EP0847427A1 - Peinture pulverulente et son utilisation en revetement interieur de recipients d'emballage - Google Patents
Peinture pulverulente et son utilisation en revetement interieur de recipients d'emballageInfo
- Publication number
- EP0847427A1 EP0847427A1 EP96930968A EP96930968A EP0847427A1 EP 0847427 A1 EP0847427 A1 EP 0847427A1 EP 96930968 A EP96930968 A EP 96930968A EP 96930968 A EP96930968 A EP 96930968A EP 0847427 A1 EP0847427 A1 EP 0847427A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- powder coating
- particle size
- particles
- phenolic
- 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.)
- Ceased
Links
- 238000000576 coating method Methods 0.000 title claims description 167
- 239000000843 powder Substances 0.000 title claims description 118
- 239000011248 coating agent Substances 0.000 title claims description 103
- 238000012856 packing Methods 0.000 title 1
- 239000002245 particle Substances 0.000 claims description 78
- 239000004848 polyfunctional curative Substances 0.000 claims description 39
- 239000003822 epoxy resin Substances 0.000 claims description 38
- 229920000647 polyepoxide Polymers 0.000 claims description 38
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 33
- 238000009826 distribution Methods 0.000 claims description 30
- 238000004806 packaging method and process Methods 0.000 claims description 28
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 24
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 229940106691 bisphenol a Drugs 0.000 claims description 14
- 239000000314 lubricant Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- -1 Polypropylene Polymers 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 8
- 239000001993 wax Substances 0.000 claims description 8
- 229920003986 novolac Polymers 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 235000013824 polyphenols Nutrition 0.000 description 17
- 239000000463 material Substances 0.000 description 13
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 8
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 7
- 229930185605 Bisphenol Natural products 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000007859 condensation product Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000004310 lactic acid Substances 0.000 description 4
- 235000014655 lactic acid Nutrition 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 235000013361 beverage Nutrition 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000009928 pasteurization Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical group CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical group NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical group CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 229910052916 barium silicate Inorganic materials 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- NJXBVBPTDHBAID-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 NJXBVBPTDHBAID-UHFFFAOYSA-M 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 235000015122 lemonade Nutrition 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
Definitions
- the present invention relates to powder coatings, in particular for the interior coating of packaging containers, based on epoxy resins and phenolic hardeners, and a
- the present invention also relates to a method for
- Packaging containers such as cans, two and three-piece beverage cans u. ⁇ ., Are provided on the inside with a coating, on the one hand to protect the contents from being impaired by detached components of the metal sheet, and on the other hand to avoid corrosion of the metal sheet by aggressive contents.
- thermosetting powder coatings for covering weld seams in metal containers which are used to hold food or beverages.
- These thermosetting powder coatings contain as binder a mixture of an aromatic epoxy resin with an average of a maximum of 2 epoxy groups per molecule and an aromatic epoxy resin with an average of more than 2 epoxy groups per molecule.
- the condensation product of the diglycidyl ether of bisphenol A with bisphenol A with an equivalent weight of 220 to 280 based on phenolic hydroxyl groups or an acidic polyester or a mixture thereof is used as the hardener.
- EP-B-119164 neither contains instructions on how to use these powder coatings for the interior coating of packaging containers, nor does it contain instructions on how to modify these powder coatings for use as internal protective coatings. In particular, EP-B-119 164 does not contain any information about particle sizes and particle size distributions of the powder coating materials. However, the use of these powder coatings of EP-B-119 164 with a particle size distribution customary for powder coatings leads to coatings which have too high a porosity in the case of the small layer thicknesses _ ⁇ 15 ⁇ m which are customary for interior coatings.
- DE-PS 23 12 409 heat-curable, solvent-containing and solvent-free coating compositions for the coating of automobile bodies, machines, systems and containers are known, which consist of an epoxy resin with more than one 1,2-epoxy group per molecule and a polyol with more than a phenolic OH group per molecule and other conventional auxiliaries and additives.
- DE-PS 23 12409 a powder coating with a particle size of at most 0.044 mm in a dry film layer thickness of 25 ⁇ m is applied for the production of automotive cover sheets. Neither the particle size nor the particle size distribution of the powder coating particles is described for powder coating materials which are suitable for the production of interior coatings for packaging containers.
- DE-PS 23 12 409 also contains no indication that the particle size and particle size distribution can be set in a targeted manner depending on the application of the powder coating materials. Powder coatings with a maximum particle size of 44 ⁇ m and a usual particle size distribution are, however, unsuitable for the production of interior coatings for packaging containers with the usual low layer thickness _ ⁇ _ 15 ⁇ m, since the resulting coatings have too high a porosity.
- a disadvantage of the powder coatings described in US Pat. No. 3,962,486 is that which is caused by the use of amine hardeners insufficient sterilization resistance of the resulting coatings.
- Another disadvantage is that epoxy resins cured with amines tend to become brittle and have very poor elasticities. Acid anhydride hardeners have the disadvantage that they are highly irritating and special precautions are therefore necessary when formulating the powder coatings.
- powder coatings for the internal coating of cans are known from US Pat. No. 4,183,974, which also contain an epoxy resin and an amine hardener. These powder coatings have average particle sizes between 1 and 100 ⁇ m, preferably between 1 and 10 ⁇ m. Although the resulting coatings already have the required low porosity at layer thicknesses of ⁇ _ 13 ⁇ m, the resistance to sterilization of the resulting coatings in turn needs to be improved. Another disadvantage is that epoxy resins cured with amines tend to become brittle and have very poor elasticities.
- German patent application P 40 38 681.3 discloses powder coatings based on epoxy resins which, when the particle size distribution of the powder coating particles is set appropriately, are suitable both for coating the inside of packaging containers and for covering weld seams. These powder coatings contain polyester containing carboxyl groups as hardener. The use of phenolic hardeners is not described in this patent application.
- the present invention is therefore based on the object of providing powder coatings which, when used for the inner coating of packaging containers, also meet the requirements which are usually placed on inner coatings of cans even when applied with small layer thicknesses of ⁇ _ 15 ⁇ m.
- these inner coatings should not be porous (determined with the aid of the so-called enamel rater test), show good adhesion to the substrate, have high elasticity and be stable under the usual pasteurization and sterilization conditions.
- the powder coatings should be able to be hardened during the short drying times customary for can coating.
- This object is surprisingly achieved by a powder coating based on epoxy resins and phenolic hardeners, in particular for the interior coating of packaging containers
- Groups from 100 to 500,
- the powder coating has a particle size distribution such that a) at least 90 percent by mass of the powder coating particles have a particle size between 1 and 60 ⁇ m,
- the maximum particle size for at least 99 percent by mass of the powder coating particles is ⁇ _ 100 ⁇ m
- the average particle size of the powder coating particles is between 5 and 20 ⁇ m and
- the invention relates to methods for the inner coating of packaging containers, in which these powder coatings are applied.
- the invention also relates to the use of the powder coating materials for the interior coating of packaging containers.
- the powder coatings according to the invention can be hardened quickly, are easy to handle and easy to apply, have good processing speed, good flexibility and transparency after coating.
- the powder coatings according to the invention are distinguished in that coatings with only a very small layer thickness of j ⁇ 15 ⁇ m have the properties required by the can manufacturers for interior coatings. In particular, these coatings have the required low porosity even with a small layer thickness of ⁇ 15 ⁇ m.
- these coatings are characterized by good adhesion, high flexibility and good resistance to pasteurization and sterilization.
- the epoxy resins used in the powder coating materials of the invention are solid epoxy resins with an epoxy equivalent weight of 300 to 5500.
- Aromatic, aliphatic and / or cycloaliphatic epoxy resins are suitable.
- Aromatic epoxy resins based on bisphenol-A and / or bisphenol-F and / or epoxy resins of the novolak type are preferably used.
- Epoxy resins based on bisphenol-A or bisphenol-F used with particular preference have an epoxy equivalent weight of 500 to 2000.
- Novolak-type epoxy resins used with particular preference have an epoxy equivalent weight of 500 to 1000.
- Epoxy resins based on bisphenol-A or bisphenol-F generally have a functionality of at most 2 and epoxy resins of the novolak type generally have a functionality of at least 2.
- the epoxy resins based on bisphenol-A or bisphenol-F can also be brought to a functionality of more than 2 by branching, for example by means of trimethylolpropane, glycerol, pentaerythritol or other branching reagents.
- branching for example by means of trimethylolpropane, glycerol, pentaerythritol or other branching reagents.
- other epoxy resins such as, for example, alkylene glycol diglycidyl ether or their branched secondary products
- epoxy resins based on bisphenol A or F oa which have been flexibilized with alkylene glycols can also be used. Mixtures of various of the epoxy resins mentioned are also suitable.
- Suitable epoxy resins are, for example, the following
- AralditR GT 6064, GT 7072, GT 7203, GT 7004, GT 7304, GT 7097 and GT 7220 from Ciba Geigy.
- All solid compounds with more than one phenolic OH group, preferably 1.8 to 4, particularly preferably j ⁇ 3, very particularly preferably 1.8 to 2.2 phenolic OH groups per molecule and a hydroxyl equivalent weight are suitable as hardener components , based on phenolic OH groups, from 100 to 500, preferably 200 to 300.
- a particularly preferred hardener is the condensation product of the diglycidyl ether of bisphenol-A or bisphenol-F with bisphenol-A or bisphenol-F, in particular the condensation product with an equivalent weight of 220 to 280 based on phenolic hydroxyl groups.
- These condensation products are usually prepared by reaction of generally excess bisphenol with a bisphenol digiycidyl ether in the presence of a suitable catalyst.
- the condensation product is preferably produced by reacting the Diglycidyl ether with the bisphenol in a weight ratio of 0.5 to 2.
- These hardeners based on these condensation products of the bisphenol diglycidyl ether with a bisphenol generally have a functionality of at most 2, it being possible in turn to set higher functionalities by using branching reagents .
- reaction products of bisphenols with epoxy resins of the novolak type are also suitable as hardeners.
- These hardeners are preferably obtained by reacting the epoxy resin with the bisphenol in a weight ratio of 0.5 to 2 in the presence of a suitable catalyst.
- A is a divalent hydrocarbon radical with 1 to 6 carbon atoms or the radicals
- X is a hydrogen or alkyl having 1 to 4 carbon atoms n an average value of 1 to 9, preferably 2 to 7 and y assumes a value of 0 or 1.
- the phenolic hardeners described in DE-OS 3027 140 can also be used.
- hardeners modified with branching reagents and / or flexible hardeners are also suitable. Mixtures of different hardeners mentioned can also be used. FDA-approved hardeners are preferred.
- the epoxy resin component is usually used in the powder coatings according to the invention in an amount of 29 to 80% by weight, preferably 39 to 60% by weight, in each case based on the total weight of the powder coating.
- the hardener component is usually used in the powder coatings according to the invention in an amount of 10 to 50% by weight, preferably 15 to 40% by weight, in each case based on the total weight of the powder coating.
- the powder coatings according to the invention contain at least one curing catalyst, usually in an amount of 0.01 to 5.0% by weight, preferably 0.05 to 2.0% by weight, in each case based on the total weight of the powder coating.
- the catalyst is imidazole, 2-methylimidazole, ethyltriphenylphosphonium chloride or another salt thereof, a quinoline derivative, as described for example in EP-B-10805, a primary, secondary or tertiary aminophenol, aluminum acetylacetonate or a toluenesulfonic acid salt or a mixture of different salts Catalysts.
- the commercially available curing agents containing hydroxyl groups usually already contain a curing catalyst.
- Examples of such commercially available hydroxyl group-containing hardeners which are preferably used are the products which are commercially available under the following names: DEH R 81, DEH R 82 and
- the powder coatings according to the invention can also contain 0 to 55% by weight, preferably 15 to 25% by weight, of fillers.
- FDA-approved fillers are preferred.
- inorganic fillers e.g. titanium dioxide, e.g. Kronos 2160 from Kronos Titan, Rutil R 902 from Du Pont and RC 566 from Sachtleben, barium sulfate and silicate-based fillers such as Talc, kaolin, magnesium aluminum silicates, mica etc. used. Titanium dioxide and fillers of the quartz sand type are preferably used.
- the powder coating materials of the invention may optionally contain from 0.01 to 10% by weight, preferably 0.1 to 2% by weight, based on the total weight of the powder coating material, of further auxiliaries and additives.
- auxiliaries and additives examples include leveling agents, flow aids, deaerating agents, such as e.g. Benzoin, pigments, etc.
- the maximum particle size of the powder coating particles is ⁇ ⁇ 100 ⁇ m, preferably _ ⁇ 60 ⁇ m and particularly preferably ⁇ 40 for at least 99% by mass of the particles OK
- the average particle size of the powder coating particles is between 5 to 20 ⁇ m, particularly preferably between 5 to 12 ⁇ m. Furthermore, it is essential to the invention that when the powder coating materials are used for the inner coating of the packaging containers, the grain size distribution is adjusted so that the slope S of the grain distribution curve at the turning point is> 100, preferably> 150 and particularly preferably> 200. To achieve coatings with particularly good properties, powder coatings are very particularly preferably used in which the slope S of the grain size distribution curve is _> 300 at the turning point.
- the slope S is defined as the limit for f (x2) - f ( ⁇ l) towards zero of (ffe) - f ( x l)) / lg (( x 2 / ⁇ l)) at the point of inflection of the grain distribution curve.
- the grain distribution curve represents the plot of the cumulative mass percent (f (x)) against the absolute grain diameter (x), the grain diameter being shown on a logarithmic scale and the cumulative mass percent on a linear scale.
- Powder coatings which have only a small proportion of very fine particles (particle size ⁇ 5 ⁇ m) and at the same time only a very small proportion of coarse-particle powder coating particles (particle size> 25 ⁇ m) are therefore particularly suitable for use as the inner coating of packaging containers, i.e. a have as narrow a grain size distribution as possible.
- the respective particle size distribution of the powder coating is adjusted using suitable grinding units, if necessary in combination with suitable viewing and screening devices, e.g. With
- Fluidized bed jet mills from Alpine, Augsburg, in Combination with Turboplex fine classifiers from Alpine, Augsburg.
- lubricants are also essential to the invention. According to the invention, this is added in amounts of less than 2% by weight. Additions of less than 1% by weight are preferred. The range from 0.1 to 0.6% by weight has proven itself best. Propylene waxes, modified polyethylene waxes and acid amides are used as lubricants.
- the propylene waxes are preferably used in micronized form.
- Such waxes include under the name Hoechst-Wachs pp. 230, Hoechst-Wachs C, Hoechst-Wachs C micropowder PM and Hoechst-Wachs R 31 commercially available.
- the polyethylene waxes are generally waxes modified with polytetrafluoroethylene. These are commercially available available under the names Hoechst-Wachs PED 121, 191, 136, 153, 261, 521, 522, as well as Hostalup H 12 and Hostalup H 22.
- Acid amides which can be used according to the invention include, in particular, erucic acid amide and oleic acid amide.
- the addition of the lubricants according to the invention achieves surprising, unexpected properties, in particular when using the powder coatings for the interior coating of packaging containers.
- the paints obtained are very flexible, surface-scratch-resistant.
- the corrosion protection properties are also improved.
- the material according to the invention has excellent transparency as a coating.
- the powder coatings are produced by the known methods (see, for example, product information from BASF Lacke + Weg 80 AG, "Pulverlacke", 1990) by homogenizing and dispersing, for example using an extruder, screw kneader, etc. It is essential to the invention that the powder coatings their production can be adjusted to a grain size distribution adapted to the intended use by grinding and, if appropriate, by classifying and sieving.
- the lubricant is preferably extruded and ground together with the powder coating.
- particularly good property profiles can be achieved by this procedure.
- Other ways of wedging may be followed by sifting and application using corona systems or tribocharging.
- the result of a powder coating that has been produced and applied in the manner described is a surprisingly high matting, surface hardness, flexibility and improved adhesion.
- the packaging containers which are coated with the powder coatings according to the invention can consist of a wide variety of materials, have a wide variety of sizes and shapes and have been produced by various processes.
- metallic containers are coated with the powder coatings according to the invention. These metal containers may have been made by first rolling metal sheet and then joining it by perishing. The end pieces can then be attached to the resulting cylinder.
- the powder coatings according to the invention are used for internal coating of the can bodies, which generally already have a bottom.
- deep-drawn metal containers can also be coated on the inside with the powder coatings according to the invention.
- the powder coatings are also suitable for coating can lids and can bottoms.
- the packaging containers can consist of a wide variety of materials, such as aluminum, black plate, tin plate and various iron alloys, which may be provided with a passivation layer based on nickel, chromium and tin compounds.
- Containers of this type are usually used as containers for food and beverages, for example for beer, juices, lemonades, soups, vegetables, meat dishes, fish dishes, vegetables, but also e.g. for animal feed.
- the application is carried out according to known methods, such as are described, for example, in US Pat. No. 4,183,974.
- the powder coating particles are electrostatically charged by friction (triboelectricity).
- the powder coating particles are applied using special spray heads known to those skilled in the art.
- the powder coatings according to the invention can also be applied by the known method of electrostatic support.
- the powder coatings are usually applied in a layer thickness _ ⁇ 15 ⁇ m, preferably from 10 to 14 ⁇ m.
- the coatings meet the requirements usually placed on such films.
- the powder coatings can also be applied in higher layer thicknesses.
- the packaging container the inside of which has been provided with the powder coating according to the invention, is then subjected to a heat treatment in order to harden the powder coating.
- This heat treatment can be done in different ways.
- the containers are often transported through a continuous furnace.
- the powder coatings generally cure completely at object temperatures between 230 and 350 ° C. within a time of 5 to 30 s.
- the continuous furnace can be operated at a constant temperature or have a temperature profile that is set according to the respective circumstances.
- the invention is now explained in more detail below with the aid of exemplary embodiments. All information on parts and percentages are weight information unless expressly stated otherwise.
- the powder coatings were produced by weighing all the constituents in cans, premixing in a premixer, homogenizing at 60 to 80 ° C. using an extruder, cooling as quickly as possible and adjusting to the desired particle size distribution using grinding units.
- This powder mixture is extruded and ground together with erucic acid amide. In two experiments, an amount of 0.2% by weight and 0.5% by weight was added.
- the maximum particle size for at least 99 percent by mass of the particles is ⁇ 100 ⁇ m, the average particle size is 9 ⁇ m.
- the slope S at the inflection point of the grain distribution curve is 250.
- the result shows that the powder coating without erucic acid amide breaks when it is punched (brittle) and takes on a milky appearance.
- the powder coating with 0.2% lubricant is very flexible, can be punched well, but shows a milky appearance with 2% lactic acid. With 0.5% lubricant there are no complaints of this kind.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
L'invention concerne une peinture pulvérulente à base de résines époxy et de durcisseurs phénoliques, s'utilisant notamment pour le revêtement intérieur de récipients d'emballage, qui contient 1) au moins une résine époxy d'un poids équivalent en époxy compris entre 300 et 5500 et au moins un durcisseur comportant plus d'un groupe hydroxyle phénolique par molécule et un poids équivalent en hydroxyle compris entre 100 et 500, par rapport aux groupes OH phénoliques; la peinture pulvérulente présentant une répartition granulométrique telle a) qu'au moins 90 % en poids des particules de peinture pulvérulente présentent une dimension particulaire comprise entre 1 et 60 νm, b) que la dimension particulaire maximale des particules de peinture pulvérulente soit « 100 νm pour au moins 99 % en poids des particules, c) que la dimension particulaire moyenne des particules de peinture pulvérulente soit comprise entre 5 et 20 νm et d) que la pente de la courbe de répartition granulométrique soit » 100 au point d'inflexion et 2) un lubrifiant, de préférence dans un volume « 2 %.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19531585 | 1995-08-28 | ||
| DE19531585A DE19531585A1 (de) | 1995-08-28 | 1995-08-28 | Pulverlack und dessen Verwendung zur Innenbeschichtung von Verpackungsbehältern |
| PCT/EP1996/003769 WO1997008257A1 (fr) | 1995-08-28 | 1996-08-27 | Peinture pulverulente et son utilisation en revetement interieur de recipients d'emballage |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0847427A1 true EP0847427A1 (fr) | 1998-06-17 |
Family
ID=7770566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96930968A Ceased EP0847427A1 (fr) | 1995-08-28 | 1996-08-27 | Peinture pulverulente et son utilisation en revetement interieur de recipients d'emballage |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0847427A1 (fr) |
| JP (1) | JPH11511490A (fr) |
| KR (1) | KR19990044235A (fr) |
| CN (1) | CN1198767A (fr) |
| BR (1) | BR9610296A (fr) |
| CA (1) | CA2226956A1 (fr) |
| DE (1) | DE19531585A1 (fr) |
| WO (1) | WO1997008257A1 (fr) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19829790A1 (de) * | 1998-07-03 | 2000-01-05 | Gkn Automotive Ag | Pulverlack |
| DE10029548C2 (de) * | 2000-06-15 | 2002-07-04 | Basf Coatings Ag | Selbstvernetzender Pulverlack auf der Basis von Epoxidharzen und seine Verwendung |
| DE10152829A1 (de) * | 2001-10-25 | 2003-05-15 | Basf Coatings Ag | Pulverförmiger Beschichtungsstoff und funktionale Beschichtungen für hohe Dauergebrauchstemperaturen |
| ATE419293T1 (de) * | 2005-07-11 | 2009-01-15 | Akzo Nobel Coatings Int Bv | Pulverbeschichtungsmaterialien |
| CN101709195A (zh) * | 2009-12-25 | 2010-05-19 | 广州擎天实业有限公司 | 一种用于电木板涂装的纯环氧型粉末涂料及其制备方法 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4038681A1 (de) * | 1990-12-05 | 1992-06-11 | Basf Lacke & Farben | Pulverlack und dessen verwendung zur innenbeschichtung von verpackungsbehaeltern und zur schweissnahtabdeckung |
| DE4204266C2 (de) * | 1992-02-13 | 1996-04-18 | Basf Lacke & Farben | Pulverlack und Verfahren zur Innenbeschichtung von Verpackungsbehältern |
-
1995
- 1995-08-28 DE DE19531585A patent/DE19531585A1/de not_active Withdrawn
-
1996
- 1996-08-27 CA CA002226956A patent/CA2226956A1/fr not_active Abandoned
- 1996-08-27 BR BR9610296A patent/BR9610296A/pt not_active Application Discontinuation
- 1996-08-27 WO PCT/EP1996/003769 patent/WO1997008257A1/fr not_active Ceased
- 1996-08-27 EP EP96930968A patent/EP0847427A1/fr not_active Ceased
- 1996-08-27 KR KR1019980701471A patent/KR19990044235A/ko not_active Withdrawn
- 1996-08-27 CN CN96196590A patent/CN1198767A/zh active Pending
- 1996-08-27 JP JP9509851A patent/JPH11511490A/ja active Pending
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9708257A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19531585A1 (de) | 1997-03-06 |
| JPH11511490A (ja) | 1999-10-05 |
| WO1997008257A1 (fr) | 1997-03-06 |
| BR9610296A (pt) | 1999-03-16 |
| CA2226956A1 (fr) | 1997-03-06 |
| CN1198767A (zh) | 1998-11-11 |
| MX9801566A (es) | 1998-05-31 |
| KR19990044235A (ko) | 1999-06-25 |
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