JP3846946B2 - Polyamide resin powder for paint and method for producing the same - Google Patents
Polyamide resin powder for paint and method for producing the same Download PDFInfo
- Publication number
- JP3846946B2 JP3846946B2 JP27793396A JP27793396A JP3846946B2 JP 3846946 B2 JP3846946 B2 JP 3846946B2 JP 27793396 A JP27793396 A JP 27793396A JP 27793396 A JP27793396 A JP 27793396A JP 3846946 B2 JP3846946 B2 JP 3846946B2
- Authority
- JP
- Japan
- Prior art keywords
- polyamide resin
- melamine
- polyamide
- powder
- resin powder
- 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.)
- Expired - Fee Related
Links
- 239000000843 powder Substances 0.000 title claims description 62
- 229920006122 polyamide resin Polymers 0.000 title claims description 55
- 239000003973 paint Substances 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title description 7
- 238000000576 coating method Methods 0.000 claims description 41
- 239000011248 coating agent Substances 0.000 claims description 31
- 229920000877 Melamine resin Polymers 0.000 claims description 27
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 21
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 12
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 description 25
- 229920002647 polyamide Polymers 0.000 description 25
- 239000000654 additive Substances 0.000 description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 15
- 230000000996 additive effect Effects 0.000 description 10
- 235000011007 phosphoric acid Nutrition 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- -1 cyanphenine Chemical compound 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000299 Nylon 12 Polymers 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229920000571 Nylon 11 Polymers 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 125000005341 metaphosphate group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- LTURHSAEWJPFAA-UHFFFAOYSA-N sulfuric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OS(O)(=O)=O.NC1=NC(N)=NC(N)=N1 LTURHSAEWJPFAA-UHFFFAOYSA-N 0.000 description 2
- HCITUYXHCZGFEO-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.N=C1NC(=N)NC(=N)N1 HCITUYXHCZGFEO-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004687 Nylon copolymer Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- AQQVTZBWWYVEGR-UHFFFAOYSA-N [NH4+].[O-][PH2]=O Chemical compound [NH4+].[O-][PH2]=O AQQVTZBWWYVEGR-UHFFFAOYSA-N 0.000 description 1
- YDHWWBZFRZWVHO-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O YDHWWBZFRZWVHO-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- PYCBFXMWPVRTCC-UHFFFAOYSA-N ammonium metaphosphate Chemical compound N.OP(=O)=O PYCBFXMWPVRTCC-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 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
- 239000000539 dimer Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical group 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 description 1
- 229940099402 potassium metaphosphate Drugs 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- SIGUVTURIMRFDD-UHFFFAOYSA-M sodium dioxidophosphanium Chemical compound [Na+].[O-][PH2]=O SIGUVTURIMRFDD-UHFFFAOYSA-M 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は塗料用ポリアミド樹脂粉体に関する。本発明によれば、汎用性があり、有効にエッジ部の塗膜不良（以下「エッジ切れ」と称する。）を防止する塗料用ポリアミド樹脂粉体を提供することができる。
【０００２】
【従来の技術】
近年、環境への配慮から粉体塗装が多く使用されている。粉体塗装に使用される樹脂粉体のうちでもポリアミド粉体は、その優れた耐薬品性や耐候性から屋外等の厳しい環境下で使用されることが多い。
【０００３】
従来の塗料用ポリアミド樹脂粉体は、被塗物の平坦部においては非常に優れた耐久性や光沢性を有する塗膜を形成する一方、被塗物の鋭利な部位では、ポリアミドの結晶性に起因すると思われるエッジ切れがしばしば見受けられる。
【０００４】
塗料用ポリアミド樹脂粉体の製造法には、（１）機械粉砕法、（２）化学粉砕法、（３）乳化重合法、（４）造粒噴霧法、およびこれらの組み合わせが一般的に知られている。これらのうちでは、機械粉砕法が実用的であり、最も広範囲な分野において使用されている。ポリアミド粉体において、機械粉砕による粉体製造方法では、ポリアミド樹脂を化学的に安定な構造にした上で、各種添加剤（耐熱安定剤、耐候安定剤、着色剤など）を混練し、次に冷凍粉砕するのが一般的である。この方法において得られるポリアミド粉体は、形状が不均一であるだけでなく、添加剤による結晶化速度の上昇が観察される。このため、エッジ切れをより起きやすくしている。
【０００５】
エッジ切れに対する対策はこれまでもいくつかの試みが報告されている。しかし、これらはいずれも多大な費用を要したり、あるいは特殊な製法にしか使用できないという欠点を有していた。
【０００６】
また、エッジ切れの対策のうち最も簡単で安価な方法は、粉体にある種の添加剤を混合することである。これまでに報告されているエッジ切れ対策のうちにも、添加剤を混合することで末端基を利用した化学反応による分子量の増大によるものが多くある。例えば、樹脂の末端カルボキシル基とエポキシ樹脂との反応を利用する方法（特公平７−１０９５８号公報）、１２０℃以下の融点を有するナイロン共重合体を、ナイロン１１，ナイロン１２などのポリアミド樹脂に添加する方法（特開昭５５−６６９６９号公報）、分岐ポリエステル樹脂とブロック化イソシアネート又はエポキシ樹脂とを含む粉体塗料用樹脂組成物（特公昭５９−２１４９号公報，特公昭５６−５４７０号公報）、エポキシ樹脂と（メタ）アクリル酸エステル系重合体微粒子とを含む粉体塗料用樹脂組成物（特開平６−３２９９５５号公報）などである。しかしながら、反応性があまり高い反応では、ポリアミド粉体の保存中に反応が一部開始してしまい、長期間にわたり粉体を使用することができなくなってしまう。一方、反応性が小さ過ぎてもその効果を十分に発揮できない。
【０００７】
なお、成形性の向上を図るために、特開昭６２−６２８５４号公報、特開昭６２−６１３０３号公報には、ポリアミドにリン酸メラミンを添加した組成物が開示されている。しかし、これらの文献には、高い流動性による成形性の向上については開示されてはいるが、粉末塗装に用いることやエッジ切れを防止することについては、何ら記載も開示もされていない。
【０００８】
【発明が解決しようとする課題】
従って、本発明の目的は、添加剤の添加という簡単な組成でエッジ切れを有効に防止できる塗料用ポリアミド樹脂粉体およびその製造方法、並びに塗料用ポリアミド樹脂粉体を用いた粉体塗料を提供することにある。
【０００９】
また、本発明の他の目的は、添加剤の添加にも拘らず、長期間に亘って安定かつ有効に、エッジ切れを防止できる塗料用ポリアミド樹脂粉体およびその製造方法、並びに塗料用ポリアミド樹脂粉体を用いた粉体塗料を提供することにある。
【００１０】
【課題を解決するための手段】
本発明者らは、前記目的を達成するため、エッジ切れを防止する作用を有する添加剤を鋭意検討の結果、ポリアミド粉体にトリアジン環を有する化合物（特に、メラミン又はその誘導体（メラミンと酸との反応物、メラミンオリゴマー、リン酸メラミンオリゴマー））を混合すると、エッジ切れを有効に防止することができることを見いだし、本発明を完成した。
すなわち、本発明の塗料用ポリアミド樹脂粉体は、ポリアミド樹脂粉体と、メラミン、メラミンと酸との反応物、メラミンオリゴマー及びリン酸メラミンオリゴマーから選択された少なくとも一種のトリアジン環を有する化合物とで構成されている。この塗料用ポリアミド樹脂粉体において、ポリアミド１００重量部に対して前記トリアジン環を有する化合物の割合が０．１〜２０重量部程度であってもよい。
【００１１】
さらに本発明は、前記ポリアミド樹脂を含む粉体塗料も提供する。また本発明は、前記塗料用ポリアミド樹脂粉体を用いる粉体塗料のエッジ切れ防止方法も提供する。
【００１２】
【発明の実施の形態】
本発明のポリアミド樹脂粉体は、ポリアミド樹脂とトリアジン環を有する化合物とで構成されている。また、本発明のポリアミド樹脂粉体は、ポリアミド樹脂粉粒体とトリアジン環を有する化合物粉粒体との混合物であっても、ポリアミド樹脂とトリアジン環を有する化合物との溶融組成物の粉粒体であってもよい。さらに、必要により酸又はその塩、有機金属化合物、金属酸化物などの添加剤を含んでいてもよい。以下に、これらの成分について説明する。
【００１３】
［トリアジン環を有する化合物］
トリアジン環を有する化合物は、三つの窒素原子を含む六員複素環およびその誘導体、またはこれらを含む化合物をいい、例えばメラミン、シアフェニン、シアヌル酸、パラシアンギ酸などが例示できる。
【００１４】
好ましいトリアジン環を有する化合物は、メラミン（１，３，５−トリアジン−２，４，６−トリアミン）又はその誘導体、すなわちメラミン骨格（シアヌリル環とアミノ基）を有する化合物又はその誘導体である。メラミン又はその誘導体としては、例えば、メラミン、リン酸メラミン、硫酸メラミンなどのメラミンと酸との反応物、メラミン樹脂（オリゴマーを含む）、リン酸メラミンオリゴマーなどが例示できる。これらのメラミン又はその誘導体は、単独で又は二種以上組み合わせて使用できる。
リン酸メラミン、又は硫酸メラミンは、メラミンとリン酸又は硫酸とを反応させることにより得られる。リン酸メラミンに使用されるリン酸には、例えば、オルトリン酸、ピロリン酸、メタリン酸、三リン酸、四リン酸、ポリリン酸、亜リン酸などが含まれる。これらのリン酸は、単独で又は二種以上組み合わせて使用できる。
また、メラミン樹脂（リン酸メラミンオリゴマーを含む）は、メラミン又はメラミン誘導体（リン酸メラミンなど）とホルムアルデヒドとの付加重合により得られるメチロールメラミンにかぎられず、メラミン樹脂をメタノール、エタノール、ブタノールなどのアルコールでエーテル化したアルコキシメチルメラミン、共縮合成分（例えば、グアナミン樹脂オリゴマー、フェノール、ユリア、グアナミン類など）と共縮合した共縮合体であってもよい。
【００１５】
［ポリアミド樹脂］
本発明の塗料用ポリアミド樹脂粉体に使用可能なポリアミド樹脂の種類は特に限定されず、例えば、Ｃ6-20のラクタムの開環重合体（例えば、ポリアミド６、ポリアミド１２など）、Ｃ6-20のアミノカルボン酸の重縮合体（例えば、ポリアミド９、ポリアミド１１など）、Ｃ4-20のジアミンとＣ6-20のジカルボン酸の重縮合体（例えば、ポリアミド４−６、ポリアミド６−６、ポリアミド６−１０、ポリアミド６−１２、ＭＸＤ−６など）およびこれらの各原料の共縮合体（例えば、ポリアミド６−１１、ポリアミド１１−１２、ポリアミド６／６−１０、ポリアミド６／６−６／６−１０／１２など）、非晶性芳香族含有透明ポリアミド、変性ポリオレフィンを混合あるいはグラフト重合させた高耐衝撃性ポリアミド、ダイマー酸または水添ダイマー酸を一成分とするポリアミドやポリアミドにホルムアルデヒドとアルコールを反応させたＮ−アルコキシメチルポリアミドと呼ばれる変性ポリアミドなどが挙げられる。これらのポリアミド樹脂は単独で又は二種以上組み合わせて使用できる。
好ましいポリアミド樹脂は、結晶化しにくく、成膜性、耐薬品性、耐候性に優れるポリアミド樹脂である。特に、ポリアミド樹脂は、ポリアミド１１又はポリアミド１２の構成単位を含むポリアミド樹脂、なかでもポリアミド１１又はポリアミド１２の単独又は共重合体である。
また、好ましいポリアミド樹脂は、末端にカルボキシル基を有するポリアミド樹脂である。ポリアミド樹脂のカルボキシル基濃度は、適当に選択することができ、例えば、酸価４０〜１２０ｍｇ ｅｑ／ｋｇのポリアミド樹脂が含まれる。このようなポリアミド樹脂は、ポリアミドにジカルボン酸又は酸無水物を過剰に用いて反応させることにより得ることができる。
これらのポリアミド樹脂の数平均分子量は、粉砕の際の衝撃に対する十分な抵抗力を有し、かつ、容易に粉末化できる程度、例えば、５０００〜５００００（例えば、７０００〜３００００）である。
【００１６】
トリアジン環を有する化合物（メラミン又はその誘導体など）の使用量は、被塗物の形状や加熱温度を考慮しつつ、樹脂粉体にエッジ切れを防止できる範囲で適当に選択できる。トリアジン環を有する化合物の使用量は、例えば、ポリアミド１００重量部に対して、０．１〜２０重量部（例えば、１〜１５重量部）、好ましくは２〜１３重量部（２〜１０重量部）程度であり、３〜５重量部程度である場合が多い。なお、最適混合量は、塗膜の表面状態（光沢、色など）や塗膜に要求される機械特性などに応じて適宜選択できる。
【００１７】
［添加剤］
本発明のトリアジン環を有する化合物とポリアミド樹脂粉体とを含む組成物は、更に、別個の添加剤、例えば、酸又はその塩［例えば、リン酸又はその塩（例えば、リン酸、リン酸アンモニウム、リン酸ナトリウムなどのリン酸金属塩）、リン酸水素塩（例えば、リン酸水素アンモニウム、リン酸水素カリウム、リン酸水素ナトリウムなどのリン酸水素アルカリ金属塩）、メタリン酸塩（メタリン酸アンモニウム、メタリン酸ナトリウム、メタリン酸カリウムなどのメタリン酸アルカリ金属塩）、ホスフィン酸塩（ホスフィン酸アンモニウム、ホスフィン酸ナトリウムなどのホスフィン酸アルカリ金属塩）］、有機金属化合物（例えば、ジブチルスズオキサイドなど）、又は金属酸化物（例えば、シリカ、アルミナ、ガラス、酸化チタン、酸化亜鉛、酸化ジルコニウムなど）、水酸化アルミニウム、タルク、炭酸カルシウム、ケイ砂、石英などを添加してもよい。これらの添加剤は、単独または２種以上組み合わせて使用できる。これらの添加剤のうち、リン酸又はその塩、有機金属化合物及び金属酸化物は触媒として機能するようである。一般に、これらの添加剤のうち、リン酸またはその塩（アンモニウム塩、アルカリ金属塩など）、金属酸化物が使用される。このような添加剤を用いると、エッジ切れの防止効果を安定に得ることができる。これらの添加剤の添加量は、エッジ切れを防止できる程度（触媒量）、例えば、ポリアミド１００重量部に対して０．１〜５重量部（例えば、０．５〜３重量部）である。
【００１８】
また、本発明の塗料用ポリアミド樹脂粉体は、添加剤、例えば、耐熱性、耐候性を改善するための酸化防止剤や紫外線吸収剤、耐熱安定剤（フェノール系、イオウ系、アミン系、リン系化合物など）、着色剤、難燃剤、帯電防止剤などを含有していてもよい。
【００１９】
［製造方法］
本発明の塗料用ポリアミド樹脂粉体は、ポリアミド樹脂粉体と前記トリアジン環を有する化合物とを混合することにより製造できる。混合においては、例えば、ヘンシェルミキサー、タンブラーミキサーなどの慣用の混合機を用いて各成分を混合してもよい。このような方法によれば、混合という簡単な操作でエッジ切れを防止できるという利点がある。また、ポリアミド樹脂と前記トリアジン環を有する化合物との溶融混合物や添加剤との溶融混合物を粉末化することも可能である。
また、本発明の塗料用ポリアミド樹脂粉末の製造は、機械粉砕法に制限されるものではなく、化学粉砕法、乳化重合法、造粒噴霧法、及びこれらを組み合わせて行うことができる。
本発明の塗料用ポリアミド樹脂粉体は、機械粉砕法によって製造された不均一な形状の粉体であっても、エッジ切れを有効に防止できるという利点がある。従って、本発明の塗料用ポリアミド樹脂粉体の形状は均一である必要はなく、不均一（例えば、球状、楕円状などや破砕物などの不定形）であってもよい。この塗料用ポリアミド樹脂粉体の平均粒径は、例えば、１０〜３００μｍ（例えば、２０〜２８０μｍ）程度であり、好ましくは５０〜２５０μｍ（例えば、６０〜２４０μｍ）程度である。しかし、塗料用ポリアミド樹脂粉体は、樹脂の付着性、塗膜の均一性などを高めるために、それぞれの加工法や被塗物の材質、目的などを考慮して、最適の粒径、粒度分布を有する粉末を選択し、使用することが必要である。
【００２０】
［粉体塗料］
本発明のポリアミド樹脂粉体を使用する塗装は、粉末塗装、特に流動浸漬により行う場合が多い。粉末塗装は、基材（被塗物、例えば、金属材料やセラミックスなど）に対する耐薬品性、耐磨耗性、防錆の付与や、着色のためなどに行われる。特に、流動浸漬は、鋭利な角度のエッジ部を有する基材を塗装するために、有用な方法である。エッジ部に角度は特に制限されず、例えば、１０〜９０°、特に１０〜５０°程度であってもよい。流動浸漬は、ポリアミド樹脂粉体の種類に応じた適当な条件、例えば、８０〜３００℃、好ましくは１００〜２８０℃程度の温度で行うことができる。また、塗装は、流動浸漬に制限されるものではなく、静電塗装や溶射により行うことも可能である。
【００２１】
【実施例】
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。
実施例１〜１２、参考例１及び比較例１〜３
ポリアミド１２を含むポリアミド粉体（ダイセル・ヒュルス社製：商品名ダイアミドＺ２０７３Ａ）１００重量部に表に示す所定量のメラミン又はその誘導体と表に示す所要量の添加物を加え、ヘンシェルミキサーを用いて撹拌し、ポリアミド樹脂粉体を調製した。
塗装は、端部に約３０度の鋭利な角度を有する厚さ３ｍｍの鉄板（７ｃｍ×９ｃｍ）を、表面温度が２８０℃になるまで加熱し、次いで、これを熱いうちに、空気でよく流動させた粉体の中に浸漬させ、粉体の流動層の中で、鉄板を揺すりながら約７秒間浸漬させた後、室温でゆっくり冷却させて行った。
塗装後の鉄板の端部（エッジ）の状態を観察し、エッジからの塗膜剥離が起きているかどうかを観察した。室温静置１日後に剥離が起きているエッジの数を数えることにより、エッジ切れに対するメラミン又はその誘導体の効果を評価した。結果を表１に示す。
【００２２】
【表１】
【００２３】
【発明の効果】
本発明の塗料用ポリアミド樹脂粉体は、トリアジン環を有する化合物を混合しているため、エッジ切れを有効に防止することができる。また、本発明の塗料用ポリアミド樹脂はトリアジン環を有する化合物を混合することにより、添加剤の添加にも拘らず、長期間に亘って安定かつ有効に、エッジ切れを防止できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyamide resin powder for paint. ADVANTAGE OF THE INVENTION According to this invention, the polyamide resin powder for coating materials which is versatile and can prevent the coating-film defect of an edge part (henceforth "edge breakage") effectively can be provided.
[0002]
[Prior art]
In recent years, powder coating is often used for environmental considerations. Of the resin powders used for powder coating, polyamide powder is often used in harsh environments such as outdoors due to its excellent chemical resistance and weather resistance.
[0003]
Conventional polyamide resin powders for paints form a coating film having very excellent durability and glossiness on the flat part of the coating object, while improving the crystallinity of polyamide in the sharp part of the coating object. Edge breaks that are likely to be caused are often seen.
[0004]
Generally known methods for producing polyamide resin powders for coatings are (1) mechanical pulverization method, (2) chemical pulverization method, (3) emulsion polymerization method, (4) granulation spraying method, and combinations thereof. It has been. Of these, the mechanical grinding method is practical and used in the widest range of fields. In the powder production method by mechanical pulverization of polyamide powder, after making the polyamide resin chemically stable, various additives (heat stabilizer, weather stabilizer, colorant, etc.) are kneaded, and then It is common to freeze and grind. The polyamide powder obtained by this method not only has a non-uniform shape, but an increase in the crystallization rate due to the additive is observed. For this reason, edge breakage is more likely to occur.
[0005]
Several attempts have been reported to deal with edge breaks. However, they all have the disadvantage that they are very expensive or can only be used for special production processes.
[0006]
Further, the simplest and cheapest method for preventing edge breakage is to mix certain additives into the powder. Among the countermeasures against edge breakage that have been reported so far, many are due to an increase in molecular weight due to a chemical reaction utilizing end groups by mixing additives. For example, a method using a reaction between a terminal carboxyl group of a resin and an epoxy resin (Japanese Patent Publication No. 7-10958), a nylon copolymer having a melting point of 120 ° C. or less is converted into a polyamide resin such as nylon 11 or nylon 12 Addition method (Japanese Patent Laid-Open No. 55-66969), resin composition for powder coating containing branched polyester resin and blocked isocyanate or epoxy resin (Japanese Patent Publication No. 59-2149, Japanese Patent Publication No. 56-5470) ), A resin composition for powder coatings containing an epoxy resin and (meth) acrylic acid ester polymer fine particles (Japanese Patent Laid-Open No. 6-329955). However, in a reaction having a very high reactivity, the reaction partially starts during storage of the polyamide powder, and the powder cannot be used for a long period of time. On the other hand, even if the reactivity is too small, the effect cannot be exhibited sufficiently.
[0007]
In order to improve moldability, JP-A Nos. 62-62854 and 62-61303 disclose compositions in which melamine phosphate is added to polyamide. However, although these documents disclose improvement of formability due to high fluidity, there is no description or disclosure about use in powder coating or prevention of edge breakage.
[0008]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a polyamide resin powder for coating that can effectively prevent edge breakage with a simple composition of adding an additive, a method for producing the same, and a powder coating using the polyamide resin powder for coating. There is to do.
[0009]
Another object of the present invention is to provide a polyamide resin powder for coating material which can prevent edge breakage stably and effectively over a long period of time despite the addition of an additive, a method for producing the same, and a polyamide resin for coating material. The object is to provide a powder coating using powder.
[0010]
[Means for Solving the Problems]
In order to achieve the above object, the present inventors have intensively studied an additive having an action of preventing edge breakage, and as a result, a compound having a triazine ring in a polyamide powder (especially melamine or a derivative thereof (melamine and acid). The present inventors have found that edge breakage can be effectively prevented by mixing the reaction product, melamine oligomer, and melamine phosphate oligomer)) ).
That is, the polyamide resin powder for paints of the present invention comprises a polyamide resin powder and a compound having at least one triazine ring selected from melamine, a reaction product of melamine and acid, a melamine oligomer, and a melamine phosphate oligomer. It is configured. In this polyamide resin powder for paints , the ratio of the compound having a triazine ring to 100 parts by weight of polyamide may be about 0.1 to 20 parts by weight.
[0011]
Furthermore, this invention also provides the powder coating material containing the said polyamide resin. The present invention also provides a method for preventing edge breakage of a powder paint using the polyamide resin powder for paint.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The polyamide resin powder of the present invention is composed of a polyamide resin and a compound having a triazine ring. Further, the polyamide resin powder of the present invention may be a mixture of a polyamide resin powder and a compound powder having a triazine ring, or a melt of a polyamide resin and a compound having a triazine ring. It may be. Furthermore, an additive such as an acid or a salt thereof, an organometallic compound, or a metal oxide may be included as necessary. Below, these components are demonstrated.
[0013]
[Compound having a triazine ring]
The compound having a triazine ring refers to a six-membered heterocyclic ring containing three nitrogen atoms and a derivative thereof, or a compound containing these, and examples thereof include melamine, cyanphenine, cyanuric acid, and paracyanic acid.
[0014]
A preferred compound having a triazine ring is melamine (1,3,5-triazine-2,4,6-triamine) or a derivative thereof, that is, a compound having a melamine skeleton (cyanuryl ring and amino group) or a derivative thereof. Examples of melamine or a derivative thereof include a reaction product of melamine and acid such as melamine, melamine phosphate, and melamine sulfate, melamine resin (including oligomer), and melamine phosphate oligomer. These melamines or derivatives thereof can be used alone or in combination of two or more.
Melamine phosphate or melamine sulfate is obtained by reacting melamine with phosphoric acid or sulfuric acid. Examples of phosphoric acid used for melamine phosphate include orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, triphosphoric acid, tetraphosphoric acid, polyphosphoric acid, phosphorous acid, and the like. These phosphoric acids can be used alone or in combination of two or more.
Melamine resins (including melamine phosphate oligomers) are not limited to methylol melamine obtained by addition polymerization of melamine or melamine derivatives (such as melamine phosphate) and formaldehyde, and melamine resins are alcohols such as methanol, ethanol, and butanol. It may be a co-condensate co-condensed with alkoxymethylmelamine etherified with a co-condensation component (for example, guanamine resin oligomer, phenol, urea, guanamines, etc.).
[0015]
[Polyamide resin]
The type of polyamide resin that can be used in the polyamide resin powder for coatings of the present invention is not particularly limited, and examples thereof include C 6-20 lactam ring-opening polymers (for example, polyamide 6, polyamide 12 and the like), C 6- Polycondensates of 20 aminocarboxylic acids (eg polyamide 9, polyamide 11 etc.), polycondensates of C 4-20 diamines and C 6-20 dicarboxylic acids (eg polyamide 4-6, polyamide 6-6) , Polyamide 6-10, polyamide 6-12, MXD-6, etc.) and cocondensates of these raw materials (for example, polyamide 6-11, polyamide 11-12, polyamide 6 / 6-10, polyamide 6 / 6-6) 6 / 6-10 / 12, etc.), amorphous aromatic-containing transparent polyamides, high impact polyamides mixed or graft polymerized with modified polyolefins, dimer acid or hydrogenated And modified polyamide called the immersion acid polyamide or polyamides one component by reacting formaldehyde and alcohol N- alkoxymethyl polyamides. These polyamide resins can be used alone or in combination of two or more.
A preferred polyamide resin is a polyamide resin that is difficult to crystallize and is excellent in film formability, chemical resistance, and weather resistance. In particular, the polyamide resin is a polyamide resin containing structural units of polyamide 11 or polyamide 12, and in particular, polyamide 11 or polyamide 12 alone or a copolymer.
A preferred polyamide resin is a polyamide resin having a carboxyl group at the terminal. The carboxyl group concentration of the polyamide resin can be appropriately selected, and includes, for example, a polyamide resin having an acid value of 40 to 120 mg eq / kg. Such a polyamide resin can be obtained by reacting polyamide with an excess of dicarboxylic acid or acid anhydride.
The number average molecular weight of these polyamide resins is sufficient to have an impact resistance against pulverization and can be easily powdered, for example, 5000 to 50000 (for example, 7000 to 30000).
[0016]
The amount of the compound having a triazine ring (such as melamine or a derivative thereof) can be appropriately selected within a range in which the edge of the resin powder can be prevented while considering the shape of the article to be coated and the heating temperature. The amount of the compound having a triazine ring is, for example, 0.1 to 20 parts by weight (for example, 1 to 15 parts by weight), preferably 2 to 13 parts by weight (2 to 10 parts by weight) with respect to 100 parts by weight of polyamide. ) And is often about 3 to 5 parts by weight. The optimum mixing amount can be appropriately selected according to the surface state (gloss, color, etc.) of the coating film and the mechanical properties required for the coating film.
[0017]
[Additive]
The composition containing the compound having a triazine ring of the present invention and the polyamide resin powder may further contain a separate additive such as an acid or a salt thereof [eg, phosphoric acid or a salt thereof (eg, phosphoric acid, ammonium phosphate). , Metal phosphates such as sodium phosphate), hydrogen phosphates (eg, alkali metal hydrogen phosphates such as ammonium hydrogen phosphate, potassium hydrogen phosphate, sodium hydrogen phosphate), metaphosphates (ammonium metaphosphate) , Alkali metal salts of metaphosphates such as sodium metaphosphate and potassium metaphosphate), phosphinates (alkali metal phosphinates such as ammonium phosphinate and sodium phosphinate)], organometallic compounds (for example, dibutyltin oxide), or Metal oxide (eg, silica, alumina, glass, titanium oxide, acid Zinc, etc. zirconium oxide), aluminum hydroxide, talc, calcium carbonate, silica sand, or the like may be added quartz. These additives can be used alone or in combination of two or more. Of these additives, phosphoric acid or its salts, organometallic compounds and metal oxides appear to function as catalysts. Generally, among these additives, phosphoric acid or a salt thereof (ammonium salt, alkali metal salt, etc.) or a metal oxide is used. When such an additive is used, the effect of preventing edge breakage can be stably obtained. The amount of these additives added is such that edge breakage can be prevented (catalytic amount), for example, 0.1 to 5 parts by weight (for example, 0.5 to 3 parts by weight) with respect to 100 parts by weight of polyamide.
[0018]
In addition, the polyamide resin powder for coatings of the present invention contains additives such as antioxidants, ultraviolet absorbers, heat stabilizers (phenolic, sulfur-based, amine-based, phosphorous for improving heat resistance and weather resistance). System compounds), colorants, flame retardants, antistatic agents, and the like.
[0019]
[Production method]
The polyamide resin powder for paints of the present invention can be produced by mixing the polyamide resin powder and the compound having a triazine ring. In mixing, for example, each component may be mixed using a conventional mixer such as a Henschel mixer or a tumbler mixer. According to such a method, there is an advantage that edge breakage can be prevented by a simple operation of mixing. It is also possible to pulverize a molten mixture of a polyamide resin and the compound having a triazine ring or a molten mixture of an additive.
Further, the production of the polyamide resin powder for coating of the present invention is not limited to the mechanical pulverization method, and can be performed by a chemical pulverization method, an emulsion polymerization method, a granulation spray method, and a combination thereof.
The polyamide resin powder for coatings of the present invention has an advantage that edge breakage can be effectively prevented even if the powder is a non-uniform shape produced by a mechanical pulverization method. Therefore, the shape of the polyamide resin powder for coating of the present invention does not need to be uniform, and may be non-uniform (for example, spherical, elliptical, or irregular shapes such as crushed materials). The average particle size of the polyamide resin powder for coating is, for example, about 10 to 300 μm (for example, 20 to 280 μm), and preferably about 50 to 250 μm (for example, 60 to 240 μm). However, the polyamide resin powder for coatings has an optimum particle size and particle size in consideration of each processing method and the material and purpose of the object to be coated in order to improve the adhesion of the resin and the uniformity of the coating film. It is necessary to select and use a powder having a distribution.
[0020]
[Powder paint]
The coating using the polyamide resin powder of the present invention is often performed by powder coating, particularly fluid immersion. Powder coating is performed for imparting chemical resistance, wear resistance, rust prevention, coloring, and the like to a substrate (a substrate to be coated, such as a metal material or ceramic). In particular, fluid dipping is a useful method for coating substrates having sharp angled edges. The angle in the edge portion is not particularly limited, and may be, for example, about 10 to 90 °, particularly about 10 to 50 °. The fluid immersion can be performed under appropriate conditions according to the type of polyamide resin powder, for example, at a temperature of about 80 to 300 ° C., preferably about 100 to 280 ° C. The coating is not limited to fluid immersion, and can be performed by electrostatic coating or thermal spraying.
[0021]
【Example】
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
Examples 1 to 12, Reference Example 1 and Comparative Examples 1 to 3
A polyamide powder containing polyamide 12 (manufactured by Daicel Huls Co., Ltd .: trade name: Daiamide Z2073A) is added with a predetermined amount of melamine or a derivative thereof shown in the table and a required amount of additives shown in the table, using a Henschel mixer. Stirring to prepare polyamide resin powder.
For coating, a 3 mm thick steel plate (7 cm × 9 cm) having a sharp angle of about 30 degrees at the end is heated until the surface temperature reaches 280 ° C., and then it flows well with air while it is hot. The sample was immersed in the powder, and immersed in the fluidized bed of the powder for about 7 seconds while shaking the iron plate, and then slowly cooled at room temperature.
The state of the edge part (edge) of the iron plate after coating was observed, and whether or not the coating film was peeled off from the edge was observed. The effect of melamine or a derivative thereof on edge breakage was evaluated by counting the number of edges where peeling occurred one day after standing at room temperature. The results are shown in Table 1.
[0022]
[Table 1]
[0023]
【The invention's effect】
Since the polyamide resin powder for coatings of the present invention is mixed with a compound having a triazine ring, edge breakage can be effectively prevented. Moreover, the polyamide resin for coatings of the present invention can prevent edge breakage stably and effectively over a long period of time by adding a compound having a triazine ring, regardless of the addition of an additive.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27793396A JP3846946B2 (en) | 1996-10-21 | 1996-10-21 | Polyamide resin powder for paint and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27793396A JP3846946B2 (en) | 1996-10-21 | 1996-10-21 | Polyamide resin powder for paint and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10120978A JPH10120978A (en) | 1998-05-12 |
| JP3846946B2 true JP3846946B2 (en) | 2006-11-15 |
Family
ID=17590310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27793396A Expired - Fee Related JP3846946B2 (en) | 1996-10-21 | 1996-10-21 | Polyamide resin powder for paint and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3846946B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3831866B2 (en) * | 2000-11-29 | 2006-10-11 | アルケマ株式会社 | Polyamide flame retardant powder coating composition |
| JP4003156B2 (en) * | 2000-11-29 | 2007-11-07 | アルケマ株式会社 | Polyamide flame retardant powder coating composition |
| CN114262456A (en) * | 2021-11-19 | 2022-04-01 | 江苏双星彩塑新材料股份有限公司 | Thin polyester film and preparation method thereof |
-
1996
- 1996-10-21 JP JP27793396A patent/JP3846946B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10120978A (en) | 1998-05-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5593735A (en) | Aminoresin based coatings containing 1,3,5-triazine tris-carbamate co-crosslinkers | |
| US5907006A (en) | Compositions for the coating of substrates of matt appearance | |
| CA1091236A (en) | Substantially fully methylolated glycoluril derivative | |
| CA1085989A (en) | Cross linkable powder coating compositions | |
| CA1267242A (en) | Using pulverulent coating means based on polyamides with at least nine carbon atoms on the average per carbonamide group | |
| US4053682A (en) | Process for improving the adhesion of hot melts to metal substrates | |
| JPH06508172A (en) | powder coating composition | |
| JP3846946B2 (en) | Polyamide resin powder for paint and method for producing the same | |
| JP4754662B2 (en) | Self-adhesive composition for coating metal substrates with improved penetration resistance | |
| JPH09501454A (en) | Polyamide-based powder composition for coating metal substrates | |
| US5643682A (en) | Sulfonimide catalysts for coatings | |
| EP0866736B1 (en) | Coating of un-primed metals with polyamide powder coating compositions | |
| US4066462A (en) | Anti-corrosive organic pigment | |
| KR20030076391A (en) | Coating powder compositions and method | |
| CA1312694C (en) | Aminoplast catalyst and composition | |
| KR20230084549A (en) | Easily recyclable colored powder composition for substrate coating | |
| JPS63309563A (en) | Powder for polyamide base coating and coated substrate | |
| US3927141A (en) | Polyamide base powder coating material containing an aminoplast carrying alkoxyalkyl groups | |
| JPS6330071B2 (en) | ||
| EP0851893A1 (en) | Formaldehyde-free crosslinkers | |
| JPH111634A (en) | Powder resin composition and its production | |
| EP0668334B1 (en) | Powder coating composition and method of coating a substrate therewith | |
| JPS60228524A (en) | Non-gelling synthetic resin | |
| JP4003156B2 (en) | Polyamide flame retardant powder coating composition | |
| EP0453730B1 (en) | Sulfonimide catalysts for coatings |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040518 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040601 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040802 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060523 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060721 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20060815 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060822 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090901 Year of fee payment: 3 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090901 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100901 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110901 Year of fee payment: 5 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110901 Year of fee payment: 5 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |