EP1716199A2 - Procede de production de resines polyester a additifs nanoscalaires pour peinture pulverulente - Google Patents
Procede de production de resines polyester a additifs nanoscalaires pour peinture pulverulenteInfo
- Publication number
- EP1716199A2 EP1716199A2 EP05706180A EP05706180A EP1716199A2 EP 1716199 A2 EP1716199 A2 EP 1716199A2 EP 05706180 A EP05706180 A EP 05706180A EP 05706180 A EP05706180 A EP 05706180A EP 1716199 A2 EP1716199 A2 EP 1716199A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- nanoscale
- powder coating
- coating formulation
- additives
- additive
- 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.)
- Withdrawn
Links
- 239000000843 powder Substances 0.000 title claims abstract description 98
- 238000000576 coating method Methods 0.000 title claims abstract description 81
- 239000000654 additive Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 56
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 44
- 239000004645 polyester resin Substances 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000011248 coating agent Substances 0.000 title abstract description 39
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 239000000049 pigment Substances 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- 239000008385 outer phase Substances 0.000 claims abstract description 7
- 239000008199 coating composition Substances 0.000 claims description 33
- 230000000996 additive effect Effects 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- 229920000728 polyester Polymers 0.000 claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- QPYKYDBKQYZEKG-UHFFFAOYSA-N 2,2-dimethylpropane-1,1-diol Chemical group CC(C)(C)C(O)O QPYKYDBKQYZEKG-UHFFFAOYSA-N 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001923 silver oxide Inorganic materials 0.000 claims description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229910003437 indium oxide Inorganic materials 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910000859 α-Fe Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002734 clay mineral Substances 0.000 claims description 3
- -1 ethanol 1 Chemical class 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- QOFLTGDAZLWRMJ-UHFFFAOYSA-N 2-methylpropane-1,1-diol Chemical compound CC(C)C(O)O QOFLTGDAZLWRMJ-UHFFFAOYSA-N 0.000 claims description 2
- YHFGMFYKZBWPRW-UHFFFAOYSA-N 3-methylpentane-1,1-diol Chemical compound CCC(C)CC(O)O YHFGMFYKZBWPRW-UHFFFAOYSA-N 0.000 claims description 2
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 2
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims 2
- 239000002121 nanofiber Substances 0.000 claims 2
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 claims 2
- 229910001887 tin oxide Inorganic materials 0.000 claims 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims 1
- WMJLXPDZFWBSPE-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol methanol Chemical compound C1(CCCCC1)(CO)CO.CO WMJLXPDZFWBSPE-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 20
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000009472 formulation Methods 0.000 abstract description 11
- 230000000052 comparative effect Effects 0.000 description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 19
- 239000002105 nanoparticle Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000009969 flowable effect Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy 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
- C09D5/033—Powdery paints characterised by the additives
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/80—Processes for incorporating ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/046—Carbon nanorods, nanowires, nanoplatelets or nanofibres
Definitions
- the present invention relates to a process for the preparation of nanoscale additives containing nanodispersed polyester resins as binders for powder coatings.
- the invention further relates to a method for producing a powder coating formulation and a powder coating formulation itself.
- Powder coatings have been widely used due to the high cost-effectiveness of the process and the favorable assessment from the point of view of environmental protection when coating materials such as metal, glass, ceramics, etc.
- powder coatings which contain nanoparticles are provided, for example, by EP 1 164 159 AI, EP 1 361 257 AI and WO 02/051922 A2.
- Nanoscale particles come very close to this endeavor. Due to their extremely high specific surface (area / mass, e.g. m 2 / g), they are highly effective wherever, for example, it is about interacting with electromagnetic radiation from the environment via their surface or by means of diffusion a constant flow of material to the surrounding matrix. In addition, they can be evenly distributed in other substances down to the submicroscopic range, which within such a material leads to a property profile that is orders of magnitude more homogeneous than the distribution of microscale particles. Due to their special delicacy, they are not only invisible as such, the substances they contain often do not even have a cloudiness and appear transparent. Due to quantum effects, nanoparticles usually have new and different properties than the micro- and bulk materials of the same chemistry.
- Nanoparticulate titanium dioxide and zinc oxide absorb UV radiation even at concentrations that are irrelevant from a coloristic point of view. Relocated coatings are able to reliably and - in contrast to organic UV absorbers, which degrade over time - permanently shield the surface from high-energy and material-damaging UV rays.
- Nanocrystalline tin-doped indium oxide (ITO) has a number of special properties in accordance with the brochure “NRC Trade Trends”, Issue 2, October 2002, page 15 by Nordmann, Rassmann GmbH, which relate to an ITO called Nano®ITO such as transparency, coupled with electrical conductivity, antistatic, electromagnetic shielding and adsorption / reflection of heat radiation.
- Nano®ITO which is given by the dealer, can be used to refine polymers or varnishes by incorporation and these with attractive properties such as electrical conductivity, Equip antistatic or largely impermeable to heat radiation.
- nanoscale ferrite particles absorb microwaves scaled silver particles are able to due to their high specific surface to emit a steady stream of silver ions to the matrix surrounding them and to provide them with an antimicrobial effect.
- biocidal treatment of a powder coating which, as disclosed, for example, in US Pat. No.
- 5,980,620 A is equipped with an organic biocide homogeneously distributed in the coating matrix, for example a polychlorinated aromatic compound as active ingredient, the extremely fine, but heterogeneously distributed, nanoscale silver particles the guarantee that the biocidal effect of the powder coating equals the life of the coating, since a loss of the effect due to migration of the particles to the surface with subsequent loss of active ingredient is excluded and the particles, as long-term studies have shown, are not consumed over the years.
- Nanoscale zirconium dioxide, silicon dioxide, aluminum oxide, barium sulfate as well as corresponding clay minerals are able to give powder coating formulations a significantly improved hardness and scratch resistance.
- Nano®ITO IR-absorbing powder coating material
- a powder coating formulation which otherwise corresponded to the prior art. It was expected that due to the absorption behavior, such a powder coating formulation should be curable particularly quickly and / or with reduced radiation output by IR radiation.
- the powder coating raw materials used - binder components, pigments, filler, additives such as leveling agents and hardening accelerators - together with the state-of-the-art Nano®ITO were first thoroughly mixed in a high-speed mixer and then extruded; the introduction of the particles into the powder coating was therefore also carried out in analogy to that referred to in the aforementioned WO 02/051922 A2 as "melt extrusion"("meltextrusion") Method.
- the further course of the production of the powder coating and its application and curing on sample sheets in an IR curing system proceeded according to the prior art.
- Sample sheets with the relevant coatings - no matter which process is produced - have a very inhomogeneous surface image which cannot be reduced by reducing the
- Curing radiation energy used showed influence. Also an increase in
- GPTS glycidoxypropyltrimethoxysilane
- TEOS tetraethoxysilane
- the described ultrasonication of the particles in a low-viscosity liquid is certainly much more efficient for the production of a nanodisperse sol than the methods of the three aforementioned documents.
- the disadvantage of the compositions produced by the process described is that after the powder coating has been applied and stoved on, a further coating system is required in order to obtain coatings with scratch resistance and hardness.
- Another disadvantage is that this additional coating to be applied is a liquid system, so that in addition to a system for applying powder coating, another is required for applying a liquid system.
- a transfer of the above process to powder coatings is not a viable option, since it is not possible to dissolve the powder coating binders which are solid at room temperature and the above-mentioned coating sols, as is the case with the compositions disclosed.
- Nanoparticles that are obtained in powder form agglomerate very easily. Nanoparticles in such agglomerates are often irreversibly bound to one another and can only be brought into a nanodisperse state with great effort, if at all, using conventional methods. Since only solid raw materials can be used in powder coating production, it is economically impossible to incorporate nanoparticles nanodispersed in powder coatings. However, nanoparticles are often produced in liquid media, which means that nucleation and growth can be precisely controlled. In the liquid phase, the nanoparticles can be prevented from agglomeration and stable nanodisperse liquids can be produced. However, such liquids cannot be used in the production of powder coatings according to the prior art.
- the present invention has for its object to provide a method according to which nanoparticulate additives - as functional carriers - can be incorporated in such a way in polyester resins serving as binders for powder coatings and subsequently in powder coating formulations that they are efficiently distributed and therefore allow economical use of those additives.
- Another object of the invention is to provide powder coatings which are visually and uniformly represented in their paint properties.
- the object of providing a corresponding method for producing nanoscale additives containing polyester resins in a nanodispersed distribution as binders for powder coatings is achieved according to the invention by introducing the nanoscale additives in the form of a suspension in a liquid outer phase into the reaction mixture in the course of resin synthesis.
- the invention provides that the nanoscale additives are introduced in the initial phase of the resin synthesis.
- the invention also relates to a process for producing a powder coating formulation based on polyester resins as a binder component and, if appropriate, pigments, fillers and additives customary for powder coatings.
- this method is characterized in that polyester resins which contain nanoscale additives in nanodisperse form are used in accordance with the method according to one of claims 1 to 24. If polyester resins produced in accordance with the invention in this way are used for the production of powder coatings, this results in the possibility of efficiently equipping powder coatings with functionality-creating nanoparticles with a significantly lower amount of material compared to the “dry” method described above, the powder coatings that can be produced therewith being visual and functional in terms of their coating technology Properties are uniform.
- the invention also relates to a powder coating formulation based on polyester resins as a binder component and, if appropriate, pigments, fillers and additives which are customary for powder coatings, which powder coating formulation is characterized in that it contains nanoscale additives in a nanodispersed distribution in the binder matrix. Only the nanodisperse distribution allows maximum use of the nano-specific properties.
- Polyester resins as binders for powder coatings have been state of the art for decades. According to the raw materials used, they are primarily carboxyl and / or hydroxyl functional and can be used, for example, in combination with polyfunctional epoxy or isocyanate compounds or else ß-hydroxyalkylamides for the production of heat-curable powder coatings.
- An example is DE 2 163 962 AI, which discloses thermosetting powder coatings based on carboxyl-functional polyesters.
- DE 2 105 777 A1 discloses heat-curable powder coatings based on hydroxyl-functional polyester.
- terminal carboxyl and / or hydroxyl groups which are primarily obtained in the production of the polyester can be used to react the above-mentioned intermediates with, for example, epoxy- or isocyanate-containing intermediates Add functionalities to the polyester in question.
- WO 95/25762 AI which is also to be regarded as a disclosure for semi-crystalline polyester resins (predominantly amorphous polyester resins are used as binders for powder coatings) and EP 0 741 763 AI.
- EP 1 236 765 AI describes the production of dispersions with a flowable outer phase, containing polymerizable monomers, oligomers and / or polymers, and a disperse phase consisting of nanoscale amorphous silicon dioxide.
- dispersions in which - according to the examples - the surface of the silicon dioxide particles have been organically modified by reaction with alkoxysilanes can, according to the disclosure of this document, be used as a filler for the production of polymeric materials with high contents of amorphous silica.
- a high filler content has a positive effect on the fracture mechanical properties and the electrical insulation capacity of materials in numerous applications.
- EP 1 236 765 AI does not provide information on how nano®ITO or other highly specific and efficient nanoparticles can be introduced nanodisperse in powder coatings in such a way that the potential of these particles can be exploited to the best possible extent and inhomogeneities which are recognizable - often in small amounts - are added to these particles the resulting powder coatings can be avoided.
- the flowable outer phase of the dispersions used according to the invention is water in the simplest way. Since numerous nanoparticles are produced in aqueous solutions using wet chemical methods, water is particularly obvious as the outer phase. The majority of the water fed to the reaction mixture with the dispersion leaves the reactor, in part as steam from the start of the esterification reaction and thus increases the amount of by-product water obtained during the esterification.
- Solvents which are neutral in the synthesis of the polyesters according to the invention represent a further group of liquids which can be used according to the invention. Examples are aromatic hydrocarbons, lower alcohols, ethers or else Ketones. However, their use is less preferred for ecological as well as economic reasons. As previously described for water, solvents are also removed from the batch by evaporation.
- the flowable outer phase can be liquid substances which are used as reaction participants in the polyester synthesis anyway.
- these are diols which are liquid at room temperature, such as ethanediol 1,2, propanediol 1,2 and propanediol 1,3, 2-methylpropanediol 1,3, butanediol 1,4, pentanediol 1.5 and 3-methylpentanediol 1.5.
- diols or polyols which are solid at room temperature but mixed with water or lower alcohol but are liquid, such as, for example, 2,2-dimethylpropanediol 1,3 or cyclohexanedimethanol with water or cyclohexanedimethanol with methanol.
- esters of dicarboxylic acids with lower alcohols for example dimethyl adipate, dimethyl glutarate or dimethyl succinate.
- the inner esters of hydroxycarboxylic acids such as ⁇ -caprolactone or ⁇ -butyrolactone also offer themselves as an external flowable phase. These reactants are predominantly - except for the alcoholic components of carboxylic acid esters - built into the resulting resin, so there is hardly any need to evaporate liquids, which is advantageous in terms of energy requirements for resin production.
- the dispersions required for the use of the nanoscale additives according to the invention can usually be obtained from the manufacturer of these substances and represent the preferred source for nanodisperse preparations. Where this is not possible in individual cases, the user himself can also produce corresponding dispersions in suitable liquid phases with good success become. Suitable dispersing machines for this are, for example, dissolvers or bead mills, possibly in combination with ultrasound. The state of the art is described for example by A. Goldschmidt / H.-J. Streitberger, BASF manual for coating technology, Vincentz-Verlag, 2002. In a “bottom up” synthesis, nanoparticles are preferably produced and stabilized directly nanodisperse by nucleation and controlled growth in the liquid phase. This prevents agglomeration from the start.
- the amounts of nanoscale functional carriers to be added to the polyester and thus to the final powder coating are extremely variable - they comprise a concentration range that extends over at least 3 powers of ten - and primarily depend on the type of additive in question and the desired effect.
- the temperature in the reaction vessel was then reduced to 190 ° C. and 153.70 g of trimellitic anhydride were added to the hydroxy-functional polyester.
- the mixture was kept at this temperature with stirring for 70 minutes and then emptied into a tin cup, where it solidified with cooling.
- the finished resin ultimately had an acid number of 72.6 mg KOH / g polyester resin.
- Comparative Example B Carboxyl-Containing Polyester Resin - Not According to the Invention: In a heatable 2-1 reaction vessel equipped with a stirrer, temperature sensor and inert gas inlet (nitrogen), 1146 g of granulated polyester resin according to Comparative Example A were gently heated to 180 ° C.
- melt blending 3 g of dry, solid Nano®ITO (nanocrystalline tin-doped indium oxide from Nanogate Technologies) were introduced into the melt and kept at constant for one hour The mixture was then poured into a tin cup, where it solidified under cooling.
- Example 1 Carboxyl Group-Containing Polyester Resin with Nanoscale and Nanodispersed Nano®ITO - According to the Invention:
- Example 3 Carboxyl Group-Containing Polyester Resin with Nanoscale and Nanodisperse Carbon (C-Nonotubes) - According to the Invention: 482.16 g of 2,2-dimethylpropanediol 1,3 and 37.25 g of ethylene glycol were placed in the reaction vessel described in Comparative Example A, and 38.64 g of a 1% nanodisperse suspension of C-nanotubes in water (Fa. Melted nanoledge) and heating to a maximum of 140 ° C under a nitrogen atmosphere. The further procedure for the production of the polyester was then completely analogous to Comparative Example A. The finished resin ultimately had an acid number of 72.8 mg KOH / g polyester resin and had a content of 0.03% C nanotubes.
- Example 4 Carboxyl Group-Containing Polyester Resin with Nanoscale and Nanodisperse Silver / Titanium Dioxide - According to the Invention:
- Comparative Examples C, D and E contain only polyester from Comparative Examples A and B as the polyester component; the polyesters from Examples 1-4 were used for the formulation of Examples 5-8.
- Example 8 The formulation of Example 8 was instead applied to aluminum test panels. Subsequently, the test plates with the formulations C - E and 5 - 7 were cured by medium to long-wave IR radiation in an electrically operated curing system - 4 radiators from Heraeus (2 carbon radiators medium wave, 2 conventional radiators medium wave), both transverse to the Direction of delivery attached and fed with a maximum lamp temperature ⁇ 1000 ° C. The belt speed was chosen so that the samples covered the curing distance in approx. 3.5 minutes happened. The surface temperature was approx. 100 ° C for the first 30 seconds, then an average of 135 ° C.
- Table 2 describes the chemical resistance of the test subjects in question to the action of a solvent (methyl ethyl ketone).
- the chemical resistance feature is used to assess the crosslink density of the powder coating achieved by baking.
- Methyl ethyl ketone is dripped onto the surface to be tested at room temperature and the time in minutes is measured after which the varnish can be wiped off at least partially from the surface with a cellulose cloth under moderate pressure. If the powder coating resists the solvent for 10 minutes, the test is ended and the test is passed.
- Comparative Example C In Comparative Example C (the addition of 0.01% Nano®ITO was not made according to the invention), no curing is achieved by the heat treatment in the curing system (the powder coating can be washed off). An increase in the amount added in D tenfold (0.1% Nano®ITO in the powder coating) compared to comparative example C and compared to examples 5 and 6 according to the invention results in a marginal, but still completely inadequate hardening. Comparative example E - likewise contains 0.1% Nano®ITO in the powder coating like comparative example C - shows a tendency to improve compared to this, but here too there is no question of hardening.
- the antimicrobial effect (bacteria, fungi, yeasts) of the coating from the above formulation was confirmed by the Institut Fresenius (Taunusstein, Hessen) based on ASTM Standard E2180.
- Example 9 Carboxyl Group-Containing Polyester Resin with Nanoscale and Nanodisperse Ferrite (Fe 3 O 4 ) - According to the Invention:
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Abstract
L'invention concerne un procédé permettant de produire des résines polyester contenant des additifs nanoscalaires répartis de manière nanodispersée, qui s'utilisent comme liants pour peintures pulvérulentes. Les additifs nanoscalaires sont introduits sous forme de suspension dans une phase liquide extérieure, dans la charge de réaction de départ, au cours de la synthèse des résines. L'invention concerne également un procédé permettant de produire une formulation de peinture pulvérulente à base de résines polyester comme constituants liants, ainsi qu'éventuellement de pigments, de charges et d'additifs habituels dans des peintures pulvérulentes, les résines polyester utilisées contenant des additifs nanoscalaires répartis de manière nanodispersée. L'invention comprend également une formulation de peinture pulvérulente. L'invention concerne également une formulation de peinture pulvérulente à base de résines polyester comme constituants liants, ainsi qu'éventuellement de pigments, de charges et d'additifs habituels dans des peintures pulvérulentes, la formulation de peintures pulvérulentes contenant quant à elle des additifs nanoscalaires répartis de manière dispersée dans la matrice de liants.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0018104A AT413699B (de) | 2004-02-06 | 2004-02-06 | Verfahren zur herstellung von polyesterharzen sowie solche polyesterharze umfassende pulverlackformulierungen |
| PCT/AT2005/000036 WO2005075548A2 (fr) | 2004-02-06 | 2005-02-04 | Procede de production de resines polyester a additifs nanoscalaires pour peinture pulverulente |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1716199A2 true EP1716199A2 (fr) | 2006-11-02 |
Family
ID=34831630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP05706180A Withdrawn EP1716199A2 (fr) | 2004-02-06 | 2005-02-04 | Procede de production de resines polyester a additifs nanoscalaires pour peinture pulverulente |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20070276072A1 (fr) |
| EP (1) | EP1716199A2 (fr) |
| AT (1) | AT413699B (fr) |
| CA (1) | CA2554418A1 (fr) |
| WO (1) | WO2005075548A2 (fr) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008081384A (ja) * | 2006-09-29 | 2008-04-10 | Fuji Xerox Co Ltd | カーボンナノチューブ分散液およびカーボンナノチューブ構造体の製造方法、並びにカーボンナノチューブ構造体 |
| EP2089467A2 (fr) * | 2006-11-07 | 2009-08-19 | Basf Se | Procédé pour produire des polymères remplis d'oxydes métalliques nanométriques |
| DE102007026253A1 (de) | 2007-03-06 | 2008-09-11 | Electrovac Ag | Beschichtungsmaterial bzw. Lack mit verbesserter Wärmeübertragung sowie Wärme übertragende Oberfläche mit einer unter Verwendung des Beschichtungsmaterials hergestellten Beschichtung |
| US20100009185A1 (en) * | 2008-07-14 | 2010-01-14 | Ta Ya Electric Wire & Cable Co., Ltd. | Enameled wire containing a nano-filler |
| CN106146894B (zh) * | 2015-03-23 | 2018-07-10 | 李佳怡 | 一种高透明性高隔热性热相变材料的制备方法 |
| CN104946003A (zh) * | 2015-07-14 | 2015-09-30 | 山东朗法博粉末涂装科技有限公司 | 粉末涂料用疏松剂的添加方法 |
| CN107722799B (zh) * | 2017-09-05 | 2022-10-04 | 浙江旗创新材料科技有限公司 | 一种提升粉末涂料生产成品率的生产工艺 |
| CN114085363B (zh) * | 2021-12-13 | 2023-01-03 | 安徽神剑新材料股份有限公司 | 一种高填充粉末涂料用聚酯树脂及其制备方法、高填充粉末涂料 |
| CN116082924B (zh) * | 2022-11-07 | 2023-10-24 | 东莞浩川新材料有限公司 | 一种低温固化的薄涂层绝缘粉末涂料及其制备方法 |
| CN117535002A (zh) * | 2023-12-15 | 2024-02-09 | 江苏睿浦树脂科技有限公司 | 一种聚酯型透明粉末涂料及其制备方法 |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK0525870T3 (da) * | 1991-07-22 | 1994-11-28 | Akzo Nobel Nv | Pulvermalingsammensætning indeholdende en harpiks,en hærder og zink |
| US5716679A (en) * | 1991-09-13 | 1998-02-10 | Institut Fur Neue Materialien Gemeinnutzige Gmbh | Optical elements containing nanoscaled particles and having an embossed surface and process for their preparation |
| US5385963A (en) * | 1992-01-30 | 1995-01-31 | Gencorp Inc. | Unsaturated polyester-modified flexible copolymers for use in sheet molding compositions |
| US5932309A (en) * | 1995-09-28 | 1999-08-03 | Alliedsignal Inc. | Colored articles and compositions and methods for their fabrication |
| US6652967B2 (en) * | 2001-08-08 | 2003-11-25 | Nanoproducts Corporation | Nano-dispersed powders and methods for their manufacture |
| US6514453B2 (en) * | 1997-10-21 | 2003-02-04 | Nanoproducts Corporation | Thermal sensors prepared from nanostructureed powders |
| DE19857316A1 (de) * | 1998-12-11 | 2000-06-15 | Inst Neue Mat Gemein Gmbh | Pulverlackierte Substrate mit einem Decklack auf Basis epoxidgruppenhaltiger Silane |
| US6337362B1 (en) * | 2000-06-12 | 2002-01-08 | Elementis Specialties, Inc. | Ultraviolet resistant pre-mix compositions and articles using such compositions |
| US20020115777A1 (en) * | 2000-12-15 | 2002-08-22 | Bin Wu | Nanocomposites in powder coatings |
| EP1236765A1 (fr) * | 2001-02-28 | 2002-09-04 | hanse chemie GmbH | Dispersion de silice |
| DE10138568A1 (de) * | 2001-08-06 | 2003-03-06 | Arteva Tech Sarl | Verfahren zur Herstellung eines antimikrobiellen Polyester, antimikrobieller Polyester und seine Verwendung |
| CA2426916C (fr) * | 2002-04-30 | 2008-06-17 | Rohm And Haas Company | Poudres de revetement, methodes pour les produire et articles ainsi produits |
| EP1371693A3 (fr) * | 2002-06-14 | 2004-01-07 | Rohm And Haas Company | Revêtements, couches et articles résistants aux dommages et comprenant des nanoparticules réticulées |
| AT412555B (de) * | 2003-01-24 | 2005-04-25 | Tigerwerk Lack Und Farbenfabri | Kunststoffbindemittel zur herstellung von pulverlacken |
| DE10311645A1 (de) * | 2003-03-14 | 2004-09-23 | Degussa Ag | Nanoskaliges Indium-Zinn-Mischoxidpulver |
| DE10311709A1 (de) * | 2003-03-17 | 2004-12-16 | Saehan Industries Inc. | Gesättigter Polyester zur Formgebung mit hervorragender Kristallinität |
| WO2005119772A2 (fr) * | 2004-06-02 | 2005-12-15 | Douglas Joel S | Revetements comprenant des nanotubes de carbone |
| US7598315B2 (en) * | 2005-01-24 | 2009-10-06 | Lubrizol Advanced Materials, Inc. | Aqueous dispersions of nanoparticle/polyurethane composites |
-
2004
- 2004-02-06 AT AT0018104A patent/AT413699B/de not_active IP Right Cessation
-
2005
- 2005-02-04 EP EP05706180A patent/EP1716199A2/fr not_active Withdrawn
- 2005-02-04 CA CA002554418A patent/CA2554418A1/fr not_active Abandoned
- 2005-02-04 US US10/588,346 patent/US20070276072A1/en not_active Abandoned
- 2005-02-04 WO PCT/AT2005/000036 patent/WO2005075548A2/fr not_active Ceased
Non-Patent Citations (1)
| Title |
|---|
| None * |
Also Published As
| Publication number | Publication date |
|---|---|
| US20070276072A1 (en) | 2007-11-29 |
| ATA1812004A (de) | 2005-09-15 |
| AT413699B (de) | 2006-05-15 |
| WO2005075548A3 (fr) | 2006-01-19 |
| CA2554418A1 (fr) | 2005-08-18 |
| WO2005075548A2 (fr) | 2005-08-18 |
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