧乾燥し白色固体のビスマス組成物（Ａ７）：７７．５ｇを得た。ＥＤＴＡキレート滴定を用いてビスマス含量を測定したところ、５１．２％であった。ＧＣ分析を用いて４−メトキシカルボニル安息香酸を定量したところ、４４．１％であった。質量％をモル換算するとモル比（４−メトキシカルボニル安息香酸／ビスマス）＝１．００となる。ＩＲ測定すると１５１６ｃｍ−１に、ＣＯＯＢiのＣＯ伸縮に相当するピークを確認した。ビスマス組成物（Ａ７）には、４−メトキシカルボニル安息香酸から調製した配位子が存在していることが示唆される。
(Production Example 7) Production of bismuth composition (A7) Bismuth oxide (Bi 2 O 3 ): 46.6 g (0.100 mol), in a 500 mL 4-neck round bottom flask equipped with a stirrer, a thermometer, and a cooler. 4-methoxycarbonylbenzoic acid represented by the chemical formula (11): 36.0 g (0.200 mol), ion-exchanged water: 100 g, 1,1-dimethylpropanol: 100 g were charged and heated with stirring to raise the internal temperature to 90. The temperature was raised to ° C., and the reaction was carried out at 90 ° C. to 95 ° C. for 8 hours. Then, the mixture was cooled to 25 ° C. with stirring, suction filtered and dried under reduced pressure to obtain 77.5 g of a white solid bismuth composition (A7). The bismuth content was measured using EDTA chelatometric titration and found to be 51.2%. When 4-methoxycarbonylbenzoic acid was quantified using GC analysis, it was 44.1%. When the mass% is converted into moles, the molar ratio (4-methoxycarbonylbenzoic acid / bismuth) = 1.00. When IR measurement was performed, a peak corresponding to CO expansion and contraction of COOBi was confirmed at 1516 cm -1 . It is suggested that the bismuth composition (A7) has a ligand prepared from 4-methoxycarbonylbenzoic acid.
（製造例８）ビスマス組成物（Ａ８）の製造
窒素雰囲気下、攪拌装置、温度計、冷却器を備えた１０Ｌ４つ口丸底フラスコに、塩化ビスマス（和光純薬工業社製）：５００ｇ（１．５８ｍｏｌ）、エタノール：３６５ｇ、トルエン：２１７５ｇを加え攪拌し、加熱昇温して３０分間還流させた。２０％ナトリウムエトキシドエタノール溶液（和光純薬工業社製）：１６２０ｇ（４．７６ｍｏｌ）を加熱還流下４時間かけて滴下し、その後３時間加熱還流した。その後、攪拌しながら２０℃まで冷却し、不溶物を窒素雰囲気下、吸引濾過し、ビスマストリエトキシド溶液：４３４０ｇを得た。ＥＤＴＡキレート滴定を用いてビスマス濃度を測定したところ、Ｂｉ濃度：０．３３６ｍｏｌ／ｋｇであった。
(Production Example 8) Production of bismuth composition (A8) Bismuth chloride (manufactured by Wako Pure Chemical Industries, Ltd.): 500 g (1) in a 10 L 4-necked round-bottom flask equipped with a stirrer, a thermometer, and a cooler under a nitrogen atmosphere. .58 mol), ethanol: 365 g, toluene: 2175 g were added, stirred, heated to a high temperature, and refluxed for 30 minutes. 20% sodium ethoxide ethanol solution (manufactured by Wako Pure Chemical Industries, Ltd.): 1620 g (4.76 mol) was added dropwise over 4 hours under heating under reflux, and then heated at reflux for 3 hours. Then, the mixture was cooled to 20 ° C. with stirring, and the insoluble material was suction-filtered under a nitrogen atmosphere to obtain 4340 g of a bismuth triethoxyde solution. When the bismuth concentration was measured using EDTA chelatometric titration, the Bi concentration was 0.336 mol / kg.
窒素雰囲気下、攪拌装置、温度計、冷却器を備えた１Ｌ４つ口丸底フラスコに、ビスマストリエトキシド０．３３６ｍｏｌ／ｋｇ溶液：３００ｇ（０．１０ｍｏｌ）を仕込み、安息香酸１１．０ｇ（０．０９０ｍｏｌ）をトルエン１００ｇに溶解した溶液を内温２０〜３０℃に保ちながら１５分間かけて滴下した。そのまま同温度範囲で１時間攪拌した後、加熱昇温し内温が１００℃になるまで溶媒を常圧で留去した。攪拌しながら内温を２０℃まで冷却し、イオン交換水：４．５ｇ（０．２５ｍｏｌ）を内温２０〜３０℃の範囲で５分間かけて滴下し、同温度範囲でそのまま１時間攪拌した。反応液を５００ｍＬナスフラスコに移し、６０℃の湯浴で加熱しながら減圧濃縮して濃縮液６０ｇを得た。攪拌装置、温度計、冷却器を備えた３Ｌ４つ口丸底フラスコにヘプタン：７００ｇを仕込み、攪拌しながら上記濃縮液を内温２０〜３０℃の範囲で３０分間かけて滴下し、トルエン：１０ｇで洗いこんだ。同温度範囲でそのまま１時間攪拌した。得られたスラリー溶液を吸引濾過し、減圧乾燥して淡黄色固体のビスマス組成物（Ａ８）を３２．０ｇ得た。キレート滴定を用いてビスマス含量を測定したところ、６３．０％であった。ＧＣ分析を用いて安息香酸を定量したところ、３３．１％であった。質量％をモル換算するとモル比（安息香酸／ビスマス）＝０．９０となる。ＩＲ測定すると１５１８ｃｍ−１に、ＣＯＯＢiのＣＯ伸縮に相当するピークを確認した。 In a nitrogen atmosphere, a 1 L 4-neck round-bottom flask equipped with a stirrer, a thermometer, and a cooler was charged with bismastriethoxydo 0.336 mol / kg solution: 300 g (0.10 mol), and 11.0 g (0) of benzoic acid. A solution prepared by dissolving .090 mol) in 100 g of toluene was added dropwise over 15 minutes while maintaining an internal temperature of 20 to 30 ° C. After stirring as it was in the same temperature range for 1 hour, the temperature was raised by heating and the solvent was distilled off at normal pressure until the internal temperature reached 100 ° C. The internal temperature was cooled to 20 ° C. with stirring, and 4.5 g (0.25 mol) of ion-exchanged water was added dropwise over an internal temperature range of 20 to 30 ° C. over 5 minutes, and the mixture was stirred as it was for 1 hour in the same temperature range. .. The reaction solution was transferred to a 500 mL eggplant flask and concentrated under reduced pressure while heating in a hot water bath at 60 ° C. to obtain 60 g of a concentrated solution. Heptane: 700 g was charged into a 3 L 4-neck round bottom flask equipped with a stirrer, a thermometer, and a cooler, and the concentrated solution was added dropwise over 30 minutes at an internal temperature of 20 to 30 ° C. while stirring, and toluene: 10 g. I washed it with. The mixture was stirred as it was in the same temperature range for 1 hour. The obtained slurry solution was suction-filtered and dried under reduced pressure to obtain 32.0 g of a pale yellow solid bismuth composition (A8). The bismuth content was measured using chelatometric titration and found to be 63.0%. When benzoic acid was quantified using GC analysis, it was 33.1%. When the mass% is converted into moles, the molar ratio (benzoic acid / bismuth) = 0.90. When IR measurement was performed, a peak corresponding to CO expansion and contraction of COOBi was confirmed at 1518 cm- 1 .
（製造例９）ビスマス組成物（Ａ９）の製造
窒素雰囲気下、攪拌装置、温度計、冷却器を備えた１Ｌ４つ口丸底フラスコに、ビスマストリエトキシド０．３３６ｍｏｌ／ｋｇ溶液３００ｇ（０．１０ｍｏｌ）を仕込み、攪拌しながら、化学式（１２）で表される１，３−ジフェニル−１，３−プロパンジオン（以下、ジベンゾイルメタンと記載）：９．０ｇ（０．０４０ｍｏｌ）をトルエン５０ｇに溶解した溶液を内温２０〜３０℃に保ちながら１５分間かけて滴下し、続いて安息香酸：６．１ｇ（０．０５０ｍｏｌ）をトルエン５０ｇに溶解した溶液を同温度範囲に内温を保ちながら１５分間かけて滴下した。そのまま同温度範囲で１時間攪拌した後、加熱昇温し内温が１００℃になるまで溶媒を常圧で留去した。攪拌しながら内温を２０℃まで冷却し、イオン交換水：４．５ｇ（０．２５ｍｏｌ）を内温２０〜３０℃の範囲で５分間かけて滴下し、同温度範囲でそのまま１時間攪拌した。以下製造例８と同様の操作を行い、淡黄色固体のビスマス組成物（Ａ９）を３６．１ｇ得た。キレート滴定を用いてビスマス含量を測定したところ、５６．１％であった。ＧＣ分析を用いて有機成分を定量したところ、安息香酸が１６．４％、ジベンゾイルメタンが２４．０％であった。質量％をモル換算するとモル比（安息香酸／ビスマス）＝０．５０、モル比（ジベンゾイルメタン／ビスマス）＝０．４０となる。
(Production Example 9) Production of Bismas Composition (A9) Under a nitrogen atmosphere, 300 g (0. 10 mol) was charged, and while stirring, 1,3-diphenyl-1,3-propanedione represented by the chemical formula (12) (hereinafter referred to as dibenzoylmethane): 9.0 g (0.040 mol) was added to 50 g of toluene. The solution dissolved in is dropped over 15 minutes while keeping the internal temperature at 20 to 30 ° C., and then the solution prepared by dissolving 6.1 g (0.050 mol) of benzoic acid in 50 g of toluene is kept at the same temperature range. It was added dropwise over 15 minutes. After stirring as it was in the same temperature range for 1 hour, the temperature was raised by heating and the solvent was distilled off at normal pressure until the internal temperature reached 100 ° C. The internal temperature was cooled to 20 ° C. with stirring, and 4.5 g (0.25 mol) of ion-exchanged water was added dropwise over an internal temperature range of 20 to 30 ° C. over 5 minutes, and the mixture was stirred as it was for 1 hour in the same temperature range. .. Hereinafter, the same operation as in Production Example 8 was carried out to obtain 36.1 g of a pale yellow solid bismuth composition (A9). The bismuth content was measured using chelatometric titration and found to be 56.1%. When the organic components were quantified using GC analysis, benzoic acid was 16.4% and dibenzoylmethane was 24.0%. When the mass% is converted into moles, the molar ratio (benzoic acid / bismuth) = 0.50 and the molar ratio (dibenzoylmethane / bismuth) = 0.40.
（製造例１０）ビスマス組成物（Ａ１０）の製造
窒素雰囲気下、攪拌装置、温度計、冷却器を備えた１Ｌ４つ口丸底フラスコに、ビスマストリエトキシド０．３３６ｍｏｌ／ｋｇ溶液３００ｇ（０．１０ｍｏｌ）を仕込み、攪拌しながら、ジベンゾイルメタン２．３ｇ（０．０１ｍｏｌ）をトルエン３０ｇに溶解した溶液を内温２０〜３０℃に保ちながら１５分間かけて滴下し、続いて安息香酸８．５ｇ（０．０７０ｍｏｌ）をトルエン７０ｇに溶解した溶液を同温度範囲に内温保ちながら１５分間かけて滴下した。そのまま同温度範囲で１時間攪拌した後、加熱昇温し内温が１００℃になるまで溶媒を常圧で留去した。攪拌しながら内温を２０℃まで冷却し、イオン交換水：４．５ｇ（０．２５ｍｏｌ）を内温２０〜３０℃の範囲で５分間かけて滴下し、同温度範囲でそのまま１時間攪拌した。以下製造例８と同様の操作を行い、ビスマス組成物（Ａ１０）を３２．２ｇ得た。キレート滴定を用いてビスマス含量を測定したところ、６４．７％であった。ＧＣ分析を用いて有機成分を定量したところ、安息香酸が２６．１％、ジベンゾイルメタンが６．５％であった。質量％をモル換算するとモル比（安息香酸／ビスマス）＝０．７０、モル比（ジベンゾイルメタン／ビスマス）＝０．０９となる。
(Production Example 10) Production of bismuth composition (A10) Under a nitrogen atmosphere, 300 g (0. 10 mol) was charged, and a solution of 2.3 g (0.01 mol) of dibenzoylmethane dissolved in 30 g of toluene was added dropwise over 15 minutes while maintaining an internal temperature of 20 to 30 ° C., followed by benzoic acid 8. A solution prepared by dissolving 5 g (0.070 mol) in 70 g of toluene was added dropwise over 15 minutes while maintaining the internal temperature within the same temperature range. After stirring as it was in the same temperature range for 1 hour, the temperature was raised by heating and the solvent was distilled off at normal pressure until the internal temperature reached 100 ° C. The internal temperature was cooled to 20 ° C. with stirring, and 4.5 g (0.25 mol) of ion-exchanged water was added dropwise over an internal temperature range of 20 to 30 ° C. over 5 minutes, and the mixture was stirred as it was for 1 hour in the same temperature range. .. Hereinafter, the same operation as in Production Example 8 was carried out to obtain 32.2 g of the bismuth composition (A10). The bismuth content was measured using chelatometric titration and found to be 64.7%. When the organic components were quantified using GC analysis, benzoic acid was 26.1% and dibenzoylmethane was 6.5%. When the mass% is converted into moles, the molar ratio (benzoic acid / bismuth) = 0.70 and the molar ratio (dibenzoylmethane / bismuth) = 0.09.
＜硬化性官能基含有樹脂（Ｂ）の製造＞
（製造例１１）水酸基含有アクリル樹脂Ｂ３の製造
窒素導入缶、攪拌装置、温度計、冷却器及び滴下漏斗を備えた反応器に、キシレン６５部を仕込み攪拌しながら１３０℃に加熱した。そこへ予め秤量混合したモノマー開始剤混合物（メタクリル酸メチル：６０部、メタクリル酸ブチル：３０部、メタクリル酸２−ヒドロキシエチル：１０部、ｔ−ブチルパーオキシ−２−エチルヘキサノエート：５部）を、内温１２７〜１３３℃に保ち３時間かけて滴下した。同温度範囲で３０分間攪拌し、ｔ−ブチルパーオキシ−２−エチルヘキサノエート：０．１部をキシレン７部に溶解した溶液を滴下し、同温度範囲で１時間攪拌し、キシレンを減圧により留去して水酸基含有アクリル樹脂Ｂ３を得た。水酸基価を測定したところ４１ｍｇＫＯＨ／ｇであった。
<Manufacturing of curable functional group-containing resin (B)>
(Production Example 11) Production of hydroxyl group-containing acrylic resin B3 65 parts of xylene was charged into a reactor equipped with a nitrogen-introducing can, a stirrer, a thermometer, a cooler and a dropping funnel, and heated to 130 ° C. while stirring. Monomer initiator mixture pre-weighed and mixed there (methyl methacrylate: 60 parts, butyl methacrylate: 30 parts, 2-hydroxyethyl methacrylate: 10 parts, t-butylperoxy-2-ethylhexanoate: 5 parts ) Was added dropwise over 3 hours while maintaining an internal temperature of 127 to 133 ° C. Stir for 30 minutes in the same temperature range, add a solution of t-butylperoxy-2-ethylhexanoate: 0.1 part dissolved in 7 parts of xylene, stir for 1 hour in the same temperature range, and reduce the pressure of xylene. Distilled off to obtain a hydroxyl group-containing acrylic resin B3. The hydroxyl value was measured and found to be 41 mgKOH / g.
＜粉体塗料組成物の製造＞
＜＜実施例・比較例＞＞
下記の硬化性官能基含有樹脂、硬化剤、触媒、添加剤、顔料を表１〜表４に記載の配合比率（質量部）にてヘンシルミキサーで混合し、約１００℃で押し出し混練し、吐出した混練物を粉砕して１６０メッシュ篩で分級して粉体塗料組成物を得た。
<Manufacturing of powder coating composition>
<< Examples / Comparative Examples >>
The following curable functional group-containing resin, curing agent, catalyst, additive, and pigment are mixed with a hensyl mixer at the blending ratios (parts by mass) shown in Tables 1 to 4, extruded and kneaded at about 100 ° C. The discharged kneaded product was pulverized and classified with a 160 mesh sieve to obtain a powder coating composition.
硬化性官能基含有樹脂（Ｂ）
Ｂ１：ＡＧＣ社製、水酸基含有フッ素樹脂 ルミフロンＬＦ７１０Ｆ、水酸基価４５ｍｇＫＯＨ／ｇ
Ｂ２：ＤＩＣ社製、水酸基含有ポリエステル樹脂 ファインディックＭ−８０２０、水酸基価２８ｍｇＫＯＨ／ｇ
Ｂ３：製造例１１の水酸基含有アクリル樹脂、水酸基価４１ｍｇＫＯＨ／ｇ
Curable functional group-containing resin (B)
B1: AGC, hydroxyl group-containing fluororesin Lumiflon LF710F, hydroxyl value 45 mgKOH / g
B2: DIC, hydroxyl group-containing polyester resin Finedick M-8020, hydroxyl value 28 mgKOH / g
B3: Hydroxyl-containing acrylic resin of Production Example 11, hydroxyl value 41 mgKOH / g
硬化剤（Ｃ）
Ｃ１：Ｃｏｖｅｓｔｒｏ社、ε−カプロラクタムブロックポリイソシアネートＣｒｅｌａｎ ＵＩ、全ＮＣＯ量：１１．５％
Ｃ２：Ｃｏｖｅｓｔｒｏ社、ポリウレトジオン化合物Ｃｒｅｌａｎ ＥＦ４０３、全ＮＣＯ量：１３．５％
Hardener (C)
C1: Covestro, ε-caprolactam block polyisocyanate Crelan UI, total NCO amount: 11.5%
C2: Covestro, polyuretdione compound Crelan EF403, total NCO amount: 13.5%
触媒：
安息香酸ビスマス（ＩＩＩ）：Ｂｉ（Ｃ６Ｈ５ＣＯ２）３、三津和化学薬品社製
酢酸酸化ビスマス（ＩＩＩ）：ＢｉＯ（ＣＨ３ＣＯ２）、三津和化学薬品社製
クエン酸ビスマス（ＩＩＩ）：［Ｏ２ＣＣＨ２Ｃ（ＯＨ）（ＣＯ２）ＣＨ２ＣＯ２］Ｂｉ、Ａｌｄｒｉｃｈ社製
アルミン酸ビスマス水和物：Ｂｉ（ＡｌＯ２）３・ ＸＨ２Ｏ、Ａｌｄｒｉｃｈ社製
catalyst:
Bismuth benzoate (III): Bi (C 6 H 5 CO 2 ) 3 , manufactured by Mitsuwa Chemical Co., Ltd.
Bismuth acetate (III): BiO (CH 3 CO 2 ), manufactured by Mitsuwa Chemicals Co., Ltd. Bismuth citrate (III): [O 2 CCH 2 C (OH) (CO 2 ) CH 2 CO 2 ] Bi, Aldrich Made of bismuth aluminate hydrate: Bi (AlO 2 ) 3. XH 2 O, manufactured by Aldrich
その他添加剤：
表面調整剤：ＢＡＳＦ社製、アクロナール４Ｆ（アクリルポリマー）
ベンゾイン：東京化成工業社製
酸化チタン：古川ケミカルズ社製、ＦＲ−４１
Other additives:
Surface conditioner: BASF, Acronal 4F (acrylic polymer)
Benzoin: Tokyo Chemical Industry Co., Ltd. Titanium oxide: Furukawa Chemicals Co., Ltd., FR-41
＜硬化性評価＞
粉体塗料組成物をリン酸亜鉛処理した鋼板に静電塗装し２００℃２０分間焼付けした硬化塗膜をメチルイソブチルケトンに浸したガーゼで約２ｋｇ／ｃｍ３の圧力で３０回擦り、外観を目視で判定し、以下の基準で塗膜の硬化性を評価した。評価結果を表１〜表４に示す。
<Evaluation of curability>
The powder coating composition was electrostatically coated on a steel sheet treated with zinc phosphate and baked at 200 ° C. for 20 minutes. The cured coating film was rubbed with gauze soaked in methyl isobutyl ketone 30 times at a pressure of about 2 kg / cm 3 to visually check the appearance. The curability of the coating film was evaluated according to the following criteria. The evaluation results are shown in Tables 1 to 4.
○：変化なし
Ｘ：表面に多量の傷、及び又は、塗膜が溶解し試験板素地が露出
◯: No change X: A large amount of scratches on the surface and / or the coating film is dissolved and the test plate base is exposed.
実施例の粉体塗料組成物は硬化性が良好であった。一方、比較例の粉体塗料組成物は硬化性が劣っていた。 The powder coating composition of the example had good curability. On the other hand, the powder coating composition of the comparative example was inferior in curability.
Claims (7)
前記ビスマス組成物（Ａ）は、芳香族カルボン酸配位子の数／ビスマス原子の数で定義される芳香族カルボン酸平均配位数が０．１〜２．０であり、
前記芳香族カルボン酸配位子は、下記化学式（１）で表される芳香族カルボン酸から調製した配位子である、粉体塗料組成物用触媒。
The bismuth composition (A) has an average aromatic carboxylic acid coordination number of 0.1 to 2.0, which is defined by the number of aromatic carboxylic acid ligands / the number of bismuth atoms.
The aromatic carboxylic acid ligand is a ligand prepared from an aromatic carboxylic acid represented by the following chemical formula (1), and is a catalyst for a powder coating composition.
前記ビスマス組成物（Ａ）は、下記化学式（２）で表される基を有するビスマス化合物を含有する、触媒。
The bismuth composition (A) is a catalyst containing a bismuth compound having a group represented by the following chemical formula (2).
前記ビスマス組成物（Ａ）は、ジケトン配位子の数／ビスマス原子の数で定義されるジケトン平均配位数が０．１〜２．０であり、
前記ジケトン配位子は、下記化学式（３）で表されるβジケトンから調製した配位子である、触媒。
The bismuth composition (A) has a diketone average coordination number of 0.1 to 2.0, which is defined by the number of diketone ligands / the number of bismuth atoms.
The diketone ligand is a catalyst prepared from β-diketone represented by the following chemical formula (3).
前記ビスマス組成物（Ａ）は、下記化学式（４）で表される構造を有するビスマス化合物を含有する、触媒。
The bismuth composition (A) is a catalyst containing a bismuth compound having a structure represented by the following chemical formula (4).
前記触媒は、請求項１〜請求項４の何れか１つに記載の粉体塗料組成物用触媒であり、
前記樹脂は、硬化性官能基を有する、粉体塗料組成物。 A powder coating composition containing a catalyst and a resin (B).
The catalyst is the catalyst for a powder coating composition according to any one of claims 1 to 4.
The resin is a powder coating composition having a curable functional group.
前記樹脂（Ｂ）がブロックイソシアネート基とウレトジオン基の少なくとも一方を有するか、又は前記粉体塗料組成物が硬化剤（Ｃ）を含有し、
前記硬化剤（Ｃ）は、ブロックポリイソシアネート化合物とポリウレトジオン化合物の少なくとも一方を含有する、粉体塗料組成物。 The powder coating composition according to claim 5.
The resin (B) has at least one of a blocked isocyanate group and a uretdione group, or the powder coating composition contains a curing agent (C).
The curing agent (C) is a powder coating composition containing at least one of a blocked polyisocyanate compound and a polyuretdione compound.
前記硬化性官能基が水酸基である、粉体塗料組成物。 The powder coating composition according to claim 5 or 6.
A powder coating composition in which the curable functional group is a hydroxyl group.
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| WO2015166745A1 (en) * | 2014-04-28 | 2015-11-05 | 日東化成株式会社 | Electrodeposition coating material composition and catalyst for electrodeposition coating material |
| JP2015534590A (en) * | 2012-09-11 | 2015-12-03 | シーカ・テクノロジー・アーゲー | Two-component polyurethane composition |
| JP2016534106A (en) * | 2013-08-15 | 2016-11-04 | ダウ グローバル テクノロジーズ エルエルシー | Process for producing polycarbamate, polycarbamate produced thereby, and coating composition comprising polycarbamate |
| JP2018530637A (en) * | 2015-08-11 | 2018-10-18 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ | Coating system based on Bi catalyst and aromatic carboxylic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015534590A (en) * | 2012-09-11 | 2015-12-03 | シーカ・テクノロジー・アーゲー | Two-component polyurethane composition |
| JP2016534106A (en) * | 2013-08-15 | 2016-11-04 | ダウ グローバル テクノロジーズ エルエルシー | Process for producing polycarbamate, polycarbamate produced thereby, and coating composition comprising polycarbamate |
| WO2015166745A1 (en) * | 2014-04-28 | 2015-11-05 | 日東化成株式会社 | Electrodeposition coating material composition and catalyst for electrodeposition coating material |
| JP2018530637A (en) * | 2015-08-11 | 2018-10-18 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ | Coating system based on Bi catalyst and aromatic carboxylic acid |
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