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WO1991014746A1 - Procedes de peinture - Google Patents

Procedes de peinture Download PDF

Info

Publication number
WO1991014746A1
WO1991014746A1 PCT/GB1991/000481 GB9100481W WO9114746A1 WO 1991014746 A1 WO1991014746 A1 WO 1991014746A1 GB 9100481 W GB9100481 W GB 9100481W WO 9114746 A1 WO9114746 A1 WO 9114746A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
paint
aluminium
polyester
aoc
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
Application number
PCT/GB1991/000481
Other languages
English (en)
Inventor
Adrian Keith Arnold-Smith
John Walter Wright
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rio Tinto Alcan International Ltd
Original Assignee
Alcan International Ltd Canada
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Alcan International Ltd Canada filed Critical Alcan International Ltd Canada
Publication of WO1991014746A1 publication Critical patent/WO1991014746A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • 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

Definitions

  • Coated metal strip has a wide field of application ranging from cladding for buildings to office filing cabinets and bottle tops. Outstanding weathering behaviour of sheet intended as external cladding for buildings is required, when 40 plus years life expectancy are sought.
  • amino-resins such as hexamethoxymethylmelamine have dominated the markets for factory-applied metal coatings.
  • the advantageous properties of amino-resins include hardness and freedom from undesirable colour.
  • amino-resins suffer from the disadvantages of brittleness and poor adhesion. It is therefore necessary to blend the resin with plasticising components such as compatible alkyds, saturated polyesters or acrylic resins.
  • a phenomenon which has become recognised recently in amino-resin/saturated polyester films is that of film degradation due to thermal depolymerisation. This is potentially a very serious problem with implications for resin manufacturers, metal coating companies and owners of buildings and equipment coated with such systems.
  • This invention stems from work designed to replace the amino-resins, presently used in amino- resin/polyester coating compositions for metal strip, with aluminium organic compounds.
  • the inventors surprisingly found that amino-resins and aluminium organic compounds can act synergistically to provide polyester paint systems giving rise to films having outstanding long-term weathering properties.
  • This invention provides a paint based on a saturated polyester and comprising 5 to 50% of an amino resin, and 1 to 20% of an aluminium organic compound, percentages being by weight on the weight of the polyester.
  • Resin A is a commercially available oil-free polyester.lt has a resin solids content of 75% and an acid value of 17-21 mg KOH/g. (AROPLAZ 3256 from Ashland Chemicals) .
  • Resin B was an oil incorporated modification to Resin A which included some dimer acid. This contained about 20% by weight of methylene chains and a trace of unsaturation.
  • Resin B has a number average molecular weight of 880, a weight average molecular weight of 2655, an acid value of 5.4 mg KOH/g, a hydroxyl value of 85.8 mg KOH/g and a resin solids content of 75%. (Ashland EP 2580T) .
  • Resin C is an experimental oil free polyester with number average molecular weight of 1905, a weight average molecular weight of 9920, an acid value of 2.1 mg KOH/g, a hydroxyl value of 51.5 mg KOH/g and a resin solids content of 55%.
  • melamine-formaldehyde resin in which the melamine has been partly or completely alkylated to reduce its tendency to hydrolyse.
  • alkylated denotes the replacement of amino-hydrogen atoms by alkyl groups which may o themselves be substituted e.g. methoxymethyl groups.
  • commercially available melamine resins include:-
  • the proportion of amino-resin needs to be sufficient to cross-link the polyester, but not so Q high that the brittleness and poor adhesion properties of the amino-resin manifest themselves.
  • the proportion should be 5 to 50%, preferably 10 to 30%, by weight on the weight of the polyester.
  • the paints of this invention When the paints of this invention are c intended to be cured by stoving, they preferably include a blocked catalyst for the purpose. Suitable catalysts are available commercially, one used in the Examples below being an amine-blocked para-toluene sulphonic acid catalyst. (Cycat 4045 from Cyanamid) .
  • the paint preferably includes an aluminium organic compound including at least one group
  • X is derived from HX which is an alcohol or phenol, a carboxylic acid, a 1 ,3-diketone, an alkyl acetoacetate or an alkyl half-ester of a dicarboxylic acid and may be unsubstituted or substituted.
  • the aluminium organic compound may include one or two hydroxyl groups attached to Al. Or the AOC may have the formula A1X_, where X is defined above.
  • the AOC may contain more than one Al atom per molecule, by virtue of having the formula
  • X is derived from HX which may be water but is organic in at least one position in the molecule and is preferably: - a C1 to C30 aliphatic alcohol or a phenol which may be substituted; a C1 to C30 carboxylic acid, which may be aliphatic, alicyclic or aromatic and which may be substit ted; a 1,3-diketone such as acetylacetone; a C1 to C12 alkyl acetoacetate, which may be substituted in the alkyl group; a C1 to C12 alkyl half-ester of a C1 to C12 aliphatic, alicyclic or aromatic dicarboxylic acid, which may be substituted.
  • X may be the same or different at different parts of the molecule.
  • CH-COCH-COOR where R is C1 to C12 alkyl. They are believed to co-ordinate to Al through both ketonic oxygen atoms, in similar manner to carboxylates and to acetylacetone. All these AOC compositions have at least one substituent, an alkoxide or an oxo linkage, which is capable of addition or substitution reaction with a carboxylic acid or hydroxylic or epoxy group of the polyester resin with which it is compounded, to provide a reaction product resistant to hydrolysis or dissociation. These substituents may also have an ester substituent which, we have discovered, can transesterify with hydroxyl groups present in the resin.
  • This invention is based on the discovery that AOCs can inhibit thermal depolymerisation of amino-resin/polyester coatings on metals.
  • the inhibition of thermal depolymerisation improves as the concentration of the AOC increases.
  • increase in the AOC concentration of the paint may reduce the initial properties of the paint film.
  • the AOCs act to improve long-term film properties on stoving, they must be unreactive in the paints at ambient temperatures. Any significant cross-linking activity at ambient temperatures will tend to cause gel formation and make paints unusable.
  • the components are preferably dissolved or dispersed in a volatile liquid medium which may be water but is preferably organic.
  • Other components may be present, such as are conventionally present in amino- resin/polyester compositions. These include pigments, fillers, flow additives, driers and antioxidants.
  • the paints of this invention are useful for painting to metal sheet in the form of coil. Suitable metals include steel and aluminium, the surface of which may carry a chromate or other strongly adherent inorganic non-metallic coating, or may (in the case of aluminium) b anodised.
  • the method involves uncoiling a coil of the metal sheet, applying to the sheet a coating of the paint described above, stoving the coated sheet to cure the paint film and preferably thereafter re-coiling the coated sheet.
  • Techniques for applying and curing the paint can be conventional.
  • Polyester resins Three resins were used: A, B and C (see above) . 2.
  • Melamine resins Two resins were used: Y and Z (see above) .
  • AOC 1020A was a commercially available aluminium compound. The Al content is 5%.
  • AOC 101OX was a commercially available Q aluminium compound. The Al content is 9.4%.
  • AOC 1010C was an experimental aluminium compound in which the substituent groups were derived from ethylacetoacetate, an amino alcohol and water. Displaced 5 isopropanol was effectively present as a solvent. The Al content was 6.8%.
  • AOC 2050X was a commercially available oxo-aluminium compound. The Al content was 9.8%.
  • AOC 2010 was an experimental oxo-aluminium compound containing ethylacetoacetate and a glycol ether. White spirit was added as a diluent. The Al content was 5.9%.
  • AOC 1020 Mn was an experimental aluminium compound similar to AOC 1020A but additionally contained some manganese acetate. The Mn content was 0.7% and the Al content was 5.9%. (5) Formulation and Stovin ⁇ Conditions
  • the formulated resin mixtures were drawn down onto pretreated (chromated) aluminium plates (25 x 10cm).
  • the plates were 0.56 mm in thickness.
  • the wet film applied thickness was 25 um, giving dried films of approximately 15 um, unless otherwise stated in the Tables.
  • the temperature of the stoving oven was set at 255 C.
  • a standard 40 s bake produced a peak metal temperature of about 215°C.
  • aluminium compounds used were as noted in the Tables.
  • the amount of aluminium added to the formulation (0.069g) was related to the acid value of the polyester resin.
  • the important properties required of a durable coating on aluminium are a combination of hardness, flexibility, ability to withstand impact, chemical and - weather resistance. Depolymerisation was assessed by remeasuring some of these properties after subjecting the coated panels to elevated temperatures (about 113°C) for periods of up to 180 hours.
  • Table 2 illustrates the effect of varying the amount of AOC 2010 in the coating formulations (Panels A1 to A4) . It appears that increasing the aluminium concentrations led to improved film properties on ageing. Panels B1 and B2, and C1 and C2 demonstrate that, in the absence of aluminium, zinc octoate and manganese octoate are not very effective at the addition levels employed. Panels D1 to D3 again demonstrate the improved film stability of films incorporating aluminium even when an improved resin is employed (Panel D1 vs Panel A1 ) .
  • Zinc octoate was not effective (Panel E1 and E2), but manganese octoate did appear to enhance the film stability (Panels F1 and F2), perhaps as a result of a trace of unsaturation in resin B in which manganese stimulates some oxidative cross-linking.
  • Table 3 illustrates the effect of incorporating polyester resin A with AOC 2010, AOC 2010 plus PTSA catalyst and AOC 2010 plus PTSA catalyst and melamine. In the first instance it can be observed that, under the stoving conditions employed, the initial film properties were unsatisfactory. However, on ageing for 14 days, a H pencil hardness and 20 MEK double rubs indicated further curing. The additional presence of blocked PTSA was of no benefit. In the third row a hard, solvent resistant film was initially formed and was still intact after 14 days.
  • Table 4 compares initial film properties and ageing properties of a range of six aluminium alkoxides or oxo-aluminium compounds.
  • the levels of aluminium chosen were 1 , 2 and 3 equivalents per polyester acid group.
  • Panel 1-0 was the control formulation containing no aluminium..
  • the initial film properties of 1-0 were satisfactory. After 12 days the film had become slightly sticky, offered no solvent resistance and exhibited a ring fracture on the reverse impact test.
  • Panels 1-1 to 1-3 exhibit the influence of AOC 1020A.
  • the initial pencil hardness results were somewhat lower than in the control panel but gave better MEK resistance results at the two higher concentrations. On heat ageing the properties did not deteriorate as rapidly as the control, 1-0.
  • a mill base was prepared to the following formulation: parts weight Titanium Dioxide 150
  • EAA Ethoxyethylacetate
  • the base was milled to less than 7 fineness on Hegmann gauge and used to prepare a base paint as follows:
  • the AOC was added to the base paint as a 50% solution in a 50:50 mixture of Solvesso 200:EEA.
  • the paints were applied to metal panels, and the coated panels subjected to UV light for 950 hours.
  • the accompanying graph shows the 60° gloss reading against time of exposure. Although the gloss readings of all paints decreased with time over the first 500 hours, at all times, the paints II and III containing AOCs gave better gloss readings than the paint I not containing any AOC.
  • Unpigmented paints contained the following:- Polyester B Resin Z Catalyst (PTSA) - concentration varies AOC 2050X - concentration varies
  • the paints were applied to metal panels, and the coated panels exposed to florida sunlight for 1 year. Resistances to MEK before and after exposure were measured and are reported in Table 5 below.
  • the properties of the exposed paint films improve with increasing AOC content.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Peinture à base de polyester saturé comprenant de 5 à 50 % d'une résine aminée telle qu'une résine de mélamine alcoylée et de 1 à 20 % d'un composé organique d'aluminium, les pourcentages s'exprimant en poids par rapport au poids du polyester, de préférence dans un milieu liquide volatil. Le composé organique d'aluminium peut inclure des groupes alcoxy ou éthylacétoacétate. Quand on les utilise sur du métal, notamment des tôles d'aluminium, ces peintures possèdent des propriétés améliorées de résistance à long terme aux intempéries.
PCT/GB1991/000481 1990-03-28 1991-03-28 Procedes de peinture Ceased WO1991014746A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB909006902A GB9006902D0 (en) 1990-03-28 1990-03-28 Polyester amino resin paint systems
GB9006902.2 1990-03-28

Publications (1)

Publication Number Publication Date
WO1991014746A1 true WO1991014746A1 (fr) 1991-10-03

Family

ID=10673386

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1991/000481 Ceased WO1991014746A1 (fr) 1990-03-28 1991-03-28 Procedes de peinture

Country Status (3)

Country Link
AU (1) AU7546291A (fr)
GB (1) GB9006902D0 (fr)
WO (1) WO1991014746A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0598886A4 (fr) * 1991-08-15 1994-11-17 Basf Corp PROCEDE DE PRODUCTION D'UN POLYMERE RETICULE AVEC UN COMPOSE -g(b)-DICARBONYLE.
GB2327050A (en) * 1997-07-08 1999-01-13 H & H Products Limited Coating metallic articles

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5155590A (en) * 1990-03-20 1992-10-13 Scientific-Atlanta, Inc. System for data channel level control

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1281610B (de) * 1959-06-08 1968-10-31 Glidden Co UEberzugsmittel fuer Metalle
JPS5859269A (ja) * 1981-10-06 1983-04-08 Toshiba Corp 絶縁塗料
US4597998A (en) * 1982-12-10 1986-07-01 Mostafa Yehia A High solids oil free polyester industrial protective coating

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1281610B (de) * 1959-06-08 1968-10-31 Glidden Co UEberzugsmittel fuer Metalle
JPS5859269A (ja) * 1981-10-06 1983-04-08 Toshiba Corp 絶縁塗料
US4597998A (en) * 1982-12-10 1986-07-01 Mostafa Yehia A High solids oil free polyester industrial protective coating

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 7, no. 147 (C-173)(1292) 28 June 1983, & JP, A, 58-59269 (TOKYO SHIBAURA DENKI K.K.) 08 April 1983, see the whole document *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0598886A4 (fr) * 1991-08-15 1994-11-17 Basf Corp PROCEDE DE PRODUCTION D'UN POLYMERE RETICULE AVEC UN COMPOSE -g(b)-DICARBONYLE.
GB2327050A (en) * 1997-07-08 1999-01-13 H & H Products Limited Coating metallic articles

Also Published As

Publication number Publication date
AU7546291A (en) 1991-10-21
GB9006902D0 (en) 1990-05-23

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